HK1193424B

HK1193424B - Polycarbonate copolymer having high fluidity, method for producing aromatic polycarbonate resin having high molecular weight, and aromatic polycarbonate compound

Info

Publication number: HK1193424B
Application number: HK14106857.3A
Authority: HK
Inventors: 伊佐早祯则; 平岛敦; 原田英文; 伊藤真树; 早川淳也; 矶部刚彦; 德竹大地; 新开洋介
Original assignee: 三菱瓦斯化学株式会社
Priority date: 2011-05-19
Filing date: 2012-05-18
Publication date: 2017-10-13

Description

High-fluidity polycarbonate copolymer, method for producing high-molecular aromatic polycarbonate resin, and aromatic polycarbonate compound

Technical Field

The present invention relates to novel high flow polycarbonate copolymers. In detail, the present invention relates to a polycarbonate copolymer having a specific structure which exhibits high fluidity despite having a high molecular weight (high polymerization degree).

The present invention also relates to a method for producing a novel high molecular weight polycarbonate resin. More specifically, the present invention relates to a method for producing a high molecular weight polycarbonate resin, in which an aromatic polycarbonate is reacted with an aliphatic diol compound having a specific structure, and a cyclic carbonate produced as a by-product is removed to increase the molecular weight of the polycarbonate resin.

The present invention also relates to a novel aromatic polycarbonate compound. More specifically, the present invention relates to an aromatic polycarbonate compound having a low terminal hydroxyl group concentration which is suitable for the production of a high-molecular aromatic polycarbonate resin including a step of reacting with a specific aliphatic diol compound to increase the molecular weight, and a prepolymer material containing the same.

Background

Polycarbonate is excellent in heat resistance, impact resistance and transparency, and has been widely used in many fields in recent years.

A large number of studies have been made on the method for producing the polycarbonate. Among them, polycarbonates derived from aromatic dihydroxy compounds, for example, from 2, 2-bis (4-hydroxyphenyl) propane (hereinafter referred to as "bisphenol a") are industrially produced by two production methods, i.e., interfacial polymerization and melt polymerization.

According to this interfacial polymerization method, polycarbonate is produced from bisphenol a and phosgene, but toxic phosgene must be used. Further, there have been still left as technical problems, such as a problem of corrosion of the apparatus due to by-produced hydrogen chloride, sodium chloride, and chlorine-containing compounds such as methylene chloride used in a large amount as a solvent, and a problem of difficulty in removing impurities such as sodium chloride and residual methylene chloride which affect the physical properties of the polymer.

On the other hand, as a method for producing a polycarbonate from an aromatic dihydroxy compound and a diaryl carbonate, for example, a melt polymerization method has been known since long in which bisphenol a and diphenyl carbonate are subjected to a transesterification reaction in a molten state, and an aromatic monohydroxy compound produced as a by-product is removed and polymerized. The melt polymerization method has an advantage that a solvent is not used unlike the interfacial polymerization method, but has an essential problem that the viscosity of the polymer in the system rapidly increases with the progress of the polymerization, it is difficult to efficiently remove the aromatic monohydroxy compound produced as a by-product out of the system, the reaction rate extremely decreases, and it is difficult to increase the polymerization degree.

In order to solve this problem, various proposals have been made for removing an aromatic monohydroxy compound from a polymer in a high viscosity state. For example, patent document 1 (Japanese patent publication (Kokoku) No. 50-19600) discloses a screw type polymerization reactor having a vent part, and patent document 2 (Japanese patent application laid-open No. 2-153923) also discloses a method using a combination of a thin film evaporation apparatus and a horizontal type polymerization apparatus.

Further, patent document 3 (U.S. Pat. No. 5,521,275) discloses a method of converting the molecular weight of an aromatic polycarbonate under a reduced pressure condition in the presence of a catalyst by using an extruder having a polymer sealing part and a vent part.

However, the molecular weight of the polycarbonate cannot be sufficiently increased by the methods disclosed in these publications. If the amount of the catalyst is increased by a method using a large amount of the catalyst or the polymer is increased under severe conditions in which high shear is applied, there is a problem that the influence on the resin such as deterioration of the hue of the resin or occurrence of a crosslinking reaction increases.

In addition, a method of increasing the degree of polymerization of polycarbonate by adding a polymerization accelerator to the reaction system in the melt polymerization method is known. The increase in molecular weight is achieved with a short reaction residence time and a low reaction temperature, the yield of polycarbonate can be improved, and a simple and inexpensive reactor can be easily designed.

Patent document 4 (european patent No. 0595608) discloses a method of reacting several diaryl carbonates at the time of molecular weight conversion, but a significant increase in molecular weight cannot be obtained. Further, patent document 5 (U.S. Pat. No. 5,696,222) discloses a method for producing a polycarbonate having an improved degree of polymerization by adding a polymerization accelerator, for example, an aryl ester compound of carbonic acid and dicarboxylic acid typified by bis (2-methoxyphenyl) carbonate, bis (2-ethoxyphenyl) carbonate, bis (2-chlorophenyl) carbonate, bis (2-methoxyphenyl) terephthalate, and bis (2-methoxyphenyl) adipate. Patent document 5 teaches that when an ester is used as a polymerization accelerator, an ester bond is introduced, and as a result, a polyester carbonate copolymer is produced (instead of a homopolymer), and the hydrolytic stability is low.

Patent document 6 (japanese patent No. 4112979) discloses a method of reacting salicylic carbonate in some cases to increase the molecular weight of an aromatic polycarbonate.

Patent document 7 (japanese unexamined patent publication No. 2008-514754) discloses a method of introducing a polycarbonate oligomer, disalicyl carbonate, and the like into an extruder to increase the molecular weight of the polycarbonate oligomer and the disalicyl carbonate.

Further, patent document 8 (japanese patent No. 4286914) discloses a method of increasing the amount of terminal hydroxyl groups by an active hydrogen compound (dihydroxy compound), and thereafter performing coupling of an aromatic polycarbonate whose amount of terminal hydroxyl groups is increased by a salicylate derivative.

However, the method disclosed in the above publication, in which the terminal hydroxyl group of the polycarbonate is increased, is required, and a reaction step with an active hydrogen compound and a reaction step with a salicylate derivative are required, so that the steps are complicated, and the polycarbonate having a large number of hydroxyl terminals is inferior in thermal stability, and there is a risk of deterioration of physical properties. Further, the amount of hydroxyl groups is increased by the active hydrogen compound, and as shown in non-patent documents 1to 2, a partial chain cleavage reaction is initiated, accompanied by an expansion of the molecular weight distribution. In addition, in order to obtain a sufficient reaction rate, it is necessary to use a large amount of catalyst, which may result in deterioration of physical properties during molding.

Further, several methods for producing a polycarbonate by adding a diol compound to a reaction system have been proposed. For example, patent document 9 (Japanese patent application laid-open No. 6-94501) discloses a method for producing a polymer polycarbonate by introducing 1, 4-cyclohexanediol. However, in the method disclosed herein, since the 1, 4-cyclohexanediol is charged together with the aromatic dihydroxy compound from the start of the polycondensation reaction system, the 1, 4-cyclohexanediol is consumed (oligomerized) by the polycarbonateization reaction, and then the aromatic dihydroxy compound is reacted to increase the molecular weight. Therefore, there is a disadvantage that the reaction time is long and the appearance such as hue is liable to be deteriorated.

Further, patent document 10 (jp 2009-102536 a) describes a method for producing a polycarbonate by copolymerizing a specific aliphatic diol and an ether diol. However, the polycarbonate disclosed herein has an isosorbide skeleton as a main structure, and thus cannot exhibit excellent impact resistance required for aromatic polycarbonates.

Further, there have been proposed a method of adding a cyclic carbonate compound to a reaction system (patent document 11: Japanese patent No. 3271353), a method of adding a diol having a hydroxyl group with a basicity higher than that of a dihydroxy compound to be used to a reaction system (patent document 12: Japanese patent No. 3301453, patent document 13: Japanese patent No. 3317555), and the like, but a high molecular weight polycarbonate resin having sufficiently satisfactory physical properties has not been obtained.

Accordingly, there are many technical problems with the conventional production methods of high molecular weight aromatic polycarbonates, and there is still a need for an improved production method that can achieve a sufficient high molecular weight while maintaining the good quality inherent in polycarbonates.

In addition, polycarbonate has the disadvantage of poor flowability, and injection molding of precision parts or thin objects is difficult. In order to improve the fluidity, the molding temperature and the mold temperature need to be increased. Therefore, there are problems that the molding cycle is prolonged, the molding cost is increased, or the polycarbonate is deteriorated during molding.

In order to improve the fluidity, a method of reducing the weight average molecular weight of the polycarbonate is mentioned. However, the polycarbonate obtained by this method has disadvantages of greatly reduced impact resistance and stress cracking resistance and poor solvent resistance. On the other hand, there is provided a method of improving fluidity by mixing polycarbonates having different molecular weights to broaden the molecular weight distribution (patent document 14: U.S. Pat. No. 3166606, patent document 15: Japanese unexamined patent publication No. 56-45945).

By these methods, a polycarbonate resin composition having non-Newtonian fluidity and large die swell is obtained. However, in these polycarbonates, the fluidity under high shear stress is about the same as that of a substance having a normal molecular weight distribution, but the fluidity under low shear stress is lower than that of a substance having a normal molecular weight distribution. That is, these polycarbonate resin compositions do have non-Newtonian flow properties (the ratio of the flow properties under high shear stress to that under low shear stress is large), but the flow properties themselves are not necessarily superior to those of the conventional ones. Further, since the composition has a broad molecular weight distribution, there is a possibility that the mechanical strength of a molded article obtained from a low molecular weight component is lowered, or when a polycarbonate having an extremely high molecular weight region is used for obtaining a polycarbonate having a desired molecular weight, coloring components resulting from a relatively long residence time are increased, and the hue of the molded article is deteriorated.

Patent document 9, which relates to a method for producing a polymer polycarbonate by introducing 1, 4-cyclohexanediol, discloses information on heat resistance and tensile strength, but does not disclose information on impact resistance and flowability, which are important characteristics of a polycarbonate.

In addition, various methods for improving the fluidity of polycarbonate have been proposed. For example, patent documents 16 to 18 describe methods for increasing the fluidity by adding a low molecular weight oligomer to a polycarbonate or by defining the content of the oligomer. As a method for increasing the fluidity by controlling the production conditions, methods described in patent documents 19 to 20 are cited.

As a method for increasing the fluidity by adding another resin to a polycarbonate or by copolymerization, methods described in patent documents 21 to 27 are cited. As a method for improving fluidity by changing the molecular structure of a polycarbonate polymer, there are methods described in patent documents 28 to 30. As a method for increasing the fluidity by changing the terminal structure of the polycarbonate resin and further adding another resin or additive, the methods described in patent documents 31 to 33 are exemplified. Patent documents 34 to 36 are examples of methods for improving fluidity by studying additives. Patent documents 37 to 39 are listed as a flow modifier for polycarbonate or a method for improving fluidity using the flow modifier.

However, although high fluidity can be achieved by any of the above techniques, there are disadvantages that physical properties inherent in the polycarbonate resin are impaired, that a step such as kneading operation is added, that the production process becomes complicated, that moldability other than fluidity such as mold release property is deteriorated, that the object to be used is limited, and that toxicity may be increased. Therefore, it is not easy to obtain a polycarbonate resin which can maintain the mechanical strength and heat resistance represented by impact resistance, which are useful physical properties of an aromatic polycarbonate, and has high fluidity.

Heretofore, the present inventors have found a novel method of chain extension in which terminal ends of an aromatic polycarbonate are connected by an aliphatic diol compound as a method of obtaining an aromatic polycarbonate of good quality by realizing a high polymerization rate (patent document 40: WO 2011/062220). According to this method, an aromatic polycarbonate resin having an Mw of about 30,000 to 100,000 and a high polymerization degree can be produced in a short time by chain extension of the aromatic polycarbonate by connecting the terminal ends of the aromatic polycarbonate with an aliphatic diol compound. In this method, since a polycarbonate is produced by a high-speed polymerization reaction, the occurrence of branching and crosslinking reactions due to long-term heat retention can be suppressed, and deterioration of resins such as color phase can be avoided.

In addition, the inventors of the present invention have previously proposed a method for producing a branched aromatic polycarbonate resin having a desired degree of branching, the method comprising: and a step of subjecting the aromatic polycarbonate prepolymer having a branched structure introduced thereto to an ester interchange reaction with an aliphatic diol compound in the presence of an ester interchange catalyst under reduced pressure (patent document 41: PCT/JP 2012/052988).

In addition, the aromatic polycarbonate compound as a raw material compound (prepolymer) suitable for the production of a high molecular weight polycarbonate resin using such an aliphatic diol compound is required to have specific physical properties such as a certain terminal hydroxyl group concentration.

As a method for reducing the concentration of terminal hydroxyl groups of a polycarbonate prepolymer which is a raw material compound for producing an aromatic polycarbonate resin, patent document 42 (using a catalyst combining a basic nitrogen compound and an alkali metal or an alkaline earth metal), patent document 43 (adding a specific ester compound), patent document 44 (reacting an excess amount of an aromatic carbonic acid diester), patent document 45 (defining conditions of a polycondensation step), patent document 46 (alkyl-etherifying a terminal hydroxyl group), and the like have been proposed.

Conventional methods for producing a high molecular weight aromatic polycarbonate have many technical problems, and further development of a polycarbonate resin and a method for producing a high molecular weight polycarbonate resin, which can achieve a sufficient molecular weight while maintaining the excellent quality inherent in polycarbonate, has been desired.

Prior art documents

Patent document

Patent document 1: japanese examined patent publication (Kokoku) No. 50-19600

Patent document 2: japanese patent laid-open No. 2-153923

Patent document 3: U.S. Pat. No. 5,521,275

Patent document 4: european patent No. 0595608 publication

Patent document 5: specification of U.S. Pat. No. 5,696,222

Patent document 6: japanese patent No. 4112979

Patent document 7: japanese Special Table 2008 + 514754

Patent document 8: japanese patent No. 4286914

Patent document 9: japanese examined patent publication (Kokoku) No. 6-94501

Patent document 10: japanese patent laid-open publication No. 2009-102536

Patent document 11: japanese patent No. 3271353

Patent document 12: japanese patent No. 3301453

Patent document 13: japanese patent No. 3317555

Patent document 14: specification of U.S. Pat. No. 3,166,606

Patent document 15: japanese laid-open patent publication No. 56-45945

Patent document 16: japanese patent No. 3217862

Patent document 17: japanese patent laid-open No. 5-186676

Patent document 18: japanese patent No. 3141297

Patent document 19: japanese patent No. 3962883

Patent document 20: japanese patent No. 3785965

Patent document 21: japanese laid-open patent publication No. 2008-037965

Patent document 22: japanese laid-open patent publication No. 2008-115249

Patent document 23: japanese laid-open patent publication No. 8-003397

Patent document 24: japanese Kokai publication No. 2006-509862

Patent document 25: japanese laid-open patent publication No. 6-157891

Patent document 26: japanese laid-open patent publication No. 6-073280

Patent document 27: japanese laid-open patent publication No. 5-140435

Patent document 28: japanese patent No. 4030749

Patent document 29: japanese patent laid-open publication No. 2005-060540

Patent document 30: japanese patent No. 2521375

Patent document 31: japanese patent No. 3874671

Patent document 32: japanese laid-open patent publication No. 7-173277

Patent document 33: japanese patent laid-open publication No. 2003-238790

Patent document 34: japanese patent laid-open publication No. 2004-035587

Patent document 35: japanese Kokai publication 2007-132596

Patent document 36: japanese patent laid-open No. 2007-039490

Patent document 37: japanese laid-open patent publication No. 11-181198

Patent document 38: japanese laid-open patent publication No. 61-162520

Patent document 39: japanese patent laid-open publication No. 2005-113003

Patent document 40: WO 2011/062220

Patent document 41: PCT/JP 2012/052988

Patent document 42: japanese laid-open patent publication No. 5-39354

Patent document 43: japanese laid-open patent publication No. 6-228301

Patent document 44: japanese laid-open patent publication No. 8-81552

Patent document 45: japanese patent No. 3379265

Patent document 46: japanese laid-open patent publication No. 4-366128

Non-patent document

Non-patent document 1: handbook of polycarbonates (ポリカーボネートハンドブック) (journal of Japan Industrial News Co., Ltd.), p.344

Non-patent document 2: polycarbonate resin (ポリカーボネート colophony) (news agency of daily journal industry), Plastic materials lecture (プラスチック materials standard) 5, p.144

Disclosure of Invention

Technical problem to be solved by the invention

The present invention has been made to solve the above problems, and an object of the present invention is to provide a novel polycarbonate copolymer which maintains the excellent quality inherent in polycarbonate without using other resins, additives, or the like, and has high fluidity even though it has a high molecular weight.

The present invention has been made to solve the above-mentioned problems, and an object of the present invention is to provide a method for producing an aromatic polycarbonate resin having a high molecular weight, which can maintain the excellent quality of the aromatic polycarbonate resin and can achieve a sufficient high molecular weight.

The present invention also provides an aromatic polycarbonate compound as a prepolymer suitable for the production of a high molecular weight polycarbonate using an aliphatic diol compound.

Means for solving the problems

As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention have found a novel polycarbonate copolymer characterized by having a structure comprising an aromatic polycarbonate chain having a length of at least a certain length and a structural unit derived from a specific aliphatic diol compound, and having a high molecular weight and a high fluidity, and have completed the present invention.

Further, the inventors of the present invention have made intensive studies to solve the above-mentioned technical problems, and as a result, have found that: the present inventors have found that a polycarbonate resin having a high molecular weight and high fluidity, which is excellent in quality and has a structure substantially the same as that of a product obtained by an interfacial method and good heat resistance, can be obtained by reacting an aromatic polycarbonate with an aliphatic diol compound having a specific structure in the presence of an ester exchange catalyst to increase the molecular weight of the aromatic polycarbonate and removing at least a part of a cyclic carbonate produced as a by-product of the reaction out of the reaction system.

Further, the present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, have found a novel aromatic polycarbonate compound having a terminal hydroxyl group concentration and a terminal phenyl group concentration in a certain range, thereby completing the present invention.

That is, the present invention relates to a high-fluidity polycarbonate copolymer, a method for producing an aromatic polycarbonate resin having a high molecular weight, and an aromatic polycarbonate compound, as shown below.

1) A high-fluidity polycarbonate copolymer which is substantially composed of a structural unit represented by the following general formula (I) and a structural unit represented by the following general formula (II), wherein the structural unit represented by the following general formula (I) is derived from an aliphatic diol compound having an aliphatic hydrocarbon group bonded to a terminal hydroxyl group, and the high-fluidity polycarbonate copolymer satisfies the following conditions (a) to (d).

(in the general formula (I), Q represents a hydrocarbon group having 3 or more carbon atoms which may contain a hetero atom₁～R₄Each independently represents a group selected from a hydrogen atom, an aliphatic hydrocarbon group having 1to 30 carbon atoms, and an aromatic hydrocarbon group having 1to 30 carbon atoms. n and m are each independently an integer of 0to 10. Wherein n and m each independently represent an integer of 1to 10 when Q does not include an aliphatic hydrocarbon group bonded to a terminal hydroxyl group. And R is₁And R₂And R₃And R₄At least one of which is independently selected from a hydrogen atom and an aliphatic hydrocarbon group. )

(in the general formula (II), R₁And R₂Each independently represents a halogen atom, an alkyl group having 1to 20 carbon atoms, an alkoxy group having 1to 20 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms or an aryloxy group having 6 to 20 carbon atoms. p and q represent integers of 0to 4. X represents a bond or a group selected from divalent organic groups represented by the following general formula (II'). )

(in the general formula (II'), R₃And R₄Each independently represents a hydrogen atom, an alkyl group having 1to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, R₃And R₄May combine to form an alicyclic ring. )

(a) Has a structure represented by the following general formula (III).

(in the general formula (III), k represents an integer of 4 or more, i represents an integer of 1 or more, l represents an integer of 1 or more, and k' represents an integer of 0 or 1. R represents a linear or branched hydrocarbon group, a phenyl group which may contain fluorine, or a hydrogen atom; wherein 70% by weight or more of i is 1 in the total amount of the copolymer.)

(b) The proportion of the structural unit represented by the general formula (I) is 1to 30 mol% and the proportion of the structural unit represented by the general formula (II) is 99 to 70 mol% based on the total amount of the structural units constituting the polycarbonate copolymer.

(c) The Q value (280 ℃, 160kg load) as an index of fluidity is 0.02 to 1.0 ml/s.

(d) The weight average molecular weight (Mw) is 30,000-100,000.

2) The high-fluidity polycarbonate copolymer according to (1), wherein: the value of N (structural viscosity index) represented by the following formula (1) is 1.25 or less.

N value (log (Q160 value) -log (Q10 value))/(log 160-log10) · (1)

3) The high-fluidity polycarbonate copolymer according to (1), wherein: the Mw and Q values satisfy the following formula (2).

4.61×EXP(-0.0000785×Mw)<Q(ml/s)···(2)

4) The high-fluidity polycarbonate copolymer according to (1), wherein: the Mw and Q values satisfy the following formula (3).

4.61×EXP(-0.0000785×Mw)<Q(ml/s)<2.30×EXP(-0.0000310×Mw)···(3)

5) The high-fluidity polycarbonate copolymer according to (1), wherein the aliphatic diol compound from which the structural unit represented by the general formula (I) is derived is a compound represented by the general formula (A).

HO-(CR₁R₂)n-Q-(CR₃R₄)。-OH···(A)

(in the general formula (A), Q represents a hydrocarbon group having 3 or more carbon atoms which may contain a hetero atom₁、R₂、R₃And R₄Each independently represents a group selected from a hydrogen atom, an aliphatic hydrocarbon group having 1to 30 carbon atoms, and an aromatic hydrocarbon group having 6 to 20 carbon atoms. n and m are each independently an integer of 0to 10. Wherein n and m each independently represent an integer of 1to 10 when Q does not include an aliphatic hydrocarbon group bonded to a terminal hydroxyl group. And, R₁And R₂And R₃And R₄At least one of (a) and (b) is independently selected from a hydrogen atom and an aliphatic hydrocarbon group. )

6) The high-fluidity polycarbonate copolymer according to (5), wherein the aliphatic diol compound is represented by the following general formula (i).

HO－（CR₁R₂）_n1－Q₁－（CR₃R₄）_m1－OH···（i）

(in the general formula (i), Q₁The aromatic ring-containing hydrocarbon group has 6 to 40 carbon atoms. R₁、R₂、R₃And R₄Each independently represents a group selected from a hydrogen atom, an aliphatic hydrocarbon group having 1to 30 carbon atoms, and an aromatic hydrocarbon group having 6 to 20 carbon atoms. n1 and m1 each independently represent an integer of 1to 10. )

7) The high-fluidity polycarbonate copolymer according to (6), wherein the aliphatic diol compound is a compound selected from the group consisting of 4,4 '-bis (2-hydroxyethoxy) biphenyl, 2' -bis [ (2-hydroxyethoxy) phenyl ] propane, 9-bis [4- (2-hydroxyethoxy) phenyl ] fluorene, 9-bis (hydroxymethyl) fluorene, 9-bis (hydroxyethyl) fluorene, fluorenylethylene glycol and fluorenyldiethanol.

8) The high-fluidity polycarbonate copolymer according to (5), wherein the aliphatic diol compound is represented by the following general formula (ii).

HO－（CR₁R₂）_n2－Q₂－（CR₃R₄）_m2－OH···（ii）

(in the general formula (ii), Q₂Represents a straight-chain or branched-chain hydrocarbon group having 3to 40 carbon atoms which may contain a heterocyclic ring. R₁、R₂、R₃And R₄Each independently represents a group selected from a hydrogen atom, an aliphatic hydrocarbon group having 1to 30 carbon atoms, and an aromatic hydrocarbon group having 6 to 20 carbon atoms. n2 and m2 each independently represent an integer of 0to 10. )

9) The high-fluidity polycarbonate copolymer of (8) above, wherein Q is₂Represents a C6-40 chain aliphatic hydrocarbon group having a branched chain without a heterocyclic ring.

10) The high-fluidity polycarbonate copolymer according to (9), wherein the aliphatic diol compound is selected from the group consisting of 2-butyl-2-ethylpropane-1, 3-diol, 2-diisobutylpropane-1, 3-diol, 2-ethyl-2-methylpropane-1, 3-diol, 2-diethylpropane-1, 3-diol and 2-methyl-2-propylpropane-1, 3-diol.

11) The high-fluidity polycarbonate copolymer according to (5), wherein the aliphatic diol compound is represented by the following general formula (iii).

HO－（CR₁R₂）_n3－Q₃－（CR₃R₄）_m3－OH···（iii）

(in the general formula (iii), Q₃Represents a cyclic hydrocarbon group having 6 to 40 carbon atoms. R₁、R₂、R₃And R₄Each independently represents a group selected from a hydrogen atom, an aliphatic hydrocarbon group having 1to 30 carbon atoms, and an aromatic hydrocarbon group having 6 to 20 carbon atoms. n3 and m3 each independently represent an integer of 0to 10. )

12) The high-fluidity polycarbonate copolymer according to (11), wherein the aliphatic diol compound is at least one compound selected from the group consisting of pentacyclopentadecane dimethanol, 1, 4-cyclohexane dimethanol, 1, 3-adamantane dimethanol, decalin-2, 6-dimethanol and tricyclodecane dimethanol.

13) The high-fluidity polycarbonate copolymer according to any one of (5) to (12), wherein the aliphatic diol compound has a boiling point of 240 ℃ or higher.

14) A molded article obtained by molding the polycarbonate copolymer of (1) by a molding method selected from the group consisting of injection molding, blow molding, extrusion molding, injection blow molding, rotational molding and compression molding.

15) A molded article selected from the group consisting of a sheet and a film comprising the polycarbonate copolymer described in the above (1).

16) A method for producing an aromatic polycarbonate resin having a high molecular weight, characterized by comprising a high molecular weight production step in which an aliphatic diol compound represented by the following general formula (g1) is reacted with an aromatic polycarbonate in the presence of an ester exchange catalyst to produce the aromatic polycarbonate resin having a high molecular weight.

(in the general formula (g1), Ra and Rb each independently represent a hydrogen atom, a linear or branched alkyl group having 1to 12 carbon atoms, or a phenyl group, and m represents an integer of 1to 30.)

17) The manufacturing method according to the above (16), characterized in that: m in the general formula (g1) is an integer of 2 to 8.

18) The manufacturing method according to the above (16), characterized in that: the aliphatic diol compound represented by the general formula (g1) is a compound represented by the general formula (g 2).

(in the general formula (g2), Ra and Rb each independently represent a hydrogen atom, a linear or branched alkyl group having 1to 12 carbon atoms, or a phenyl group; n represents an integer of 1to 28.)

19) The manufacturing method according to the above (18), characterized in that: n in the general formula (g2) is an integer of 1to 6.

20) The manufacturing method according to the above (18), characterized in that: the aliphatic diol compound represented by the general formula (g2) is a compound represented by the general formula (g 3).

(in the general formula (g3), Ra and Rb each independently represent a hydrogen atom, a linear or branched alkyl group having 1to 12 carbon atoms, or a phenyl group.)

21) The manufacturing method according to the above (20), characterized in that: in the general formula (g3), Ra and Rb each independently represent a hydrogen atom or a linear or branched alkyl group having 1to 5 carbon atoms.

22) The manufacturing method according to the above (20), characterized in that: in the general formula (g3), Ra and Rb each independently represent a linear or branched alkyl group having 1to 4 carbon atoms.

23) The process for producing a high-molecular aromatic polycarbonate resin according to item (22), wherein: the aliphatic diol compound is selected from the group consisting of 2-butyl-2-ethylpropane-1, 3-diol, 2-diisobutylpropane-1, 3-diol, 2-ethyl-2-methylpropane-1, 3-diol, 2-diethylpropane-1, 3-diol, and 2-methyl-2-propylpropane-1, 3-diol.

24) A method for producing an aromatic polycarbonate resin having a high molecular weight, comprising: comprises a high molecular weight increasing step of reacting an aromatic polycarbonate with an aliphatic diol compound represented by the following general formula (g4) in the presence of an ester exchange catalyst to increase the molecular weight.

(in the general formula (g4), R represents a divalent hydrocarbon group selected from the structures represented by the following formulae, and n represents an integer of 1to 20.)

25) The manufacturing method according to the above (24), characterized in that: in the above general formula (g4), R is- (CH)₂）_mA divalent hydrocarbon group represented by the formula (m is an integer of 3to 20) or-CH₂－C（CH₃）₂－CH₂N is 1to 3.

26) The production method according to the above (16) or (24), characterized by comprising: a high molecular weight increasing step of reacting an aromatic polycarbonate with an aliphatic diol compound in the presence of an ester exchange catalyst to increase the molecular weight; and a cyclic carbonate removal step of removing at least a part of the cyclic carbonate produced as a by-product in the high molecular weight production step from the reaction system.

27) The production method according to (26) above, wherein the cyclic carbonate is a compound represented by the following general formula (h 1).

(in the general formula (h1), Ra and Rb each independently represent a hydrogen atom, a linear or branched alkyl group having 1to 12 carbon atoms, or a phenyl group, and m represents an integer of 1to 30.)

28) The manufacturing method according to the above (27), characterized in that: m in the general formula (h1) is an integer of 2 to 8.

29) The manufacturing method according to the above (27), characterized in that: the cyclic carbonate represented by the general formula (h1) is a compound represented by the following general formula (h 2).

(in the general formula (h2), Ra and Rb each independently represent a hydrogen atom, a linear or branched alkyl group having 1to 12 carbon atoms, or a phenyl group; n represents an integer of 1to 28.)

30) The manufacturing method according to the above (29), characterized in that: n in the general formula (h2) is an integer of 1to 6.

31) The manufacturing method according to the above (29), characterized in that: the cyclic carbonate represented by the general formula (h2) is a compound represented by the following general formula (h 3).

(in the general formula (h3), Ra and Rb each independently represent a hydrogen atom, a linear or branched alkyl group having 1to 12 carbon atoms, or a phenyl group.)

32) The manufacturing method according to the above (31), characterized in that: in the general formula (h3), Ra and Rb each independently represent a hydrogen atom or a linear alkyl group having 1to 5 carbon atoms.

33) The production method according to the above (16) or (24), wherein the aliphatic diol compound is used in an amount of 0.01 to 1.0 mol based on 1 mol of the total terminal amount of the aromatic polycarbonate before the reaction in the high molecular weight step.

34) The production method according to the above (16) or (24), characterized in that: at least a part of the aromatic polycarbonate before the reaction in the step of increasing the molecular weight is capped.

35) The production method according to the above (16) or (24), wherein the aromatic polycarbonate before the reaction in the high molecular weight step is an end-capped prepolymer obtained by a reaction of an aromatic dihydroxy compound and a carbonic acid diester.

36) The production method according to the above (16) or (24), characterized in that: the concentration of the hydroxyl terminal groups of the aromatic polycarbonate before the reaction in the step of increasing the molecular weight is 1,500ppm or less.

37) The production method according to the above (16) or (24), characterized in that: the weight average molecular weight (Mw) of the aromatic polycarbonate resin having been subjected to high molecular weight conversion after the reaction in the high molecular weight conversion step is higher by 5,000 or more than the weight average molecular weight (Mw) of the aromatic polycarbonate resin before the reaction in the high molecular weight conversion step.

38) The production method according to the above (16) or (24), characterized in that: the aromatic polycarbonate before the reaction in the high molecular weight increasing step has a weight average molecular weight (Mw) of 5,000 to 60,000.

39) A polycarbonate resin composition characterized by: the aromatic polycarbonate resin having a high molecular weight obtained by the production method described in the above (16) or (24) is mainly used, and the cyclic carbonate represented by the following general formula (h1) is contained in an amount of 3000ppm or less.

40) The polycarbonate resin composition according to the above (39), wherein: m in the general formula (h1) is an integer of 2 to 8.

41) The polycarbonate resin composition according to the above (39), wherein: the cyclic carbonate represented by the general formula (h1) is a compound represented by the following general formula (h 2).

42) The polycarbonate resin composition according to the above (41), wherein: n in the general formula (h2) is an integer of 1to 6.

43) The polycarbonate resin composition according to the above (41), wherein: the cyclic carbonate represented by the general formula (h2) is a compound represented by the following general formula (h 3).

44) The polycarbonate resin composition according to the above (43), wherein: in the general formula (h3), Ra and Rb each independently represent a hydrogen atom or a linear alkyl group having 1to 5 carbon atoms.

45) The polycarbonate resin composition according to the above (39), wherein: the aromatic polycarbonate resin having a high molecular weight has an N value (structural viscosity index) of 1.25 or less, which is represented by the following formula (1).

N value (log (Q160 value) -log (Q10 value))/(log 160-log10) · (1)

46) An aromatic polycarbonate compound which is substantially composed of a structural unit represented by the following general formula (1) and satisfies the following conditions (A) to (C).

(in the general formula (1), R₁And R₂Each independently represents a halogen atom, an alkyl group having 1to 20 carbon atoms, an alkoxy group having 1to 20 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms or an aryloxy group having 6 to 20 carbon atoms. p and q represent integers of 0to 4. X represents a bond or a group selected from divalent organic groups represented by the following general formula (1'). )

(in the above general formula (1'), R₃And R₄Respectively independent earth surfaceAn alkyl group having 1to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, R₃And R₄May combine to form an alicyclic ring. )

(A) The weight average molecular weight (Mw) is 5,000-60,000.

(B) The concentration of terminal hydroxyl groups is 1500ppm or less.

(C) The concentration of the terminal phenyl group is 2 mol% or more.

47) The aromatic polycarbonate compound according to the above (46), wherein: the aromatic dihydroxy compound and the carbonic diester are reacted in the presence of an ester exchange catalyst at a carbonic diester/aromatic dihydroxy compound ratio of 1.0 to 1.3 (molar ratio).

48) The aromatic polycarbonate compound according to the above (46) or (47), wherein: the structural viscosity index (N value) is 1.25 or less.

49) The aromatic polycarbonate compound according to the above (46) or (47), wherein: branching agents are used to introduce branching structures and the structural viscosity index (N value) exceeds 1.25.

50) A prepolymer material for producing a high-molecular aromatic polycarbonate resin, characterized in that: an aromatic polycarbonate prepolymer used for producing a high molecular weight aromatic polycarbonate resin, the production of the high molecular weight aromatic polycarbonate resin comprising: and (3) subjecting an aromatic polycarbonate prepolymer and an aliphatic diol compound having an aliphatic hydrocarbon group bonded to a terminal hydroxyl group to transesterification reaction under reduced pressure in the presence of a transesterification catalyst, wherein the prepolymer material for producing a high-molecular-weight aromatic polycarbonate resin mainly comprises the aromatic polycarbonate compound described in the above (46) or (47), and the amount of residual carbonate monomer is 3000ppm or less.

51) The prepolymer material for producing a high-molecular-weight aromatic polycarbonate resin according to item (50), wherein the aliphatic diol compound is a compound represented by the following general formula (A).

HO-(CR₁R₂)_n-Q-(CR₃R₄)。-OH···(A)

(in the general formula (A), Q represents a hydrocarbon group having 3 or more carbon atoms which may contain a hetero atom₁～R₄Each independently represents a group selected from a hydrogen atom, an aliphatic hydrocarbon group having 1to 30 carbon atoms, and an aromatic hydrocarbon group having 6 to 20 carbon atoms. n and m are each independently an integer of 0to 10. Wherein n and m each independently represent an integer of 1to 10 when Q does not include an aliphatic hydrocarbon group bonded to a terminal hydroxyl group. And, R₁And R₂And R₃And R₄At least one of (a) and (b) is independently selected from a hydrogen atom and an aliphatic hydrocarbon group. )

Effects of the invention

The novel polycarbonate copolymer of the present invention is characterized in that: has a structure comprising an aromatic polycarbonate chain having a length of at least a certain value and a structural unit derived from a specific aliphatic diol compound, and the polycarbonate copolymer has a high molecular weight and high flowability and contains almost no branched structure (has a low N value).

Polycarbonate copolymers with this characteristic do not exist at present. Even if the copolymer has the same aromatic polycarbonate-forming unit derived from the aromatic dihydroxy compound and the same structural unit derived from the aliphatic diol compound, the copolymer cannot satisfy both the conditions of high molecular weight and high fluidity if it has a structure formed of an aromatic polycarbonate chain having a length of not less than a certain length and a structural unit derived from the aliphatic diol compound, unlike the present invention. With the fluidity improving method using an additive or the like, it is not easy to maintain the physical properties inherent in the polycarbonate resin and to increase the fluidity.

As described above, the polycarbonate copolymer of the present invention can provide a polycarbonate resin which has a high molecular weight and can realize high fluidity while maintaining the physical properties useful as an aromatic polycarbonate, such as mechanical strength including impact resistance, abrasion resistance and stress cracking resistance, and good hue and optical properties, low equilibrium water absorption, heat resistance, dimensional stability, transparency, weather resistance, hydrolysis resistance and flame retardancy without using any additive. Further, the polycarbonate resin has not only a high molecular weight and a high flowability but also a small branched structure and an isomeric structure (a small N value).

Further, according to the novel production method of the present invention, the aromatic polycarbonate is increased in molecular weight by the reaction of the aromatic polycarbonate (prepolymer) with the aliphatic diol compound having a specific structure, and the cyclic carbonate formed as a by-product is removed from the reaction system, so that the aliphatic diol compound hardly enters into the main chain of the aromatic polycarbonate resin having increased molecular weight. Therefore, the obtained high molecular weight aromatic polycarbonate resin does not leave a connecting portion in the chain, and is basically the same in structure as a polycarbonate obtained by a conventional interfacial method or a melt method. For example, a polymer having a chemical structure substantially the same as that of a general polycarbonate resin derived from bisphenol a (BPA-PC) is obtained from an aromatic polycarbonate prepolymer using bisphenol a (BPA) as an aromatic dihydroxy compound. The polycarbonate resin thus obtained has physical properties equivalent to those of conventional polycarbonates by the interfacial method, and has the advantages of low branching degree, low isomeric structure and the like in terms of quality because the resin is made to have a high molecular weight at a high speed by using an aliphatic diol compound as a binder, and the resin is greatly improved in thermal stability (heat resistance) at high temperatures because the resin does not contain a skeleton derived from the binder composed of the aliphatic diol compound.

The novel aromatic polycarbonate compound of the present invention has specific terminal physical properties, and is particularly suitable for producing a polycarbonate resin by an ester interchange reaction with a specific aliphatic diol compound having an aliphatic hydrocarbon group bonded to a terminal hydroxyl group.

By subjecting the aromatic polycarbonate compound having such characteristics to an ester interchange reaction with a specific aliphatic diol compound, it is possible to achieve a sufficient high molecular weight by a simple method while maintaining good quality of the aromatic polycarbonate resin. In particular, a polycarbonate copolymer having a high molecular weight, but high fluidity, and containing no branched structure can be produced without using an additive or the like. On the other hand, if a branching structure is introduced into the aromatic polycarbonate compound by using a predetermined amount of the branching agent, an aromatic polycarbonate resin having a desired branching degree can be easily produced.

Drawings

FIG. 1 shows a polycarbonate copolymer obtained in example 1 of the present invention¹H-NMR spectrum (A).

FIG. 2 shows a polycarbonate copolymer obtained in example 1 of the present invention¹H-NMR spectrum (B).

FIG. 3 is a graph showing the relationship between Mw and Q value (measured at 280 ℃ under a load of 160 kg) of polycarbonates obtained in examples 1to 19 of the present invention and comparative examples 1to 5.

FIG. 4 is a graph showing the relationship between Mw and N values of polycarbonates obtained in examples 1to 19 of the present invention and comparative examples 1to 5.

FIG. 5 is a drawing of the reactants of example 20 of the present invention¹H-NMR spectrum.

FIG. 6 shows a resin obtained in example 20 of the present invention¹H-NMR spectrum.

FIG. 7 shows a production process of an aromatic polycarbonate prepolymer obtained in example 34 of the present invention¹H-NMR spectrum.

Detailed Description

I. High flow polycarbonate copolymers

The high-fluidity polycarbonate copolymer of the present invention is substantially composed of the structural unit represented by the above general formula (I) and the structural unit represented by the general formula (II).

(1) A structural unit represented by the general formula (I)

The structural unit represented by the general formula (I) is derived from an aliphatic diol compound. The aliphatic diol compound referred to in the present invention is a compound having an aliphatic hydrocarbon group bonded to a terminal hydroxyl group. The terminal hydroxyl group means a hydroxyl group participating in formation of a carbonate bond with the aromatic polycarbonate prepolymer by an ester exchange reaction.

Examples of the aliphatic hydrocarbon group include an alkylene group and a cycloalkylene group, and a part of these groups may be substituted with an aromatic group, a heterocyclic ring-containing group, or the like.

In the general formula (I), Q represents a hydrocarbon group having 3 or more carbon atoms which may contain a hetero atom. The lower limit of the number of carbon atoms of the hydrocarbon group is 3, preferably 6, more preferably 10, and the upper limit is preferably 40, more preferably 30, and still more preferably 25.

Examples of the hetero atom include an oxygen atom (O), a sulfur atom (S), a nitrogen atom (N), a fluorine atom (F), and a silicon atom (Si). Among them, oxygen atom (O) and sulfur atom (S) are particularly preferable.

The hydrocarbon group may have a linear structure, a branched structure, or a cyclic structure. And Q may have a cyclic structure such as an aromatic ring or a heterocyclic ring.

In the above general formula (I), R₁、R₂、R₃And R₄Each independently represents a hydrogen atom or a carbon atom1to 30 (preferably 1to 10 carbon atoms) aliphatic hydrocarbon groups and 6 to 20 (preferably 6 to 10 carbon atoms) aromatic hydrocarbon groups.

Specific examples of the aliphatic hydrocarbon group include a linear or branched alkyl group and a cycloalkyl group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, an n-hexyl group, and an isohexyl group. As the cycloalkyl group, a cyclohexyl group can be cited. Examples of the aromatic hydrocarbon group include an aryl group and a naphthyl group. Examples of the aryl group include a phenyl group, a phenethyl group, a benzyl group, a tolyl group and an o-xylyl group, and a phenyl group is preferable.

Wherein R is₁And R₂And R₃And R₄At least one of which is independently selected from a hydrogen atom and an aliphatic hydrocarbon group.

As R₁～R₄Particularly, each of the groups independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1to 30 carbon atoms (preferably 1to 10 carbon atoms).

As a particularly preferable aliphatic hydrocarbon group, a linear or branched alkyl group is exemplified. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, and an isopentyl group.

Among them, R is most preferable₁～R₄Are all hydrogen atoms. That is, the aliphatic diol compound from which the general formula (I) can be derived is preferably a primary diol compound, and more preferably a primary diol compound other than a linear aliphatic diol.

n and m each independently represent an integer of 0to 10, preferably 0to 4. Wherein n and m each independently represent an integer of 1to 10, preferably 1to 4, in the case where Q does not include an aliphatic hydrocarbon group bonded to a terminal hydroxyl group.

The aliphatic diol compound derived from the structural unit (I) is a 2-membered compound represented by the following general formula (A)The alcoholic hydroxyl group of (1). In the general formula (A), Q, R₁～R₄N and m are the same as in the above general formula (I).

HO-(CR₁R₂)_n-Q-(CR₃R₄)。-OH···(A)

The above-mentioned terminal structure "HO- (CR)₁R₂）_n- "and" - (CR)₃R₄）_mSpecific examples of-OH "include the following structures.

Ra, Rb is hydrogen, straight chain or branched alkyl, phenyl, naphthyl, m is an integer of more than 1

The aliphatic diol compound used in the present invention is more preferably a compound having a 2-membered alcoholic hydroxyl group represented by any one of the following general formulae (i) to (iii).

HO-(CR₁R₂)_nl-Q₁-(CR₃R₄)_ml-OH···(i)

HO-(CR₁R₂)_D2-Q₂-(CR₃R₄)_m2-OH···(ii)

HO-(CR_lR₂)_n3-Q₃-(CR₃R₄)_m3-OH···(iii)

In the above general formula (i), Q₁The hydrocarbon group having 6 to 40 carbon atoms and containing an aromatic ring is preferably a hydrocarbon group having 6 to 30 carbon atoms and containing an aromatic ring. And, Q₁May contain at least one hetero atom selected from an oxygen atom (O), a sulfur atom (S), a nitrogen atom (N), a fluorine atom (F) and a silicon atom (Si).

n1 and m1 each independently represent an integer of 1to 10, preferably an integer of 1to 4. Examples of the aromatic ring include phenyl, biphenyl, fluorenyl, naphthyl and the like.

As Q₁Specific examples thereof include groups represented by the following structural formulae.

R ═ linear or branched alkyl, cyclohexyl, phenyl.

m is an integer of 0to 12

A linear or branched alkyl group having 1to 10 carbon atoms, cyclohexyl group, phenyl group

R is a linear or branched alkyl group having 1to 10 carbon atoms, cyclohexyl group or phenyl group

n is 1to 20 (preferably 1to 2)

R is a linear or branched alkyl group having 1to 30 carbon atoms, a cyclohexyl group or a phenyl group

Ra-H or methyl, Rb-C1-30 straight or branched alkyl, cyclohexyl or phenyl

In the above general formula (ii), Q₂The hydrocarbon group has 3to 40 carbon atoms and is preferably a linear or branched chain aliphatic hydrocarbon group having 3to 30 carbon atoms and may contain a heterocyclic ring. And, Q₂May contain at least one hetero atom selected from an oxygen atom (O), a sulfur atom (S), a nitrogen atom (N), a fluorine atom (F) and a silicon atom (Si). n2 and m2 each independently represent an integer of 0to 10, preferably 0to 4.

As Q₂Specific examples of the (a) to (b) include groups represented by the following structural formulae. Among them, in the following structural formula, in the case of the structural formula group having a molecular weight distribution, it is preferable to select a group having an average number of carbon atoms in the range of 6 to 40 based on the average molecular weight.

Ra and Rb are a linear or branched alkyl group other than hydrogen, which may be substituted with-NH₂and-F. And m is an integer of 1-30.

And m is an integer of 1-30.

Polycaprolactone diol, poly (1, 4-butanediol adipate) diol, poly (1, 4-butanediol succinate) diol

R is H, a linear or branched alkyl group having 1to 12 carbon atoms, or a phenyl group.

And m is an integer of 1-30.

n is 1to 20 (preferably 1to 2)

R＝-(CH₂)_m-or

（m＝3～20）

In the above general formula (iii), Q₃The group is a group containing a cyclic hydrocarbon group (cycloalkylene group) having 6 to 40 carbon atoms, preferably a group containing a cyclic hydrocarbon group having 6 to 30 carbon atoms. n3 and m3 each independently represent an integer of 0to 10, preferably an integer of 1to 4. Examples of the cycloalkylene group include cyclohexylene, bicyclodecyl (bicyclodecyl), and tricyclodecyl (tricyclodecyl).

As Q₃Specific examples of (b) include groups represented by the following structural formulae.

R is a linear or branched alkyl group having 1to 8 carbon atoms

n is 1to 20 (preferably 1to 2)

In the above general formulae (i) to (iii), R₁～R₄Each independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1to 30 carbon atoms (preferably 1to 10 carbon atoms), or an aromatic hydrocarbon group having 6 to 20 carbon atoms (preferably 6 to 10 carbon atoms). Specific examples thereof are the same as those in the above general formula (I).

Among the aliphatic diol compounds represented by any one of the above general formulae (i) to (iii), compounds represented by the general formulae (i) and (ii) are more preferable, and a compound represented by the general formula (ii) is particularly preferable.

Further, as the aliphatic diol compound represented by the above general formula (a), a primary diol compound is particularly preferable, and a primary diol compound other than the linear aliphatic diol is more preferable.

Specific examples of the aliphatic diol compound represented by the above general formula (a) include compounds having the following structures.

Ra and Rb each independently represent a hydrogen atom, a linear or branched alkyl group having 1to 30 carbon atoms, a phenyl group or a cyclohexyl group.

And m is an integer of 4-30.

Ra and Rb each independently represent a hydrogen atom, a linear or branched alkyl group having 1to 12 carbon atoms, preferably 1to 4 carbon atoms, or a phenyl group, and m represents an integer of 1to 30.

R represents an alkyl group having 1to 10 carbon atoms, Ra and Rb each independently represent a hydrogen atom, a linear or branched alkyl group having 1to 12 carbon atoms, preferably 1to 4 carbon atoms, or a phenyl group, and m represents an integer of 1to 10, preferably 1to 5.

R represents an alkyl group having 1to 10 carbon atoms, Ra, Rb, Rc and Rd each independently represents a hydrogen atom, a linear or branched alkyl group having 1to 12 carbon atoms, preferably 1to 4 carbon atoms, or a phenyl group, and m and k each represents an integer of 1to 10, preferably 1to 5.

m represents an integer of 1to 10, preferably an integer of 1to 5.

R represents an alkyl group, a phenyl group or a cyclohexyl group.

m represents an integer of 0to 20, preferably an integer of 0to 12.

R represents a linear or branched alkyl group having 1to 10 carbon atoms.

R represents a hydrogen atom, a linear or branched alkyl group having 1to 10 carbon atoms, a phenyl group or a cyclohexyl group.

Ra and Rb each independently represent a hydrogen atom, a linear or branched alkyl group having 1to 30 carbon atoms, preferably 1to 24 carbon atoms, a phenyl group or a cyclohexyl group.

R represents a linear or branched alkyl group having 1to 8 carbon atoms, preferably 1to 4 carbon atoms.

n is 1to 20 (preferably 1to 2)

Specific examples that can be used as the aliphatic diol compound represented by the above general formula (a) are classified into primary diols and secondary diols, as shown below.

(i) Primary dihydric alcohol: compounds containing 2-hydroxyethoxy groups

The aliphatic diol compound of the present invention is preferably "HO- (CH)₂)₂-O-Y-O-(CH₂)₂-OH "or a 2-hydroxyethoxy group-containing compound. Examples of Y include an organic group (a) having the following structure, an organic group (B), an organic group (C) selected from divalent phenylene and naphthylene groups, and a cycloalkylene group (D) selected from the following structural formula.

Here, X represents a single bond or a group of the following structure. R₁And R₂Each independently represents a hydrogen atom, an alkyl group having 1to 4 carbon atoms, a phenyl group or a cycloalkyl group, and may contain a fluorine atom. R₁And R₂Preferably a hydrogen atom or a methyl group. p and q each independently represent an integer of 0to 4 (preferably 0to 3).

In the above structure, Ra and Rb each independently represent a hydrogen atom, a linear or branched alkyl group having 1to 30 carbon atoms, preferably 1to 12 carbon atoms, more preferably 1to 6 carbon atoms, particularly preferably 1to 4 carbon atoms, an aryl group having 6 to 12 carbon atoms, or a cycloalkyl group having 6 to 12 carbon atoms, or may be bonded to each other to form a ring. The ring may be an aromatic ring, an alicyclic ring, a heterocyclic ring (containing O and/or S), or any combination thereof. When Ra and Rb are alkyl groups or form a ring with each other, they may contain a fluorine atom. Rc and Rd each independently represent an alkyl group having 1to 10, preferably 1to 6, and more preferably 1to 4 carbon atoms (particularly preferably methyl or ethyl), and they may contain a fluorine atom. e represents an integer of 1to 20, preferably an integer of 1to 12.

Re and Rf each independently represent a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, a cycloalkyl group having 6 to 12 carbon atoms, or an alkoxy group having 1to 20 carbon atoms, and may contain a fluorine atom. They may also combine with each other to form a ring. The straight-chain or branched alkyl group preferably has 1to 6 carbon atoms, more preferably 1to 4 carbon atoms, and particularly preferably a methyl group or an ethyl group. The alkoxy group having 1to 20 carbon atoms is preferably a methoxy group or an ethoxy group.

More specific examples of the aliphatic diol compound are as follows. In the following formula, n and m independently represent an integer of 0to 4. R₁And R₂Each independently represents a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, or a butyl groupA group, isobutyl, phenyl or cyclohexyl.

< case where Y is an organic group (A) >

Preferred compounds when Y is the organic group (A) are shown below.

< case where Y is an organic group (B) >

When Y is an organic group (B), X preferably represents-CRaRb- (Ra and Rb are each independently a hydrogen atom or an alkyl group having 1to 6 carbon atoms, preferably a methyl group). Specific examples thereof include the following compounds.

< case where Y is an organic group (C) >)

Preferred compounds in the case where Y is the organic group (C) are shown below.

Among the above-mentioned 2-hydroxyethoxy group-containing compounds, particularly preferred compounds are as follows.

(ii) Primary dihydric alcohol: hydroxyalkyl group-containing compound

The aliphatic diol compound of the present invention is preferably "HO- (CH)₂)_r-Z-(CH₂)_rA hydroxyalkyl group-containing compound represented by-OH ". Here, r is 1 or 2. That is, as the hydroxyalkyl group, hydroxymethyl and hydroxyethyl are mentioned.

Examples of Z include organic groups shown below.

Preferred hydroxyalkyl-containing compounds are shown below. In the following formula, n and m independently represent an integer of 0to 4.

(iii) Primary dihydric alcohol: carbonate diol compound

Preferable examples of the aliphatic diol compound of the present invention include carbonate diol compounds represented by the following formulae. Here, as R, an organic group having the following structure is cited. In the formula, n is an integer of 1to 20, preferably an integer of 1to 2. m is an integer of 3to 20, preferably an integer of 3to 10.

n is 1to 20 (preferably 1to 2)

The polycarbonate diol compound is preferably a diol (a dimer of cyclohexane dimethanol or neopentyl glycol) as shown below or a compound containing the diol as a main component.

The aliphatic diol compound of the present invention is preferably a primary diol selected from the group consisting of the above-mentioned (i) 2-hydroxyethoxy group-containing compound, (ii) hydroxyalkyl group-containing compound and (iii) carbonate diol compound.

The aliphatic diol compound of the present invention is not particularly limited to the specific primary diol described above, and may be a compound that can be used in the presence of a primary diol compound other than the primary diol compound described above or a secondary diol compound. Examples of other primary diol compounds or secondary diol compounds that can be used are shown below.

Wherein, in the following formula, R₁And R₂Each independently represents a hydrogen atom, a halogen atom, an amino group, a nitro group, an alkyl group having 1to 20 carbon atoms, an alkoxy group having 1to 20 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms or an aryloxy group having 6 to 20 carbon atoms, and is preferably a hydrogen atom, a fluorine atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isopentyl group, a cyclohexyl group, a phenyl group, a benzyl group, a methoxy group or an ethoxy group.

R₅、R₆、R₇、R₈Is a hydrogen atom or a C1-valent alkyl group having 1to 10 carbon atoms. R₉And R₁₀Each independently a linear or branched alkyl group having 1to 8 carbon atoms, preferably 1to 4 carbon atoms.

Ra and Rb each independently represent a hydrogen atom, a linear or branched alkyl group having 1to 30 carbon atoms (preferably 1to 12, more preferably 1to 6, particularly preferably 1to 4), an aryl group having 6 to 12 carbon atoms, or a cycloalkyl group having 6 to 12 carbon atoms, or may be bonded to each other to form a ring. The ring may be an aromatic ring, an alicyclic ring, a heterocyclic ring (containing O and/or S), or any combination thereof. When Ra and Rb are alkyl groups or form a ring with each other, they may contain a fluorine atom.

R' is an alkylene group having 1to 10 carbon atoms, preferably 1to 8 carbon atoms. Re and Rf are each independently a hydrogen atom, a halogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a butyl group, an isobutyl group, a phenyl group, a methoxy group or an ethoxy group. m' is an integer of 4 to 20, preferably an integer of 4 to 12. m' is an integer of 1to 10, preferably 1to 5. e is an integer of 1to 10.

< other primary diols >

< Secondary glycol >

More specifically, 1, 4-cyclohexanediol, 1, 4-cyclohexanedimethanol, 1, 6-cyclohexanedimethanol, and tricyclo (5.2.1.0)^2.6) Aliphatic diols having a cyclic structure such as decane dimethanol, decalin-2, 6-dimethanol, pentacyclopentadecane dimethanol, isosorbide, isomannide, 1, 3-adamantane dimethanol and the like; p-xylylene glycol, m-xylylene glycol, naphthalenediol, biphenyldimethanol, 1, 4-bis (2-hydroxyethoxy) phenyl, 4 '-bis (2-hydroxyethoxy) biphenyl, 2' -bis [ (2-hydroxyethoxy) phenyl ] methyl ester]Propane, 9-bis [4- (2-hydroxyethoxy) phenyl]Fluorene (BPEF), 9-bis (hydroxymethyl) fluorene, 9-bis (hydroxyethyl) fluorene, fluorenediol, fluorenediethanolAliphatic diols containing an aromatic ring; aliphatic polyester diols such as polycaprolactone diol, poly (1, 4-butanediol adipate) diol, and poly (1, 4-butanediol succinate) diol; branched aliphatic diols such as 2-butyl-2-ethylpropane-1, 3-diol (butylethylpropanediol), 2-diethylpropane-1, 3-diol, 2-diisobutylpropane-1, 3-diol, 2-ethyl-2-methylpropane-1, 3-diol, 2-methyl-2-propylpropanediol and 2-methyl-propane-1, 3-diol; carbonate diol compounds such as bis (3-hydroxy-2, 2-dimethylpropyl) carbonate.

The aliphatic diol compounds may be used alone or in combination of two or more. The aliphatic diol compound to be actually used may be a compound which may be used in some cases depending on the reaction conditions and the like, and may be appropriately selected depending on the reaction conditions and the like to be used.

The boiling point of the aliphatic diol compound used in the present invention is not particularly limited, and if it is considered that the aromatic monohydroxy compound produced as a by-product in the reaction of the aromatic polycarbonate prepolymer and the aliphatic diol compound is distilled off, the aliphatic diol compound used preferably has a higher boiling point than the aromatic monohydroxy compound. Further, since it is necessary to ensure the reaction by making the reaction progress by making the compound non-volatile at a certain temperature and pressure, it is often preferable to use an aliphatic diol compound having a higher boiling point. In this case, it is preferable to use an aliphatic diol compound having a boiling point at normal pressure of 240 ℃ or higher, more preferably 250 ℃ or higher.

Specific examples of such aliphatic diol compounds include 1, 4-cyclohexanedimethanol, 1, 6-cyclohexanedimethanol (boiling point: 283 ℃ C.), decalin-2, 6-dimethanol (341 ℃ C.), pentacyclopentadecalin dimethanol, 4 '-bis (2-hydroxyethoxy) biphenyl, 2' -bis [ (2-hydroxyethoxy) phenyl ] propane, 9-bis [4- (2-hydroxyethoxy) phenyl ] fluorene (BPEF), 9-bis (hydroxymethyl) fluorene, 9-bis (hydroxyethyl) fluorene, fluorenediol, 2-butyl-2-ethylpropane-1, 3-diol (271 ℃ C.), 2-diethylpropane-1, 3-diol (250 ℃ C.), and mixtures thereof, 2, 2-diisobutylpropane-1, 3-diol (280 ℃ C.), bis (3-hydroxy-2, 2-dimethylpropyl) carbonate, and the like.

On the other hand, even an aliphatic diol compound having a boiling point of less than 240 ℃ at normal pressure can be suitably used in the present invention by devising the method of addition. Specific examples of such aliphatic diol compounds include 2-ethyl-2-methylpropane-1, 3-diol (226 ℃ C.), 2-methyl-2-propylpropane-1, 3-diol (230 ℃ C.), propane-1, 2-diol (188 ℃ C.), and the like.

The upper limit of the boiling point of the aliphatic diol compound used in the present invention is not particularly limited, and may be 700 ℃ or lower.

(2) A structural unit represented by the general formula (II)

The aromatic polycarbonate-forming unit of the polycarbonate copolymer of the present invention is a structural unit represented by the general formula (II).

In the general formula (II), R₁And R₂Each independently represents a halogen atom, an alkyl group having 1to 20 carbon atoms, an alkoxy group having 1to 20 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms or an aryloxy group having 6 to 20 carbon atoms. p and q represent integers of 0to 4. X represents a bond or a group selected from divalent organic groups represented by the following general formula (II').

In the formula (II'), R₃And R₄Each independently represents a hydrogen atom, an alkyl group having 1to 10 carbon atoms or a carbon atom6 to 10 of aryl, R₃And R₄May combine to form an alicyclic ring.

Examples of the aromatic dihydroxy compound from which the structural unit represented by the above general formula (II) is derived include compounds represented by the following general formula (II '').

In the above general formula (II'), R₁～R₂P, q and X are the same as in the above general formula (II).

Specific examples of such aromatic dihydroxy compounds include bis (4-hydroxyphenyl) methane, 1-bis (4-hydroxyphenyl) ethane, 2-bis (4-hydroxyphenyl) propane, 2-bis (4-hydroxyphenyl) butane, 2-bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane, 1-bis (4-hydroxyphenyl) -1-phenylethane, bis (4-hydroxyphenyl) diphenylmethane, 2-bis (4-hydroxy-3-methylphenyl) propane, 1-bis (4-hydroxy-3-t-butylphenyl) propane, 2-bis (3, 5-dimethyl-4-hydroxyphenyl) propane, and the like, 2, 2-bis (4-hydroxy-3-phenylphenyl) propane, 2-bis (3-cyclohexyl-4-hydroxyphenyl) propane, 2-bis (4-hydroxy-3-bromophenyl) propane, 2-bis (3, 5-dibromo-4-hydroxyphenyl) propane, 1-bis (4-hydroxyphenyl) cyclopentane, 1-bis (4-hydroxyphenyl) cyclohexane, 2-bis (4-hydroxy-3-methoxyphenyl) propane, 4' -dihydroxydiphenyl ether, 4' -dihydroxy-3, 3 ' -dimethylphenyl ether, 4' -dihydroxyphenyl sulfide, 4' -dihydroxy-3, 3 ' -dimethyldiphenylsulfide, 4' -dihydroxydiphenylsulfoxide, 4' -dihydroxy-3, 3 ' -dimethyldiphenylsulfoxide, 4' -dihydroxydiphenylsulfone, 4' -dihydroxy-3, 3 ' -dimethyldiphenylsulfone, and the like.

Among these, 2-bis (4-hydroxyphenyl) propane is preferable because of stability of the monomer and easiness of obtaining a form containing a small amount of impurities.

The aromatic polycarbonate-forming unit in the present invention may be a combination of a plurality of structural units derived from the above-mentioned various monomers (aromatic dihydroxy compounds) as required for the purpose of controlling the glass transition temperature, improving the fluidity, increasing the refractive index, reducing the birefringence, and controlling the optical properties.

(3) Essential element (a)

The polycarbonate copolymer of the present invention is characterized by having a structure represented by the following general formula (III). In the general formula (III), (I) represents a structural unit represented by the general formula (I), and (II) represents a structural unit represented by the general formula (II).

In the general formula (III), R represents a linear or branched hydrocarbon group, a phenyl group which may contain fluorine, or a hydrogen atom. Specific examples thereof include methyl group, propyl group, isopropyl group, ethyl group, butyl group, isobutyl group, pentyl group, isopentyl group, hexyl group, tetrafluoropropyl group, tert-butyl-phenyl group, and pentafluorophenyl group.

In the above general formula (III), k represents an average chain length of a chain composed of aromatic polycarbonate-forming units (aromatic polycarbonate chain). The aromatic polycarbonate-forming unit is a structural unit which is a main component of the polycarbonate copolymer of the present invention, and the aromatic polycarbonate chain composed of the unit forms a main polymer structure of the polycarbonate copolymer. k is 4 or more, preferably 4 to 100, and more preferably 5 to 70. When the chain length does not have a length of more than a certain length, "- (I)_iThe structural sites indicated by "are relatively increased, and as a result, the random copolymerization property of the polycarbonate copolymer of the present invention is increased, and the heat resistance and the like inherent to the polycarbonate resin tend to be lost.

Constitutional unit "- (II)_k- "(aromatic polycarbonate)Chain) is a structural unit derived from an aromatic polycarbonate prepolymer, and the weight average molecular weight (Mw) thereof is preferably 5,000 to 60,000, more preferably 10,000 to 50,000, and still more preferably 10,000 to 40,000.

If the molecular weight of the aromatic polycarbonate chain is too low, the polycarbonate copolymer of the present invention may be more greatly affected by the physical properties of the copolymerization components. Although the physical properties can be improved by this, the effect of maintaining the useful physical properties of the aromatic polycarbonate may be insufficient.

If the molecular weight of the aromatic polycarbonate chain is too high, the polycarbonate copolymer of the present invention may not give a polycarbonate copolymer having high fluidity while maintaining useful physical properties of the aromatic polycarbonate.

I represents a site consisting of a structural unit derived from an aliphatic diol compound "- (I)_i- "average chain length. i is 1 or more, preferably 1to 5, more preferably 1to 3, particularly preferably 1to 2, and most preferably 1. The closer the average chain length is to 1, the more preferred. If the aliphatic diol moiety "- (I)_iThe average chain length of-is too long, and the heat resistance and mechanical strength are lowered, so that the effect of the present invention cannot be obtained.

l represents a structural unit "- [ - (II) composed of an aromatic polycarbonate chain and an aliphatic diol moiety_k－(I)_i－]_l- "average chain length. l is 1 or more, preferably 1to 30, more preferably 1to 20, and particularly preferably 1to 10.

k' is an integer of 0 or 1. That is, there is an aliphatic diol moiety "- (I)_iThe aromatic polycarbonate chains are often present on both sides of the substrate, or on only one side of the substrate, or on both sides of the substrate.

In the above polycarbonate copolymer, the aromatic polycarbonate chain "- (II)_k- (I) with aliphatic diol moiety_iThe ratio (molar ratio) of- "is not particularly limitedThe average value of the polycarbonate copolymer as a whole is preferably "- (II)_k－”／“－(I)_i- "0.1 to 3, more preferably 0.6 to 2.5, and particularly preferably 2. Further, k/l is not particularly limited, but is preferably 2 to 200, more preferably 4 to 100.

In the polycarbonate copolymer of the present invention, i is 1 in 70% by weight or more, preferably 80% by weight or more, more preferably 90% by weight or more, and particularly preferably 95% by weight or more of polymer molecules constituting the copolymer. That is, although the resin is usually an aggregate of high molecular compounds (polymer molecules) having various structures and molecular weights, the polycarbonate copolymer of the present invention is characterized by being an aggregate of high molecular compounds having a structure in which 70% by weight or more of a long-chain aromatic polycarbonate chain (- (II) k-) is bonded to 1 structural unit (- (I) -) derived from an aliphatic diol compound. When the amount of the polymer compound i-1 is less than 70% by weight, the proportion of the copolymerizable component is high, and thus the polymer compound is easily affected by the physical properties of the copolymerizable component, and the physical properties inherent in the aromatic polycarbonate cannot be maintained.

The proportion of the polymer compound having i-1 in the polycarbonate copolymer of the present invention may be determined by the method of preparing the polycarbonate copolymer¹H-NMR analysis was carried out.

(4) Essential element (b)

The polycarbonate copolymer of the present invention contains 1to 30 mol%, preferably 1to 25 mol%, and particularly preferably 1to 20 mol% of the structural unit represented by the general formula (I) and 99 to 70 mol%, preferably 99 to 75 mol%, and particularly preferably 99 to 80 mol% of the structural unit represented by the general formula (II), based on the whole.

If the proportion of the structural unit represented by the general formula (I) is too small, the conditions of high molecular weight and high flowability, which are characteristic of the polycarbonate copolymer, cannot be satisfied; if the amount is too large, the excellent physical properties inherent in the aromatic polycarbonate resin such as mechanical strength and heat resistance are impaired.

The polycarbonate copolymer of the present invention may contain a structure derived from another copolymerizable component within a range not departing from the gist of the present invention, but preferably the polycarbonate copolymer of the present invention is composed of 1to 30 mol% (preferably 1to 25 mol%, particularly preferably 1to 20 mol%) of a structural unit represented by the general formula (I) and 99 to 70 mol% (preferably 99 to 75 mol%, particularly preferably 99 to 80 mol%) of a structural unit represented by the general formula (II).

(5) Essential element (c)

The lower limit of the Q value (280 ℃ C., 160kg load) as an index of fluidity of the polycarbonate copolymer of the present invention is preferably 0.02ml/sec, more preferably 0.022ml/sec, still more preferably 0.025ml/sec, particularly preferably 0.027ml/sec, most preferably 0.03 ml/sec; the upper limit is preferably 1.0ml/sec, more preferably 0.5ml/sec, and has high fluidity. Usually, the melt characteristics of the polycarbonate resin may be represented by Q ═ K · P^NAnd (4) showing. Wherein Q in the formula represents the outflow (ml/sec) of the molten resin, K represents the intercept of the regression formula as an independent variable (derived from the molecular weight and structure of the polycarbonate resin), and P represents the pressure (load: 10to 160 kgf) (kg/cm) measured at 280 ℃ using an elevated rheometer²) And N represents a structural viscosity index. If the Q value is too low, injection molding of precision parts or thin objects is difficult. In this case, measures such as raising the molding temperature are required, but this may lead to gelation at high temperature, appearance of an isomeric structure, increase in the N value, and the like. If the Q value is too high, the melt tension is lowered and drooping (draw down) is likely to occur when the composition is used for blow molding, extrusion molding or the like, and a satisfactory molded article cannot be obtained. Further, when the resin composition is used for applications such as injection molding, satisfactory molded articles cannot be obtained by drawing or the like.

(6) Essential element (d)

The polycarbonate copolymer of the present invention has a weight average molecular weight (Mw) of 30,000 to 100,000, preferably 30,000 to 80,000, more preferably 35,000 to 75,000, and has high fluidity even though it has a high molecular weight.

When the weight average molecular weight of the polycarbonate copolymer is too low, the melt tension is lowered and the polycarbonate copolymer tends to sag when used for blow molding, extrusion molding or the like, and thus a satisfactory molded article cannot be obtained. Further, when the resin composition is used for applications such as injection molding, satisfactory molded articles cannot be obtained by drawing or the like. And the resulting molded article has reduced physical properties such as mechanical properties and heat resistance. Further, the oligomer region is increased, and the physical properties such as organic solvent resistance are also lowered.

If the weight average molecular weight of the polycarbonate copolymer is too high, injection molding of precision parts or thin objects is difficult, the molding cycle time is prolonged, and production costs are adversely affected. Therefore, measures such as increasing the molding temperature are required, but this may lead to gelation at high temperatures, appearance of an isomeric structure, increase in the N value, and the like.

(7) N value (structural viscosity index)

In the polycarbonate copolymer of the present invention, the N value (structural viscosity index) represented by the following formula (1) is preferably 1.3 or less, more preferably 1.28 or less, and particularly preferably 1.25 or less.

N value (log (Q160 value) -log (Q10 value))/(log 160-log10) · (1)

In the above mathematical formula (1), a Q160 value represents a melt flow volume (ml/sec) per unit time measured at 280 ℃ under a load of 160kg (measured using CFT-500D manufactured by shimadzu corporation (hereinafter the same), and calculated from a stroke of 7.0 to 10.0 mm), and a Q10 value represents a melt flow volume (ml/sec) per unit time measured at 280 ℃ under a load of 10kg (calculated from a stroke of 7.0 to 10.0 mm) (wherein the nozzle diameter is 1mm × the nozzle length is 10 mm).

The structural viscosity index "N value" is an index of the degree of branching of the aromatic polycarbonate resin. The polycarbonate copolymer of the present invention has a low N value, a small proportion of branched structures, and a high proportion of linear structures. In general, although a polycarbonate resin tends to have a higher fluidity (a higher Q value) when the proportion of the branched structure is increased (when the N value is increased) at the same Mw, the polycarbonate copolymer of the present invention achieves a higher fluidity (a higher Q value) while maintaining a low N value.

(8) Relation between Mw and Q value

In the polycarbonate copolymer of the present invention, the Mw and the Q value preferably have a relationship satisfying the following formula (2), and more preferably have a relationship satisfying the following formula (3), that is, the polycarbonate copolymer of the present invention can have both a high molecular weight (high Mw) and a high flowability (Q value). A polycarbonate copolymer satisfying the following formula (2) (preferably formula (3)) has not been known so far.

4.61×EXP(－0.0000785×Mw)<Q(ml/s)···(2)

4.61×EXP(－0.0000785×Mw)<Q(ml/s)<2.30×EXP(－0.0000310×Mw)···(3)

The conventional polycarbonate resin has reduced fluidity when it has a high molecular weight; in order to improve the fluidity, it is necessary to increase the amount of the low molecular weight component, and as a property of the polymer itself, it is not easy to achieve high fluidity and high molecular weight. In contrast, the polycarbonate copolymer of the present invention has a high molecular weight and high fluidity, and this is considered to be due to its novel molecular structure.

(9) Method for producing polycarbonate copolymer

The polycarbonate copolymer of the present invention is obtained by subjecting a polycondensate (hereinafter, sometimes referred to as "aromatic polycarbonate prepolymer") having a structure represented by the general formula (II) as a main repeating unit and an aliphatic diol compound derived from the structure represented by the general formula (I) to transesterification reaction under reduced pressure. The polycarbonate copolymer thus obtained can maintain the characteristics inherent in polycarbonate resins such as impact resistance, and has a high molecular weight but high fluidity.

In particular, the polycarbonate copolymer of the present invention is preferably an end-capped aromatic polycarbonate compound satisfying specific conditions described later.

In the production of the aromatic polycarbonate prepolymer having a repeating unit structure represented by the above general formula (II), the aromatic dihydroxy compound and a polyfunctional compound having 3 or more functional groups in one molecule may be used in combination. As such a polyfunctional compound, a compound having a phenolic hydroxyl group or a carboxyl group is preferably used.

When an aromatic polycarbonate prepolymer having a repeating unit structure represented by the above general formula (II) is used, a polyester carbonate can be produced by using the above aromatic dihydroxy compound and a dicarboxylic acid compound in combination. The dicarboxylic acid compound is preferably terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, 1, 4-cyclohexanedicarboxylic acid, or the like, and a method of reacting these dicarboxylic acids in the form of an acid chloride or an ester compound is preferably employed. In addition, in the production of a polyester carbonate resin, the amount of dicarboxylic acid used is preferably in the range of 0.5 to 45 mol%, more preferably in the range of 1to 40 mol%, based on 100 mol% of the total of the dihydroxy component and the dicarboxylic acid component.

At least a part of the aromatic polycarbonate prepolymer is preferably terminated with a terminal group derived from an aromatic monohydroxy compound or a terminal phenyl group (hereinafter, also referred to as a terminal end group). The effect is particularly remarkable when the ratio of the terminal end group to the total terminal end amount is 60 mol% or more. The concentration of the terminal phenyl group (the ratio of the terminal end group to the total structural units) is 2 mol% or more, preferably 2 to 20 mol%, and particularly preferably 2 to 12 mol%. When the concentration of the terminal phenyl group is 2 mol% or more, the reaction with the aliphatic diol compound proceeds rapidly, and the effects unique to the present invention can be particularly remarkably exhibited. The ratio of the amount of the terminal end to the total amount of the terminal end of the polymer can be determinedOf per polymers¹H-NMR analysis was carried out.

The terminal hydroxyl group concentration can be measured by spectroscopic measurement using a Ti complex. The concentration of terminal hydroxyl groups by this evaluation is preferably 1,500ppm or less, more preferably 1,000ppm or less. If the amount of the hydroxyl terminal is more than the above range or less than the above range, a sufficient effect of increasing the molecular weight cannot be obtained by the transesterification reaction with the aliphatic diol compound, and a polycarbonate copolymer satisfying the requirements (a) to (d) of the present invention may not be obtained.

The "total terminal group amount of polycarbonate" or "total terminal group amount of aromatic polycarbonate prepolymer" as used herein is calculated, for example, if 0.5 mole of unbranched polycarbonate (or chain polymer) is present, based on 1 mole of the total terminal group amount.

Specific examples of the terminal end group include a phenyl end group, a tolyl (cresyl) end group, an o-tolyl (o-tolyl) end group, a p-tolyl (p-tolyl) end group, a p-tert-butylphenyl end group, a biphenyl end group, an o-methoxycarbonylphenyl end group, a p-cumylphenyl end group and the like.

Among them, preferred are end groups composed of a low-boiling aromatic monohydroxy compound which can be easily removed from the reaction system in the transesterification reaction with the aliphatic diol compound, and particularly preferred are a phenyl end group, a p-tert-butylphenyl end group and the like.

Such an end-capping terminal group can be introduced by using a terminal terminator in the production of an aromatic polycarbonate prepolymer in the interfacial method. Specific examples of the terminal terminator include p-tert-butylphenol, phenol, p-cumylphenol, and long-chain alkyl-substituted phenol. The amount of the terminal terminator to be used may be appropriately determined depending on the amount of the desired terminal of the aromatic polycarbonate prepolymer (i.e., the molecular weight of the desired aromatic polycarbonate prepolymer), the reaction apparatus, the reaction conditions, and the like.

In the melt method, the end-capping terminal group can be introduced by using a carbonic acid diester such as diphenyl carbonate in an excess amount relative to the aromatic dihydroxy compound in the production of the aromatic polycarbonate prepolymer. Specifically, the carbonic acid diester is used in an amount of 1.00 to 1.30 moles, more preferably 1.02 to 1.20 moles, based on 1 mole of the aromatic dihydroxy compound, although it depends on the apparatus and reaction conditions used in the reaction. Thereby, an aromatic polycarbonate prepolymer satisfying the above end capping amount can be obtained.

In the present invention, as the aromatic polycarbonate prepolymer, an end-capped polycondensate obtained by reacting an aromatic dihydroxy compound with a carbonic acid diester (ester interchange reaction) is preferably used.

The aromatic polycarbonate prepolymer preferably has an Mw of 5,000 to 60,000. More preferably an aromatic polycarbonate prepolymer having Mw in the range of 10,000 to 50,000, still more preferably 10,000 to 40,000.

When the low molecular weight aromatic polycarbonate prepolymer exceeding the above range is used, the copolymer obtained in the present invention may be further affected by the physical properties of the copolymerization components. Although the physical properties can be improved by this, the effect of maintaining the useful physical properties of the aromatic polycarbonate may be insufficient.

If the aromatic polycarbonate prepolymer having a high molecular weight exceeding the above range is used, the production of the prepolymer may be required to be carried out at a high temperature and a high shear for a long time due to the high viscosity of the aromatic polycarbonate prepolymer itself, and/or the reaction with the aliphatic diol compound may be required to be carried out at a high temperature and a high shear for a long time, and thus it may be unsuitable for obtaining a polycarbonate copolymer having high fluidity while maintaining useful physical properties of the aromatic polycarbonate.

In the present invention, the aliphatic diol compound is allowed to act on the end-capped aromatic polycarbonate prepolymer under reduced pressure in the presence of the transesterification catalyst, whereby the molecular weight can be increased at high speed under mild conditions. That is, the reaction of the aliphatic diol compound with the aromatic polycarbonate prepolymer proceeds more rapidly than the reaction of producing the aliphatic polycarbonate unit by the ester interchange reaction after the aromatic polycarbonate prepolymer undergoes the cleavage reaction due to the aliphatic diol.

As a result, the amount of the polymer compound having a chain length (i value) of 1 derived from the structural unit of the aliphatic diol compound in the general formula (III) is much larger than that of the polymer compound having an aliphatic polycarbonate unit having an i value of 2 or more, and the polycarbonate copolymer of the present invention having a very high proportion of the polymer compound having an i value of 1 can be obtained.

Even if a polycarbonate copolymer containing the structural unit represented by the above general formula (I) and the structural unit represented by the general formula (II) in the same ratio as in the present invention is present in the past, a polycarbonate copolymer having an extremely high ratio of the polymer compound having an I value of 1 in the above general formula (III) cannot be obtained by a method of reacting an aromatic dihydroxy compound, an aliphatic diol compound, and a carbonate bond-forming compound together. In the polycarbonate copolymer having a low proportion of the polymer compound having an i value of 1 in the general formula (III), even if the polycarbonate resin has a high molecular weight and high fluidity while maintaining the physical properties inherent in the polycarbonate resin, a polymer having many branches (a high branching degree N value) may be formed, and gelation may occur, and the mechanical strength such as hue, impact resistance, stress cracking resistance and the like may tend to be reduced.

The polycarbonate copolymer obtained by the method of the present invention in which an aliphatic diol compound is allowed to act on an end-capped aromatic polycarbonate prepolymer under reduced pressure in the presence of an ester exchange catalyst exhibits a high molecular weight but a high Q value, preferably a low N value, and has a very small proportion of units having an isomeric structure which may bring about the effect of the present invention which is not necessarily preferred. Here, the unit having an isomeric structure means a branching point unit or the like contained in a large amount in a polycarbonate obtained by a conventional melt method. Examples of the unit having an isomeric structure include, but are not limited to, units having the following structures. Wherein (R1) p, (R2) q and X in the following formula are the same as those in the above general formula (II). Y represents a hydrogen atom, a phenyl group, a methyl group, a general formula (II), or the like.

As the aliphatic diol compound having a structure represented by the above general formula (I) which is derived from the above aromatic polycarbonate prepolymer by the ester interchange reaction, the compounds which can be used are as described above.

The amount of the aliphatic diol compound added in the present invention is preferably 0.01 to 1.0 mol, more preferably 0.1to 1.0 mol, and still more preferably 0.2 to 0.7 mol, based on 1 mol of the total terminal group of the aromatic polycarbonate prepolymer. However, when a compound having a low boiling point is used, an excess amount may be added in advance in consideration of the possibility that a part of the compound is discharged to the outside of the system without participating in the reaction, such as volatilization, due to the reaction conditions. For example, 1, 4-cyclohexanedimethanol (boiling point 283 ℃ C.), terephthalyl alcohol (boiling point 288 ℃ C.), m-benzenedimethanol (boiling point 290 ℃ C.), and a polycarbonate diol may be added in an amount of at most about 50 moles based on 1 mole of the total terminal groups of the aromatic polycarbonate prepolymer so that the amount of the structural units derived from the aliphatic diol compound in the obtained polycarbonate copolymer is within a desired range.

If the amount of the aliphatic diol compound used exceeds this range, the copolymerization ratio may be increased, and the influence on the physical properties of the structural unit derived from the aliphatic diol compound represented by the above general formula (I) as a copolymerization component may be increased. Although the physical properties can be improved by this, it is sometimes not preferable in terms of the effect of maintaining the useful physical properties of the aromatic polycarbonate. On the other hand, if the amount of the aliphatic diol compound used is less than this range, the effect of increasing the molecular weight and increasing the fluidity may be poor.

Among them, the raw material compounds such as the aromatic dihydroxy compound, the aliphatic diol compound, and the carbonate bond-forming compound used for producing the polycarbonate copolymer of the present invention are preferably high in chemical purity. The polycarbonate resin can be produced in a chemical purity of a commercially available product or an industrial grade, but when a low-purity product is used, the resin or the molded article obtained contains by-products derived from impurities and an isomeric skeleton structure, and thus the properties such as color enhancement, thermal stability and strength of the resin or the molded article obtained are lowered, and it may be difficult to maintain the properties inherent to the polycarbonate resin.

The chemical purity of the aliphatic diol compound is preferably 70% or more, more preferably 80% or more, and particularly preferably 90% or more. The chemical purity of the carbonate bond forming compound such as diphenyl carbonate is preferably 80% or more, more preferably 90% or more, and particularly preferably 95% or more. The chemical purity of the aromatic dihydroxy compound is preferably 90% or more, more preferably 95% or more, and particularly preferably 99% or more.

In the case where the aliphatic diol compound is a compound represented by the following formula (such as BPEF), impurities contained in a raw material compound mainly composed of the aliphatic diol compound, which are a main factor for reducing chemical purity, will be described.

(X in the above formula representsDirect combination, etc.)

Examples of impurities which are contained in the raw material compound mainly containing the aliphatic diol compound and which may be a factor of reducing chemical purity include the following compounds.

The content of impurities having these structures in the raw material compound mainly containing the aliphatic diol compound is 30% or less, preferably 20% or less, and particularly preferably 10% or less.

In addition, in the above-mentioned raw material compound, in addition to impurities which lower the chemical purity, chlorine, nitrogen, boron, alkali metals, alkaline earth metals, light metals, heavy metals, and the like may be contained as impurities, but it is preferable that the amount of chlorine, the amount of nitrogen, the amount of boron, the amount of alkali metals, the amount of alkaline earth metals, the amount of light metals, and the amount of heavy metals contained in the raw material compound are low.

Examples of the alkali metal include lithium, sodium, potassium, rubidium, cesium, and salts or derivatives thereof. As the alkaline earth metal, beryllium, magnesium, calcium, strontium, barium, and salts or derivatives thereof are exemplified. As the light metal, titanium, aluminum, and salts or derivatives thereof are exemplified.

Specific examples of the heavy metal include vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, niobium, molybdenum, ruthenium, rhodium, palladium, silver, cadmium, indium, tin, antimony, tantalum, tungsten, osmium, iridium, platinum, gold, thallium, lead, bismuth, arsenic, selenium, tellurium, and salts or derivatives thereof.

These impurities are preferably small in the total starting compound.

The content of impurities contained in the aliphatic diol compound is 3ppm or less, preferably 2ppm or less, more preferably 1ppm or less, nitrogen 100ppm or less, and the content of alkali metal, alkaline earth metal, titanium, and heavy metal (iron, nickel, chromium, zinc, copper, manganese, cobalt, molybdenum, and tin) is 10ppm or less, preferably 5ppm or less, more preferably 1ppm or less.

The content of impurities contained in the other raw materials (the aromatic dihydroxy compound and the carbonate bond forming compound) is 2ppm or less, preferably 1ppm or less, more preferably 0.8ppm or less, nitrogen is 100ppm or less, and the content of alkali metal, alkaline earth metal, titanium and heavy metal (iron, nickel, chromium, zinc, copper, manganese, cobalt, molybdenum and tin among them) is 10ppm or less, preferably 5ppm or less, more preferably 1ppm or less.

When the amount of the metal component to be mixed is large, the reaction may be accelerated or the reactivity may be deteriorated due to the catalytic action, and as a result, a predetermined reaction progress may be inhibited, a side reaction may occur, a branched structure naturally generated may increase, and the N value may unexpectedly increase. In addition, the obtained resin and molded article may have increased coloration and deteriorated physical properties such as thermal stability.

The temperature used for the transesterification reaction between the aromatic polycarbonate prepolymer and the aliphatic diol compound is preferably in the range of 240 to 320 ℃, more preferably 260 to 310 ℃, and still more preferably 270 to 300 ℃.

The degree of pressure reduction is preferably 13kPaA (100 torr) or less, more preferably 1.3kPaA (10 torr) or less, and still more preferably 0.67 to 0.013kPaA (5 to 0.1 torr).

The basic compound catalyst used in the transesterification reaction includes, in particular, an alkali metal compound and/or an alkaline earth metal compound, a nitrogen-containing compound, and the like.

As such a compound, organic acid salts, inorganic salts, oxides, hydroxides, hydrides or alkoxides, quaternary ammonium hydroxides, salts thereof, amines, and the like of alkali metal and alkaline earth metal compounds and the like are preferably used, and these compounds may be used alone or in combination.

Specific examples of the alkali metal compound include sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium hydroxide, sodium hydrogen carbonate, sodium carbonate, potassium carbonate, cesium carbonate, lithium carbonate, sodium acetate, potassium acetate, cesium acetate, lithium acetate, sodium stearate, potassium stearate, cesium stearate, lithium stearate, sodium borohydride, sodium phenylboronate, sodium benzoate, potassium benzoate, cesium benzoate, lithium benzoate, disodium hydrogenphosphate, dipotassium hydrogenphosphate, dilithium hydrogenphosphate, disodium phenylphosphate, sodium gluconate, disodium salt, dipotassium salt, dicesium salt, dilithium salt, sodium salt, potassium salt, cesium salt, and lithium salt of phenol.

Specific examples of the alkaline earth metal compound include magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, magnesium hydrogen carbonate, calcium hydrogen carbonate, strontium hydrogen carbonate, barium hydrogen carbonate, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate, magnesium acetate, calcium acetate, strontium acetate, barium acetate, magnesium stearate, calcium benzoate, and magnesium phenylphosphate.

Specific examples of the nitrogen-containing compound include quaternary ammonium hydroxides having an alkyl group and/or an aryl group such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide and trimethylbenzylammonium hydroxide, tertiary amines such as triethylamine, dimethylbenzylamine and triphenylamine, secondary amines such as diethylamine and dibutylamine, primary amines such as propylamine and butylamine, imidazoles such as 2-methylimidazole, 2-phenylimidazole and benzimidazole, and bases or basic salts such as ammonia, tetramethylammonium borohydride, tetrabutylammonium tetraphenylborate and tetraphenylammonium tetraphenylborate.

As the transesterification catalyst, salts of zinc, tin, zirconium, lead are preferably used, and they may be used alone or in combination.

Specific examples of the transesterification catalyst include zinc acetate, zinc benzoate, zinc 2-ethylhexanoate, tin (II) chloride, tin (IV) chloride, tin (II) acetate, tin (IV) acetate, dibutyl tin dilaurate, dibutyl tin oxide, dibutyl tin dimethoxide, zirconium acetylacetonate, zirconium glycolate, tetrabutoxyzirconium, lead (II) acetate, and lead (IV) acetate.

The catalyst was used in a proportion of 1 × 10to 1 mole of the total of the aromatic dihydroxy compounds^-9～1×10^-3Molar, preferably 1 × 10^-7～1×10^-5And (3) mol.

In the present invention, the weight average molecular weight (Mw) of the polycarbonate copolymer after the reaction by the transesterification reaction of the aromatic polycarbonate prepolymer and the aliphatic diol compound is preferably 5,000 or more, more preferably 10,000 or more, and further preferably 15,000 or more higher than the weight average molecular weight (Mw) of the aromatic polycarbonate prepolymer.

The transesterification reaction with the aliphatic diol compound may be carried out continuously or batchwise, using any known method such as the type of apparatus and the material of the reactor. The reaction apparatus used for carrying out the reaction may be a vertical apparatus equipped with an anchor-type stirring blade, a high-efficiency multifunctional (maxblend) stirring blade, a ribbon-type stirring blade, or the like, a horizontal apparatus equipped with a paddle-type blade, a lattice-type blade, a spectacle-type blade, or the like, or an extruder-type apparatus equipped with a screw, and is preferably carried out by using a reaction apparatus in which these apparatuses are appropriately combined in consideration of the viscosity of the polymer. Preferably, the apparatus is provided with a unit capable of forming a reduced pressure condition, the apparatus having a horizontal type rotating blade with high stirring efficiency.

More preferably a twin-screw extruder or horizontal reactor with polymer sealing, with devolatilization.

As the material of the device, stainless steel such as SUS310, SUS316, or SUS304, or a material such as nickel or iron nitride which does not affect the color tone of the polymer is preferable. Further, the inside of the device (the portion in contact with the polymer) may be subjected to polishing, electrolytic polishing, or metal plating with chromium or the like.

In the present invention, a deactivator of the catalyst may be used for the polymer having an increased molecular weight. In general, a method of deactivating the catalyst by adding a known acidic substance is suitably carried out. Specifically, aromatic sulfonic acids such as p-toluenesulfonic acid, aromatic sulfonic acid esters such as butyl p-toluenesulfonic acid, organic halides such as stearoyl chloride, butyryl chloride, benzoyl chloride and tosyl chloride, alkyl sulfates such as dimethyl sulfate, and organic halides such as chlorotoluene are preferably used.

After the catalyst deactivation, a step of devolatilizing and removing low boiling point compounds in the polymer at a pressure of 0.013 to 0.13kPaA (0.1 to 1 torr) and a temperature of 200to 350 ℃ may be provided, and for this purpose, a horizontal apparatus or a thin film evaporator having stirring blades excellent in surface renewal ability such as paddle blades, lattice airfoil blades, and double-hole airfoil blades is suitably used.

Preference is given to twin-screw extruders or horizontal reactors with polymer seals and venting.

In the present invention, an antioxidant, a pigment, a dye, a reinforcing agent or a filler, an ultraviolet absorber, a lubricant, a mold release agent, a crystal nucleating agent, a plasticizer, a flowability improving material, an antistatic agent, and the like may be added in addition to the thermal stabilizer and the hydrolysis stabilizer.

These additives can be incorporated into the polycarbonate resin by a conventionally known method. For example, a method of dispersing and mixing the respective components by using a high-speed mixer typified by a tumbler mixer, a henschel mixer, a ribbon blender or a super mixer, and then melt-kneading the mixture by an extruder, a banbury mixer, a roll or the like is suitably selected.

The hue evaluation of the aromatic polycarbonate is generally expressed by YI value. Generally, the YI value of the branched aromatic polycarbonate resin obtained by the interfacial polymerization method is 0.8 to 1.0. On the other hand, in general, a conventional high molecular weight polymer of an aromatic polycarbonate obtained by a melt polymerization method is reduced in quality with the production process, and the YI value is 1.7 to 2.0. However, the YI value of the polycarbonate copolymer obtained in the present invention is equivalent to that of the aromatic polycarbonate obtained by the interfacial polymerization method, and no deterioration in hue is observed.

II. Process for producing aromatic polycarbonate resin having high molecular weight

The method for producing a high-molecular aromatic polycarbonate resin of the present invention is characterized by comprising: and a high molecular weight increasing step of reacting the aromatic polycarbonate with a branched aliphatic diol compound having a specific structure among the aliphatic diol compounds in the presence of an ester exchange catalyst to increase the molecular weight of the compound.

(1) Aliphatic diol compound

The branched aliphatic diol compound used in the method for producing an aromatic polycarbonate resin having a high molecular weight according to the present invention is represented by the following general formula (g 1).

In the general formula (g1), Ra and Rb each independently represent a hydrogen atom, a linear or branched alkyl group having 1to 12 carbon atoms, or a phenyl group. m represents an integer of 1to 30, preferably an integer of 2 to 8, and more preferably an integer of 2 to 3.

In the general formula (g1), Ra and Rb are more preferably each independently a hydrogen atom or a linear or branched alkyl group having 1to 5 carbon atoms, and still more preferably a linear or branched alkyl group having 1to 4 carbon atoms. Specific examples of the particular preference include methyl, ethyl, propyl, n-butyl and isobutyl.

The aliphatic diol compound represented by the general formula (g1) is preferably a compound represented by the following general formula (g 2). In formula (g2), Ra and Rb are the same as in formula (g 1). n represents an integer of 1to 28, preferably an integer of 1to 6, more preferably an integer of 1to 3, and particularly preferably an integer of 1.

In the general formula (g2), Ra and Rb are more preferably each independently a hydrogen atom or a linear or branched alkyl group having 1to 5 carbon atoms, and still more preferably a linear or branched alkyl group having 1to 4 carbon atoms. Specific examples of the particular preference include methyl, ethyl, propyl, n-butyl and isobutyl.

The aliphatic diol compound represented by the general formula (g2) is more preferably a compound represented by the following general formula (g 3). In formula (g3), Ra and Rb are the same as in formula (g 1).

In the general formula (g3), Ra and Rb are more preferably each independently a hydrogen atom or a linear or branched alkyl group having 1to 5 carbon atoms, still more preferably a linear or branched alkyl group having 1to 4 carbon atoms, and yet more preferably a linear or branched alkyl group having 2 to 4 carbon atoms. Specific examples of the particularly preferable examples include methyl, ethyl, propyl, n-butyl and isobutyl, and ethyl, propyl, n-butyl and isobutyl are preferable.

Examples of such aliphatic diol compounds include 2-butyl-2-ethylpropane-1, 3-diol, 2-diisobutylpropane-1, 3-diol, 2-ethyl-2-methylpropane-1, 3-diol, 2-diethylpropane-1, 3-diol, 2-methyl-2-propylpropane-1, 3-diol, propane-1, 2-diol, propane-1, 3-diol, ethane-1, 2-diol (1, 2-ethanediol), 2-diisopentylpropane-1, 3-diol and 2-methylpropane-1, 3-diol.

Particularly preferred among these compounds are 2-butyl-2-ethylpropane-1, 3-diol, 2-diisobutylpropane-1, 3-diol, 2-ethyl-2-methylpropane-1, 3-diol, 2-diethylpropane-1, 3-diol and 2-methyl-2-propylpropane-1, 3-diol.

In the method for producing an aromatic polycarbonate resin having a high molecular weight according to the present invention, an aliphatic diol compound represented by the following general formula (g4) can be used.

In the general formula (g4), R is selected from a divalent hydrocarbon group represented by the following formula.

Preferably, in the general formula (g4), R represents- (CH)₂）_mA divalent hydrocarbon group represented by the formula (m is an integer of 3to 20), or-CH_2-C（CH₃）₂－CH₂-. As- (CH)₂）_m-, more preferably- (CH)₂）_mA divalent hydrocarbon group (m is an integer of 3to 8). n represents an integer of 1to 20, preferably an integer of 1to 3, more preferably an integer of 1to 2, and particularly preferably an integer of 1. Specific examples thereof include bis (3-hydroxy-2, 2-dimethylpropyl) carbonate and the like.

(2) Aromatic polycarbonate

The aromatic polycarbonate used in the method for producing a high-molecular-weight aromatic polycarbonate resin of the present invention is a polycondensate (aromatic polycarbonate prepolymer) having a structure represented by the general formula (II) as a main repeating unit, as in the case of the method for producing the polycarbonate copolymer. The manufacturing method of the present invention includes: and (b) subjecting the aromatic polycarbonate prepolymer and an aliphatic diol compound having a structure represented by the general formulae (g1) to (g4) to an ester interchange reaction under reduced pressure. Thus, an aromatic polycarbonate resin having a high molecular weight, while maintaining the characteristics inherent in polycarbonate resins such as impact resistance, and having the advantages of a polycarbonate having a high molecular weight and a high fluidity can be obtained, and the heat resistance is remarkably improved.

The aromatic polycarbonate prepolymer used in the present invention may be a prepolymer synthesized by an interfacial polymerization method, a prepolymer synthesized by a melt polymerization method, or a prepolymer synthesized by a solid-phase polymerization method, a thin-film polymerization method, or the like. Further, polycarbonate recovered from used products such as used disc-shaped molded products can also be used. These polycarbonates may be used as a polymer before reaction by mixing. For example, a polycarbonate obtained by interfacial polymerization may be used in combination with a polycarbonate obtained by melt polymerization, or a polycarbonate obtained by melt polymerization or interfacial polymerization may be used in combination with a polycarbonate recovered from a used tray-shaped molded article or the like.

The aromatic polycarbonate prepolymer in the present invention is a polycondensate having as a main repeating unit a reaction product of an aromatic dihydroxy compound and a carbonate bond-forming compound.

Therefore, such an aromatic polycarbonate prepolymer can be easily obtained by any of a known transesterification method in which an aromatic dihydroxy compound having various structures is reacted with a carbonic acid diester in the presence of a basic catalyst, and a known interfacial polycondensation method in which an aromatic dihydroxy compound is reacted with phosgene or the like in the presence of an acid bonding agent.

In particular, in the method of the present invention, it is preferable to use an end-capped aromatic polycarbonate compound satisfying specific conditions described later.

In addition, in the production of the aromatic polycarbonate prepolymer, the above-mentioned aromatic dihydroxy compound and a polyfunctional compound having 3 or more functional groups in one molecule may be used in combination. As such a polyfunctional compound, a compound having a phenolic hydroxyl group or a carboxyl group is preferably used.

Further, in the production of the aromatic polycarbonate prepolymer, the above aromatic dihydroxy compound and the dicarboxylic acid compound may be used in combination to form a polyester carbonate. The dicarboxylic acid compound is preferably terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, 1, 4-cyclohexanedicarboxylic acid, or the like, and these dicarboxylic acids are preferably reacted in the form of an acid chloride or an ester compound. In addition, in the production of a polyester carbonate resin, the amount of dicarboxylic acid used is preferably in the range of 0.5 to 45 mol%, more preferably in the range of 1to 40 mol%, based on 100 mol% of the total of the dihydroxy component and the dicarboxylic acid component.

At least a part of the aromatic polycarbonate prepolymer is preferably terminated with a terminal group derived from an aromatic monohydroxy compound or a terminal phenyl group (hereinafter, also referred to as "end-capped terminal group"). When the proportion of the terminal end group is 60 mol% or more based on the total amount of the terminal end group, the effect is particularly remarkable. The concentration of the terminal phenyl group (the ratio of the terminal end group to the total structural units) is 2 mol% or more, preferably 2 to 20 mol%, and particularly preferably 2 to 12 mol%. When the concentration of the terminal phenyl group is 2 mol% or more, the reaction with the aliphatic diol compound proceeds rapidly, and the effects unique to the present invention can be particularly remarkably exhibited. The ratio of the amount of blocked end to the total amount of end of the polymer may be determined by the polymerization¹H-NMR analysis was carried out.

The terminal hydroxyl group concentration can be measured by spectroscopic measurement using a Ti complex. The concentration of terminal hydroxyl groups by this evaluation is preferably 1,500ppm or less, more preferably 1,000ppm or less. If the amount is more than the above range or less than the above range, the effect of sufficiently increasing the molecular weight may not be obtained by the transesterification reaction with the aliphatic diol compound.

The "total terminal group amount of polycarbonate" or "total terminal group amount of aromatic polycarbonate prepolymer" as used herein is calculated, for example, if 0.5 mole of polycarbonate (or chain polymer) having no branch is present, based on 1 mole of the total terminal group amount.

Among them, preferred are end groups composed of a low-boiling aromatic monohydroxy compound which is easily removed from the reaction system in the transesterification reaction with the aliphatic diol compound, and particularly preferred are a phenyl end group, a p-tert-butylphenyl end group and the like.

In the melt method, the end-capping terminal group can be introduced by using a carbonic acid diester such as diphenyl carbonate in an excess amount relative to the aromatic dihydroxy compound in the production of the aromatic polycarbonate prepolymer. Specifically, the carbonic acid diester is used in an amount of 1.00 to 1.30 mol, more preferably 1.02 to 1.20 mol, based on 1 mol of the aromatic dihydroxy compound, although it depends on the apparatus and reaction conditions used in the reaction. Thereby, an aromatic polycarbonate prepolymer satisfying the above end capping amount can be obtained.

In the present invention, as the aromatic polycarbonate prepolymer, an end-capped polycondensate obtained by reacting an aromatic dihydroxy compound with a carbonic acid diester (ester interchange reaction) is used.

If the aromatic polycarbonate prepolymer having a high molecular weight exceeding this range is used, the aromatic polycarbonate prepolymer itself has a high viscosity, and therefore, the production of the prepolymer may require high temperature, high shear and a long time, and/or the reaction with the aliphatic diol compound may require high temperature, high shear and a long time.

In the method of the present invention, it is preferable to use an end-capped aromatic polycarbonate compound satisfying specific conditions described later.

(3) Cyclic carbonates

In the present invention, the aromatic polycarbonate prepolymer is increased in molecular weight by allowing an aliphatic diol compound to act on the end-capped aromatic polycarbonate prepolymer under reduced pressure in the presence of an ester exchange catalyst. This reaction proceeds rapidly under mild conditions, and the high molecular weight is achieved. That is, the reaction of the aliphatic diol compound with the aromatic polycarbonate prepolymer proceeds more rapidly than the reaction of producing the aliphatic polycarbonate unit by the ester interchange reaction after the aromatic polycarbonate prepolymer undergoes the cleavage reaction due to the aliphatic diol.

In the method of reacting the aliphatic diol compound having a specific structure, a cyclic carbonate having a cyclic body having a structure corresponding to the structure of the aliphatic diol compound is by-produced as the reaction of the aromatic polycarbonate prepolymer and the aliphatic diol compound proceeds. The by-produced cyclic carbonate is removed from the reaction system to increase the molecular weight of the aromatic polycarbonate prepolymer, thereby finally obtaining an aromatic polycarbonate resin having a structure substantially the same as that of a conventional homopolycarbonate (for example, a homopolycarbonate resin derived from bisphenol A).

That is, a preferred manufacturing method of the present invention includes: a high molecular weight conversion step of converting the aromatic polycarbonate into a high molecular weight by reacting the aromatic polycarbonate with an aliphatic diol compound in the presence of an ester exchange catalyst; and a cyclic carbonate removal step of removing at least a part of the cyclic carbonate produced as a by-product in the above-mentioned high molecular weight reaction out of the reaction system.

The high molecular weight increasing step and the cyclic carbonate removing step are not necessarily separate steps physically and temporally, and may be performed substantially simultaneously. The preferred manufacturing method of the present invention includes: a step of reacting an aromatic polycarbonate with an aliphatic diol compound in the presence of an ester exchange catalyst to increase the molecular weight of the product, and removing at least a part of a cyclic carbonate produced as a by-product in the reaction for increasing the molecular weight of the product from the reaction system.

The cyclic carbonate produced as a by-product is a compound having a structure represented by the following general formula (h 1).

In the general formula (h1), Ra and Rb each independently represent a hydrogen atom, a linear or branched alkyl group having 1to 12 carbon atoms, or a phenyl group. m represents an integer of 1to 30, preferably an integer of 2 to 8, and more preferably an integer of 2 to 3.

In the general formula (h1), Ra and Rb are more preferably each independently a hydrogen atom or a linear or branched alkyl group having 1to 5 carbon atoms, and still more preferably a linear or branched alkyl group having 1to 4 carbon atoms. Specific examples of the particular preference include methyl, ethyl, propyl, n-butyl and isobutyl.

The cyclic carbonate represented by the general formula (h1) is preferably a compound represented by the following general formula (h 2).

In the general formula (h2), Ra and Rb are respectively the same as those in the above general formula (h 1). n represents an integer of 1to 28, preferably an integer of 1to 6, more preferably an integer of 1to 3, and particularly preferably an integer of 1.

In the general formula (h2), Ra and Rb are more preferably each independently a hydrogen atom or a linear or branched alkyl group having 1to 5 carbon atoms, and still more preferably a linear or branched alkyl group having 1to 4 carbon atoms. Specific examples of the particular preference include methyl, ethyl, propyl, n-butyl and isobutyl.

The cyclic carbonate represented by the general formula (h2) is more preferably a compound represented by the following general formula (h 3). In the general formula (h3), Ra and Rb are respectively the same as those in the above general formula (h 2).

Specific examples of the cyclic carbonate include compounds having the structures shown below.

The method for producing an aliphatic diol compound having a structure represented by the general formulae (g1) to (g4) according to the present invention has an advantage that it can be converted into a high-molecular weight compound at a high speed as compared with a conventional method for producing a polycarbonate by a melt method. This is the same as the high molecular weight polycarbonate resin obtained by the method of linking and increasing the molecular weight using another aliphatic diol compound as a linking agent, which was found by the inventors of the present invention.

However, in the method of the present invention for producing an aliphatic diol compound having a structure represented by the general formulae (g1) to (g4), a cyclic carbonate having a specific structure is by-produced as the reaction for increasing the molecular weight proceeds. Further, a high molecular weight polycarbonate resin having substantially the same skeleton as that of the homopolycarbonate resin can be obtained by removing the cyclic carbonate produced as a by-product from the reaction system. The cyclic carbonate produced as a by-product has a structure corresponding to the aliphatic diol compound used and is considered to be a cyclic product derived from the aliphatic diol compound, but the reaction mechanism of the cyclic carbonate produced as a by-product with the increase in molecular weight is not clear.

For example, the mechanism shown in the following scheme (1) or (2) can be considered, but it is not clear. The method of the present invention for producing an aliphatic diol compound having a structure represented by the general formulae (g1) to (g4) is not limited to a specific reaction mechanism, and is a method of producing an aliphatic diol compound having a structure represented by the general formulae (g1) to (g4) in which an aliphatic diol compound having a specific structure is reacted with an aromatic polycarbonate prepolymer and a cyclic carbonate having a structure corresponding to the structure of the aliphatic diol compound formed as a by-product is removed.

Scheme (1):

scheme (2):

unlike the high-molecular-weight polycarbonate copolymer obtained by the method of linking and polymerizing by using a linking agent, the high-molecular-weight polycarbonate resin obtained by the method of producing the aliphatic diol compound having the structure represented by the general formulae (g1) to (g4) according to the present invention contains almost no copolymerized component derived from the linking agent, and the skeleton of the resin is substantially the same as that of the homopolycarbonate resin.

Therefore, compared with other high-molecular-weight polycarbonate resins obtained by a method of increasing the linking molecular weight, the resin composition does not contain a copolymerization component derived from the linking agent aliphatic diol compound in the backbone and contains a very small amount of the copolymerization component, and therefore has extremely high thermal stability and excellent heat resistance. On the other hand, a high molecular weight polycarbonate resin having substantially the same skeleton as a conventional homopolycarbonate resin and having the same advantages as other high molecular weight polycarbonate resins obtained by a method of linking to increase the molecular weight can have excellent qualities such as a low N value, a small proportion of units having an isomeric structure, and an excellent color tone. Here, the unit having an isomeric structure means a branching point unit and the like contained in a large amount in a polycarbonate obtained by a conventional melt method. Specific examples of the unit having an isomeric structure include the same units as those having an isomeric structure as mentioned above with respect to the polycarbonate copolymer, but are not limited thereto.

When the copolymerization component derived from the aliphatic diol compound is contained in the backbone of the high-molecular weight polycarbonate resin obtained by the method for producing a high-molecular weight polycarbonate resin using the aliphatic diol compound having a structure represented by the general formulae (g1) to (g4), the proportion of the structural unit derived from the aliphatic diol compound to the total amount of the structural units of the high-molecular weight polycarbonate resin is 1 mol% or less, and more preferably 0.1 mol% or less.

The amount of the aliphatic diol compound used in the present invention is preferably 0.01 to 1.0 mol, more preferably 0.1to 1.0 mol, and still more preferably 0.2 to 0.7 mol, based on 1 mol of the total terminal groups of the aromatic polycarbonate prepolymer. However, when a substance having a low boiling point is used, an excessive amount may be added in advance in consideration of the possibility that a part of the substance is volatilized by reaction conditions and is discharged to the outside of the system without participating in the reaction. For example, the amount of the polycarbonate prepolymer may be 50 mol or less, preferably 10 mol or less, more preferably 5mol or less based on 1 mol of the total terminal groups of the prepolymer.

In addition, the raw material compounds used for producing the aromatic polycarbonate resin having a high molecular weight of the present invention, such as an aromatic dihydroxy compound, an aliphatic diol compound, and a carbonate bond-forming compound, are preferably high in chemical purity. Although it can be produced in commercial or industrial grade chemical purity, when a low-purity product is used, the by-product derived from impurities and the isomeric skeleton structure are contained, and thus the obtained resin or molded article has enhanced coloring and various properties such as thermal stability and strength are deteriorated, and it is sometimes difficult to maintain the inherent properties of the polycarbonate resin.

The preferable chemical purity and allowable amount of impurities of the aliphatic diol compound are the same as those used in the production of the polycarbonate copolymer. Further, by using a raw material having a higher purity, the color tone and the molecular weight retention ratio (an index indicating how much the decrease in the molecular weight can be suppressed when heat retention is performed at a high temperature) can be further improved.

(3) Manufacturing method

The following will describe the detailed conditions of the method for producing an aliphatic diol compound of the present invention using the structures represented by the general formulae (g1) to (g 4).

(i) Addition of aliphatic diol Compound

In the method of the present invention for producing an aliphatic diol compound having a structure represented by the general formulae (g1) to (g4), an aliphatic diol compound is added to and mixed with an aromatic polycarbonate prepolymer, and a high-molecular-weight reaction (transesterification reaction) is carried out in a high-molecular-weight reactor.

The method for adding and mixing the aromatic polycarbonate prepolymer and the aliphatic diol compound is not particularly limited, but when a compound having a relatively high boiling point (a boiling point of about 240 ℃ or higher) is used as the aliphatic diol compound, the aliphatic diol compound is preferably directly supplied to the high molecular weight reactor under a high vacuum at a reduced pressure of 10torr (1333 Pa or lower). The degree of pressure reduction is more preferably 2.0torr or less (267 Pa or less), and still more preferably 0.01 to 1torr (1.3 to 133Pa or less). If the degree of pressure reduction at the time of supplying the aliphatic diol compound to the high molecular weight reactor is insufficient, a cleavage reaction of the main chain of the prepolymer due to the by-product (phenol) occurs, and it is sometimes necessary to extend the reaction time of the reaction mixture in order to increase the molecular weight.

On the other hand, when the aliphatic diol compound has a relatively low boiling point (a boiling point of about 350 ℃ C. or less), the aromatic polycarbonate prepolymer and the aliphatic diol compound can be mixed at a relatively mild reduced pressure. For example, since the aromatic polycarbonate prepolymer and the aliphatic diol compound are mixed at a pressure close to normal pressure to obtain a prepolymer mixture, and then the prepolymer mixture is subjected to a high molecular weight reaction under reduced pressure, the volatilization of the aliphatic diol compound having a low boiling point can be minimized without the necessity of excessive use.

(ii) Transesterification (high molecular weight reaction)

The temperature used for the transesterification reaction (high molecular weight reaction) between the aromatic polycarbonate prepolymer and the aliphatic diol compound is preferably in the range of 240 to 320 ℃, more preferably 260 to 310 ℃, and still more preferably 270 to 300 ℃.

The basic compound catalyst used in the present transesterification reaction includes, in particular, an alkali metal compound and/or an alkaline earth metal compound, a nitrogen-containing compound, and the like.

The catalyst was used in a ratio of 1 × 10to 1 mol of the total of the aromatic dihydroxy compounds^-9～1×10^-3Molar, preferably 1 × 10^-7～1×10^-5And (3) mol.

(iii) Cyclic carbonate removal step

In the method of the present invention, the aromatic polycarbonate prepolymer is polymerized by the above-mentioned polymerization reaction, and at least a part of the cyclic carbonate formed as a by-product in the reaction is removed to the outside of the reaction system. The reaction for increasing the molecular weight of the aromatic polycarbonate prepolymer proceeds by removing the cyclic carbonate produced as a by-product from the reaction system.

Examples of the method for removing the cyclic carbonate include a method of distilling and removing the phenol produced as a by-product from the reaction system together with the unreacted aliphatic diol compound and the like. The temperature at which the reaction mixture is distilled off from the reaction system is 260 to 320 ℃.

The removal of the cyclic carbonate is carried out with respect to at least a part of the cyclic carbonate produced as a by-product. Most preferably, all of the cyclic carbonate produced as a by-product is removed, but complete removal is generally difficult. In the case where the cyclic carbonate cannot be completely removed, the cyclic carbonate is allowed to remain in the polycarbonate resin as a product. The upper limit of the amount remaining in the product is preferably 3000 ppm. That is, according to the method for producing an aliphatic diol compound having a structure represented by the general formulae (g1) to (g4) of the present invention, a polycarbonate resin composition having a cyclic carbonate content of 3000ppm or less is obtained as described below.

The cyclic carbonate removed by distillation to the outside of the reaction system can be recovered and reused (recycle) after going through the steps of hydrolysis, purification and the like. Phenol distilled off together with the cyclic carbonate can be recovered in the same manner, supplied to the diphenyl carbonate production process, and reused.

(iv) Other manufacturing conditions

The transesterification reaction with the aliphatic diol compound may be carried out continuously or batchwise, using any known method, such as the type of apparatus and the material of the reactor. The reaction apparatus used for carrying out the reaction may be a vertical apparatus equipped with an anchor-type stirring blade, a high-efficiency multifunctional (maxblend) stirring blade, a ribbon-type stirring blade, or the like, a horizontal apparatus equipped with a paddle-type blade, a lattice-type blade, a spectacle-type blade, or the like, or an extruder-type apparatus equipped with a screw, and is preferably carried out by using a reaction apparatus in which these apparatuses are appropriately combined in consideration of the viscosity of the polymer. Preferably, the apparatus is provided with a unit capable of forming a reduced pressure condition, the apparatus having a horizontal type rotating blade with high stirring efficiency.

After the catalyst deactivation, a step of devolatilizing and removing low boiling point compounds in the polymer at a pressure of 0.013 to 0.13kPaA (0.1 to 1 torr) and a temperature of 200to 350 ℃ may be provided, and for this purpose, a horizontal apparatus or a thin film evaporator having stirring blades excellent in surface renewal ability such as paddle blades, lattice airfoil blades, and spectacle airfoil blades is suitably used.

In the present invention, an antioxidant, a pigment, a dye, a reinforcing agent or a filler, an ultraviolet absorber, a lubricant, a mold release agent, a crystal nucleating agent, a plasticizer, a flowability improver, an antistatic agent, and the like may be added in addition to the thermal stabilizer and the hydrolysis stabilizer.

The hue evaluation of the aromatic polycarbonate is generally expressed by YI value. Generally, the YI value of the branched aromatic polycarbonate resin obtained by the interfacial polymerization method is 0.8 to 1.0. On the other hand, generally, the aromatic polycarbonate obtained by the melt polymerization method has a high molecular weight and a YI value of 1.7 to 2.0, because the quality of the polymer decreases with the production process. However, the YI value of the polycarbonate copolymer obtained in the present invention is equivalent to that of the aromatic polycarbonate obtained by the interfacial polymerization method, and no deterioration in hue is observed. Further, by using a raw material having a high purity, the color tone and the molecular weight retention ratio (an index indicating how much the decrease in the molecular weight can be suppressed when heat retention is performed at a high temperature) can be further improved. Specifically, the molecular weight retention can be improved to 100%.

(4) Aromatic polycarbonate resin having high molecular weight

The aromatic polycarbonate resin having a high molecular weight obtained by the method for producing an aliphatic diol compound having a structure represented by the general formulae (g1) to (g4) according to the present invention has a weight average molecular weight (Mw) of 30,000 to 100,000, preferably 30,000 to 80,000, more preferably 35,000 to 75,000, and has high fluidity in spite of its high molecular weight. When the weight average molecular weight is too low, melt tension is lowered and sagging is likely to occur when the resin composition is used for blow molding, extrusion molding, or other applications, and a satisfactory molded article cannot be obtained. Further, when the resin composition is used for injection molding or the like, a satisfactory molded article cannot be obtained due to wire drawing or the like. And the resulting molded article has reduced physical properties such as mechanical properties and heat resistance. Further, the oligomer region is increased, and the physical properties such as organic solvent resistance are also lowered. If the weight average molecular weight is too high, injection molding of precision parts or thin objects becomes difficult, the molding cycle time is prolonged, and the production cost is adversely affected. Therefore, measures such as increasing the molding temperature are required, but gelation, an isomeric structure, an increase in the N value, and the like may occur at high temperatures.

In the aromatic polycarbonate resin having a high molecular weight of the present invention, the N value (structural viscosity index) represented by the following formula (1) is preferably 1.3 or less, more preferably 1.28 or less, and particularly preferably 1.25 or less.

N value (log (Q160 value) -log (Q10 value))/(log 160-log10) · (1)

In the above mathematical formula (1), a Q160 value represents a melt flow volume (ml/sec) per unit time measured at 280 ℃ under a load of 160kg (measured using CFT-500D manufactured by shimadzu corporation (hereinafter the same), and calculated from a stroke of 7.0 to 10.0 mm), and a Q10 value represents a melt flow volume (ml/sec) per unit time measured at 280 ℃ under a load of 10kg (calculated from a stroke of 7.0 to 10.0 mm). (wherein, the nozzle diameter is 1 mm. times. the nozzle length is 10 mm).

The structural viscosity index "N value" is an index of the degree of branching of the aromatic polycarbonate resin. The polycarbonate copolymer of the present invention has a low N value, a small proportion of branched structures, and a high proportion of linear structures. In general, although a polycarbonate resin tends to have a higher fluidity (a higher Q value) when the proportion of the branched structure is increased at the same Mw, the polycarbonate copolymer of the present invention achieves a higher fluidity (a higher Q value) while maintaining a low N value.

(4) Polycarbonate resin composition

The polycarbonate resin composition of the present invention mainly comprises the aromatic polycarbonate resin having a high molecular weight produced by the above-mentioned production method of the present invention, and contains a cyclic carbonate represented by the following general formula (h 1). That is, the aromatic polycarbonate resin having a high molecular weight obtained by the above-mentioned production method of the present invention may contain a small amount of residual cyclic polycarbonate after removing the cyclic carbonate produced as a by-product in the production process.

The content of the cyclic carbonate represented by the above general formula (h1) in the polycarbonate resin composition of the present invention is 3000ppm or less, preferably 1000ppm or less, more preferably 500ppm or less, and particularly preferably 300ppm or less. The lower limit of the content of the cyclic polycarbonate is not particularly limited. Ideally 0%, but is usually a detection limit value, preferably 0.0005ppm or more. If the content of the cyclic carbonate is too high, there may be a disadvantage such as a decrease in strength of the resin.

(5) Molded article

The polycarbonate copolymer of the present invention, the high molecular weight aromatic polycarbonate resin obtained by the method of the present invention, and the polycarbonate resin composition are preferably used for various applications such as molded articles, sheets, and films obtained by injection molding, blow molding (blow molding), extrusion molding, injection blow molding, rotational molding, and compression molding. When used in these applications, the resin of the present invention may be used alone or in admixture with other polymers. Depending on the application, a hard coat layer or a lamination process is also preferably used.

The polycarbonate copolymer of the present invention, the aromatic polycarbonate resin having a high molecular weight obtained by the method of the present invention, and the polycarbonate resin composition are particularly preferably used for extrusion molding, blow molding, injection molding, and the like. The molded article obtained may be an extrusion molded article, a hollow molded article, an injection molded article of a precision part or a thin object. Injection-molded articles of precision parts or thin objects preferably have a thickness of 1 μm to 3 mm.

Specific examples of the molded article include optical media such as Compact Discs (CDs), digital video discs, mini-discs (MDs), and magneto-optical disks, optical communication media such as optical fibers, optical components such as headlight lenses for vehicles and lenses for cameras, optical equipment components such as alarm covers and illumination covers, window glass substitutes for vehicles such as electric cars and automobiles, window glass substitutes for homes, lighting components such as sunroofs (sunroofs) and roofs of greenhouses, lenses and housings for goggles, sunglasses, glasses, housings for OA equipment such as copying machines, facsimile machines, and computers, housings for household appliances such as televisions and microwave ovens, electronic component applications such as connectors and IC trays, protective devices such as protectors and protective masks, household products such as nursing bottles, tableware and plates, medical products such as artificial dialysis cases and artificial teeth, packaging materials, and packaging materials, Writing instruments, miscellaneous goods such as stationery, and the like, but not limited thereto.

The polycarbonate copolymer of the present invention, the aromatic polycarbonate resin having a high molecular weight obtained by the method of the present invention, and the polycarbonate resin composition are preferably used in the following applications, particularly in the fields of molded articles requiring high strength and precision moldability.

As automobile parts, headlamp lenses, instrument panels, sunroofs, and the like, and substitutes for glass windows or exterior panel parts

Various films, light guide plates, and optical disk substrates for liquid crystal displays and the like.

Building Material such as transparent sheet

Casing for computer, printer, liquid crystal television, or the like as a constituent member

III. aromatic polycarbonate Compound

The aromatic polycarbonate compound of the present invention is characterized by being substantially formed from a structural unit (polycarbonate-forming unit) represented by the following general formula (1) and satisfying: (A) a weight average molecular weight (Mw) of 5,000 to 60,000, a terminal hydroxyl group concentration of 1500ppm or less, and a terminal phenyl group concentration of 2 mol% or more. That is, the aromatic polycarbonate compound of the present invention is a polycondensate having as a main repeating unit a reaction product of an aromatic dihydroxy compound and a carbonate bond-forming compound.

In the general formula (1), the two phenylene groups may be both p-phenylene, m-phenylene or o-phenylene, and may be each a different substitution position, and preferably both p-phenylene groups.

In the general formula (1), R₁And R₂Independently represents a halogen atom, a nitro group, an amino group, an alkyl group having 1to 20 carbon atoms, an alkoxy group having 1to 20 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms and an aralkyl group having 6 to 20 carbon atoms.

Examples of the alkyl group having 1to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, an isobutyl group, an n-pentyl group, and a pentyl group. Examples of the alkoxy group having 1to 20 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, and an isopropoxy group. Examples of the cycloalkyl group having 6 to 20 carbon atoms include cyclohexyl, adamantyl, bicyclodecyl, tricyclodecyl and the like. Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, a naphthyl group, and a 4-isopropyl-phenyl group. Examples of the cycloalkoxy group having 6 to 20 carbon atoms include a cyclohexyloxy group and the like. Examples of the aryloxy group having 6 to 20 carbon atoms include a phenoxy group, a naphthoxy group, a chlorophenoxy group, a bromophenoxy group and the like. Examples of the aralkyl group include a benzyl group, a 2-methoxybenzyl group, a 3-methoxybenzyl group, a 4-methoxybenzyl group, a 2-nitrobenzyl group, a 3-nitrobenzyl group, a 4-nitrobenzyl group, a 2-chlorobenzyl group, a 3-chlorobenzyl group, a 4-chlorobenzyl group, a 2-methylbenzyl group, a 3-methylbenzyl group, and a 4-methylbenzyl group.

R₁And R₂Preferable specific examples of (A) are fluorine, amino, methoxy, methyl, cyclohexyl and phenyl.

p and q represent an integer of 0to 4, preferably an integer of 0to 2. X represents a bond or a group selected from divalent organic groups represented by the following general formula (1').

In the above general formula (1'), R₃And R₄Each independently represents a hydrogen atom, an alkyl group having 1to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, R₃And R₄May combine to form an alicyclic ring.

Specific examples of X include a simple valence bond, -CH₂A divalent organic group having the following structure, and the like.

Specific examples of such a polycarbonate-forming unit include units derived from bis (4-hydroxyphenyl) methane, 1-bis (4-hydroxyphenyl) ethane, 1, 2-bis (4-hydroxyphenyl) ethane, 2-bis (4-hydroxyphenyl) propane, 2-bis (4-hydroxy-3-isopropylphenyl) propane, 2-bis (4-hydroxyphenyl) butane, 2-bis (4-hydroxyphenyl) octane, 2-bis (3-tert-butyl-4-hydroxyphenyl) propane, 2-bis (3-bromo-4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) phenylmethane, 1-bis (4-hydroxyphenyl) -1-phenylethane, 1-bis (4-hydroxyphenyl) 1-phenylethane, Bis (4-hydroxyphenyl) diphenylmethane, 2-bis (4-hydroxy-3-methylphenyl) propane, 1-bis (4-hydroxy-3-tert-butylphenyl) propane, 2-bis (3-cyclohexyl-4-hydroxyphenyl) propane, 1-bis (3-cyclohexyl-4-hydroxyphenyl) cyclohexane, 2-bis (3, 5-dimethyl-4-hydroxyphenyl) propane, 2-bis (4-hydroxy-3-phenylphenyl) propane, 2-bis (4-hydroxy-3-bromophenyl) propane, 2-bis (3, 5-dibromo-4-hydroxyphenyl) propane, 2-bis (4-hydroxy-3-bromophenyl) propane, 2, 5-dibromo-4-hydroxyphenyl) propane, 2-bis (4-hydroxyphenyl) propane, 2-bis (3, 3-hydroxy-3-hydroxyphenyl) propane, 1, 1-bis (4-hydroxyphenyl) cyclopentane, 1-bis (4-hydroxyphenyl) cyclohexane, 2-bis (4-hydroxy-3-methoxyphenyl) propane, 1-bis (4-hydroxyphenyl) -3,3, 5-trimethylcyclohexane, 4 '-dihydroxydiphenyl ether, 4' -dihydroxybiphenyl, 9-bis (4-hydroxyphenyl) fluorene, 9-bis (4-hydroxy-3-methylphenyl) fluorene, 4 '-dihydroxy-3, 3' -dimethylphenyl ether, 4 '-dihydroxyphenyl sulfide, 4' -dihydroxy-3, 3 '-dimethyldiphenyl sulfide, 4' -dihydroxydiphenyl sulfoxide, 4,4 '-dihydroxy-3, 3' -dimethyldiphenylsulfoxide, 4 '-dihydroxydiphenylsulfone, 4' -dihydroxy-3, 3 '-dimethyldiphenylsulfone, 4' -sulfonyldiphenol, 2 '-diphenyl-4, 4' -sulfonyldiphenol, 2,2 '-dimethyl-4, 4' -sulfonyldiphenol, 1, 3-bis { 2- (4-hydroxyphenyl) propyl } benzene, 1, 4-bis (4-hydroxyphenyl) cyclohexane, 1, 3-bis (4-hydroxyphenyl) cyclohexane, 4, 8-bis (4-hydroxyphenyl) tricyclo [ 5.2.1.0.^2,6Decane, 4' - (1, 3-adamantanediyl) diphenol, 1, 3-bis (4-hydroxyphenyl) -5, 7-dimethyladamantane, and the like.

Among them, a structural unit derived from 2, 2-bis (4-hydroxyphenyl) propane (bisphenol a or BPA) is preferably exemplified. The constituent units derived from a plurality of the above-mentioned various monomers (aromatic dihydroxy compounds) may be combined as necessary for the purpose of controlling the glass transition temperature, improving the fluidity, improving the refractive index, reducing the birefringence, and controlling the optical properties, etc.

The aromatic polycarbonate compound of the present invention has a weight average molecular weight (Mw) of 5,000 to 60,000, preferably 10,000 to 50,000, and more preferably 10,000 to 40,000. In the case of the low molecular weight aromatic polycarbonate compound exceeding this range, the influence of the physical properties of the aliphatic diol compound increases when reacting with the aliphatic diol compound. Although the physical properties can be improved by this, the physical properties inherent in the aromatic polycarbonate compound may be impaired, which is not preferable. In addition, in the case of the aromatic polycarbonate compound having a high molecular weight exceeding this range, the concentration of the active terminal is decreased, and the effect of the reaction with the aliphatic diol compound is poor. Further, since the compound itself has a high viscosity, it is required to be carried out at a high temperature under high shear for a long period of time as a reaction condition, and it is not preferable to obtain a high-quality aromatic polycarbonate resin.

Further, the aromatic polycarbonate compound of the present invention is characterized in that at least a part thereof is terminated with a phenyl group. The concentration of the end-capped terminal group (terminal phenyl group) is 2 mol% or more, preferably 2 to 20 mol%, and particularly preferably 2 to 12 mol%. When the concentration of the terminal phenyl group is 2 mol% or more, the reaction with the aliphatic diol compound proceeds rapidly, and the effects unique to the present invention can be particularly remarkably exhibited.

The aromatic polycarbonate compound of the present invention is obtained by reacting an aromatic dihydroxy compound (BPA or the like) with a carbonate bond forming compound (diphenyl carbonate or the like) as described later, and the polymer molecule has a phenylene group derived from the aromatic dihydroxy compound and a phenyl group derived from the carbonate bond forming compound. The terminal phenyl group of the aromatic polycarbonate compound of the present invention is a phenyl group derived from a carbonate bond-forming compound. The terminal phenyl group concentration in the present invention means: the ratio (mol%) of the terminal phenyl group to the total amount (mol%) of the structural units derived from the aromatic dihydroxy compound and the total amount (mol%) of the terminal phenyl groups derived from the carbonate bond-forming compound constituting the aromatic polycarbonate compound.

The concentration of terminal hydroxyl groups in the aromatic polycarbonate compound is 1,500ppm or less, preferably 1,300ppm or less, particularly preferably 1,000ppm or less, and more preferably 700ppm or less. In this case, the reaction with the aliphatic diol compound proceeds rapidly, and the effects unique to the present invention can be exhibited remarkably.

The "total terminal group amount" of the aromatic polycarbonate compound referred to herein is calculated, for example, if the amount of polycarbonate (or chain polymer) having no branch is 0.5 mol, based on 1 mol of the total terminal group amount. The aromatic polycarbonate compound has a terminal phenyl group concentration and a terminal hydroxyl group concentration¹H-NMR analysis was carried out.

(2) Process for producing aromatic polycarbonate compound

The aromatic polycarbonate compound of the present invention can be obtained by reacting an aromatic dihydroxy compound with a carbonate bond-forming compound. Specifically, the aromatic polycarbonate compound can be obtained by a known interfacial polycondensation method in which an aromatic dihydroxy compound having each structure is reacted with phosgene or the like in the presence of an acid bonding agent, or a known transesterification method in which an aromatic dihydroxy compound is reacted with a carbonic acid diester in the presence of a basic catalyst.

That is, the aromatic polycarbonate compound may be synthesized by an interfacial polymerization method, may be synthesized by a melt polymerization method, or may be synthesized by a method such as a solid-phase polymerization method or a thin-film polymerization method. Further, polycarbonate recovered from used products such as used disc-shaped molded products can also be used. These polycarbonates may be used as a polymer before reaction by mixing. For example, a polycarbonate obtained by interfacial polymerization may be used in combination with a polycarbonate obtained by melt polymerization, or a polycarbonate obtained by melt polymerization or interfacial polymerization may be used in combination with a polycarbonate recovered from a used tray-shaped molded article or the like.

The aromatic dihydroxy compound used in the production of the aromatic polycarbonate compound of the present invention includes compounds represented by the following general formula (2).

In the above general formula (2), R₁～R₂P, q and X are the same as in the above general formula (1).

Specific examples of such aromatic dihydroxy compounds include bis (4-hydroxyphenyl) methane, 1-bis (4-hydroxyphenyl) ethane, 1, 2-bis (4-hydroxyphenyl) ethane, 2-bis (4-hydroxyphenyl) propane, 2-bis (4-hydroxy-3-isopropylphenyl) propane, 2-bis (4-hydroxyphenyl) butane, 2-bis (4-hydroxyphenyl) octane, 2-bis (3-tert-butyl-4-hydroxyphenyl) propane, 2-bis (3-bromo-4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) phenylmethane, 1-bis (4-hydroxyphenyl) -1-phenylethane, and mixtures thereof, Bis (4-hydroxyphenyl) diphenylmethane, 2-bis (4-hydroxy-3-methylphenyl) propane, 1-bis (4-hydroxy-3-tert-butylphenyl) propane, 2-bis (3-cyclohexyl-4-hydroxyphenyl) propane, 1-bis (3-cyclohexyl-4-hydroxyphenyl) cyclohexane, 2-bis (3, 5-dimethyl-4-hydroxyphenyl) propane, 2-bis (4-hydroxy-3-phenylphenyl) propane, 2-bis (4-hydroxy-3-bromophenyl) propane, 2-bis (3, 5-dibromo-4-hydroxyphenyl) propane, 2-bis (4-hydroxy-3-bromophenyl) propane, 2, 5-dibromo-4-hydroxyphenyl) propane, 2-bis (4-hydroxyphenyl) propane, 2-bis (3, 3-hydroxy-3-hydroxyphenyl) propane, 1, 1-bis (4-hydroxyphenyl) cyclopentane, 1-bis (4-hydroxyphenyl) cyclohexane, 2-bis (4-hydroxy-3-methoxyphenyl) propane, 1-bis (4-hydroxyphenyl) -3,3, 5-trimethylcyclohexane, 4' -dihydroxydiphenyl ether, 4' -dihydroxybiphenyl, 9-bis (4-hydroxyphenyl) fluorene, 9-bis (4-hydroxy-3-methylphenyl) fluorene, 4' -dihydroxy-3, 3 ' of '-dimethylphenyl ether, 4 '-dihydroxyphenyl sulfide, 4' -dihydroxy-3, 3 '-dimethyldiphenyl sulfide, 4' -dihydroxydiphenyl sulfoxide, 4 '-dihydroxy-3, 3' -dimethyldiphenyl sulfoxide, 4 '-dihydroxydiphenyl sulfone, 4' -dihydroxy-3, 3 '-dimethyldiphenyl sulfone, 4' -sulfonyldiphenol, 2 '-diphenyl-4, 4' -sulfonyldiphenol, 2 '-dimethyl-4, 4' -sulfonyldiphenol, 1, 3-bis { 2- (4-hydroxyphenyl) propyl } benzene, 1, 4-bis { 2- (4-hydroxyphenyl) propyl } benzene, 2,4 '-dihydroxy-3, 3' -dimethyldiphenyl sulfone, 4 '-dihydroxydiphenyl sulfone, 4' -sulfonyldiphenol, and the like, 1, 4-bis (4-hydroxyphenyl) cyclohexane, 1, 3-bis (4-hydroxyphenyl) cyclohexane, 4, 8-bis (4-hydroxyphenyl) tricyclo [ 5.2.1.0^2，6Decane, 4' - (1, 3-adamantanediyl) diphenol, 1, 3-bis (4-hydroxyphenyl) -5, 7-dimethyladamantane, and the like.

Among them, 2-bis (4-hydroxyphenyl) propane (bisphenol a or BPA) is preferable because of stability as a monomer and easy availability of a form containing a small amount of impurities.

The aromatic dihydroxy compound may be prepared by combining a plurality of the above monomers (aromatic dihydroxy compound) as required for the purpose of controlling the glass transition temperature, improving the fluidity, increasing the refractive index, reducing the birefringence, and controlling the optical properties.

The dicarboxylic acid compound may be used in combination with the aromatic dihydroxy compound to prepare a polyester carbonate. The dicarboxylic acid compound is preferably terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, 1, 4-cyclohexanedicarboxylic acid, or the like, and these dicarboxylic acids are preferably reacted in the form of an acid chloride or an ester compound. In addition, in the production of a polyester carbonate resin, the amount of dicarboxylic acid used is preferably in the range of 0.5 to 45 mol%, more preferably in the range of 1to 40 mol%, based on 100 mol% of the total of the dihydroxy component and the dicarboxylic acid component.

In the present invention, the aromatic dihydroxy compound and a polyfunctional compound having 3 or more, preferably 3to 6 functional groups in one molecule may be used in combination as necessary. As such a polyfunctional compound, a compound having a phenolic hydroxyl group or a carboxyl group is preferably used.

Specific examples of the 3-functional compound include 1,1, 1-tris (4-hydroxyphenyl) ethane, 2 ', 2' '-tris (4-hydroxyphenyl) diisopropylbenzene, α -methyl- α, α', α '' -tris (4-hydroxyphenyl) -1, 4-diethylbenzene, α ', α' '-tris (4-hydroxyphenyl) -1,3, 5-triisopropylbenzene, phloroglucinol, 4, 6-dimethyl-2, 4, 6-tris (4-hydroxyphenyl) -heptane, 1,3, 5-tris (4-hydroxyphenyl) benzene, 2-bis [4, 4- (4, 4' -dihydroxyphenyl) -cyclohexyl ] -propane, trimellitic acid, and the like, 1,3, 5-benzenetricarboxylic acid, pyromellitic acid, trimethylolpropane, 1,2, 5-pentanetriol, 3, 4-dihydroxybenzyl alcohol, 1,2, 6-hexanetriol, 1,3, 5-adamantanetriol, etc.

Specific examples of the 4-or higher-functional compound include red gallophenol, 2,3,4, 4' -tetrahydroxybenzophenone, 2,3,4, 4' -tetrahydroxydiphenylmethane, pyrogallophthalein, and 2,3,3 ', 4,4', 5 ' -hexahydroxybenzophenone.

Among these, 1,1, 1-tris (4-hydroxyphenyl) ethane is more preferable because of the stability of the monomer and the availability of a form containing a small amount of impurities.

In particular, when the aromatic polycarbonate compound of the present invention is an aromatic polycarbonate compound into which a branched structure has been introduced, a branched structure can be introduced into the molecular chain in an arbitrary amount by using the polyfunctional compound as a branching agent in the reaction of the aromatic dihydroxy compound and the carbonate bond-forming compound.

The amount of the branching agent to be used (the amount of the branched structure to be introduced) may vary depending on the purpose of improving blow moldability, drip resistance, flame retardancy, etc., and is preferably 0.01 to 1 mol%, more preferably 0.1to 0.9 mol%, particularly preferably 0.2 to 0.8 mol%, based on the total amount (total number of moles) of the carbonate structural units represented by the above general formula (1) in the aromatic polycarbonate compound. Or preferably 0.01 to 1 mol%, more preferably 0.1to 0.9 mol%, and particularly preferably 0.2 to 0.8 mol%, based on the total mole number of the aromatic dihydroxy compound and the branching agent used.

In the interfacial polymerization method, carbonyl halide such as phosgene or haloformate (haloform) compound is used as the carbonate bond forming compound. Also, the reaction is generally carried out in the presence of an acid binder and a solvent. Examples of the acid binder include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and amine compounds such as pyridine. As the solvent, for example, a halogenated hydrocarbon such as dichloromethane or chlorobenzene can be used. In addition, a catalyst such as a tertiary amine or a quaternary ammonium salt may be used to promote the reaction. In this case, the reaction temperature is usually 0to 40 ℃ and the reaction time is several minutes to 5 hours.

In the interfacial method, a terminal terminator may be used in the production of the aromatic polycarbonate compound in order to obtain a desired amount of terminal end groups (terminal phenyl group concentration). Specific examples of the terminal terminator include p-tert-butylphenol, phenol, p-cumylphenol, and long-chain alkyl-substituted phenol. The amount of the terminal terminator to be used may be appropriately determined depending on the desired concentration of the terminal phenyl group in the aromatic polycarbonate compound, the reaction apparatus, the reaction conditions, and the like.

In the melt polymerization method, a carbonic acid diester is used as the carbonate bond forming compound. The carbonic acid diester compound includes a compound represented by the following general formula (3).

In the general formula (3), A is a linear, branched or cyclic 1-valent hydrocarbon group having 1to 10 carbon atoms which may have a substituent. The two A's may be the same or different.

Specific examples of the carbonic acid diester include aromatic carbonic acid diesters such as diphenyl carbonate, ditolyl carbonate, bis (2-chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate and bis (4-phenylphenyl) carbonate. Dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, and the like may also be used as necessary. Among them, diphenyl carbonate is preferable in view of reactivity, stability of the resulting resin with respect to coloring, and cost.

In the melt method, when an aromatic polycarbonate compound is produced, an end-capping terminal group can be introduced by using a carbonic acid diester in an excess amount relative to an aromatic dihydroxy compound. The aromatic polycarbonate compound of the present invention is preferably obtained by reacting an aromatic dihydroxy compound and a carbonic acid diester at a carbonic acid diester/aromatic dihydroxy compound ratio of 1.0 to 1.3 (molar ratio) in the presence of an ester exchange catalyst. That is, the carbonic acid diester is used in a proportion of 1.0 to 1.3 moles, more preferably 1.02 to 1.20 moles, based on 1 mole of the total of the aromatic dihydroxy compounds.

The melt polymerization method using a carbonic acid diester as a carbonate bond forming compound is carried out by a method of heating and stirring an aromatic dihydroxy component and a carbonic acid diester at a predetermined ratio in an inert gas atmosphere, and distilling off the produced alcohol or phenol. The reaction temperature varies depending on the boiling point of the alcohol or phenol to be produced, and is usually within a range of 120 to 350 ℃. The reaction was terminated by reducing the pressure from the initial stage and distilling off the formed alcohol or phenol. In order to promote the reaction, a transesterification catalyst such as a basic compound catalyst which is generally used may be used.

The basic compound catalyst may be, for example, an alkali metal compound and/or an alkaline earth metal compound, a nitrogen-containing compound, or a boron-containing compound.

As the alkali metal compound and/or alkaline earth metal compound, organic acid salts, inorganic salts, oxides, hydroxides, hydrides or alkoxides of alkali metals and alkaline earth metals, quaternary ammonium hydroxides, salts thereof, amines, and the like are preferably used, and these compounds may be used alone or in combination.

Specific examples of the alkali metal compound include sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium hydroxide, sodium hydrogen carbonate, sodium carbonate, potassium carbonate, cesium carbonate, lithium carbonate, sodium acetate, potassium acetate, cesium acetate, lithium acetate, sodium stearate, potassium stearate, cesium stearate, lithium stearate, sodium gluconate, sodium borohydride, sodium phenylboronate, sodium benzoate, potassium benzoate, cesium benzoate, lithium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, disodium phenyl phosphate, disodium salt, dipotassium salt, dicesium salt, dilithium salt, sodium salt, potassium salt, cesium salt, lithium salt, Ph salt, sodium salt, potassium salt, and the like₄BNa、N(CHCO₂Na)₃、PhNa₂PO₄And the like.

Specific examples of the alkaline earth metal compound include magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, magnesium hydrogen carbonate, calcium hydrogen carbonate, strontium hydrogen carbonate, barium hydrogen carbonate, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate, magnesium acetate, calcium acetate, strontium acetate, barium acetate, magnesium stearate, calcium benzoate, magnesium phenylphosphate, and the like.

Specific examples of the nitrogen-containing compound include quaternary ammonium hydroxides having an alkyl group and/or an aryl group such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide and trimethylbenzylammonium hydroxide, tertiary amines such as triethylamine, dimethylbenzylamine and triphenylamine, secondary amines such as diethylamine and dibutylamine, primary amines such as propylamine and butylamine, imidazoles such as 2-methylimidazole, 2-phenylimidazole and benzimidazole, and bases or basic salts such as ammonia, tetramethylammonium borohydride, tetrabutylammonium tetraphenylborate and ammonium tetraphenylborate.

Specific examples of the boron-containing compound include Et₄PB(OH)₄、Ph₄PBPh₄And the like.

These catalysts were used in a proportion of 1 × 10 relative to 1 mole of the total of dihydroxy compounds^-9～1×10^-3Molar, preferably 1 × 10^-7～1×10^-5And (3) mol.

The reaction temperature in the melting method is preferably in the range of 180 to 320 ℃, more preferably 180 to 310 ℃, and particularly preferably 180 to 300 ℃. The degree of pressure reduction is preferably 20kPaA (150 torr) or less, more preferably 13kPaA (100 torr) or less, still more preferably 1.3kPaA (10 torr) or less, and particularly preferably 0.67 to 0.013kPaA (5 to 0.1 torr). More specifically, the temperature is gradually raised from about 20kPaA (150 torr) to 180 ℃ and adjusted to a high vacuum state, and finally raised to 260 to 300 ℃ (more preferably 260 to 280 ℃) at 0.13kPaA (1 torr). The rapid temperature rise and high vacuum distillation may cause distillation of the carbonate bond forming compound (DPC) itself, and the appropriate reaction molar ratio may not be maintained, and the desired compound may not be obtained.

The aromatic polycarbonate compound of the present invention may have a structural viscosity index (N value) of 1.3 or less depending on the use thereof. That is, when the aromatic polycarbonate compound is reacted with an aliphatic diol compound to produce an aromatic polycarbonate resin having a high molecular weight and high fluidity and having no branched structure (a low N value), the N value of the aromatic polycarbonate compound is preferably 1.3 or less, more preferably 1.28 or less, and particularly preferably 1.25 or less. Here, the structural viscosity index "N value" is an index of the branching degree of the aromatic polycarbonate resin and is represented by the following formula (1).

N value (log (Q160 value) -log (Q10 value))/(log 160-log10) · (1)

In the above formula (I), Q160 represents a melt flow volume (ml/sec) per unit time measured at 280 ℃ under a load of 160kg (measured using CFT-500D manufactured by shimadzu corporation (the same applies hereinafter) and calculated from a stroke of 7.0 to 10.0 mm), and Q10 represents a melt flow volume (ml/sec) per unit time measured at 280 ℃ under a load of 10kg (calculated from a stroke of 7.0 to 10.0 mm) (wherein the nozzle diameter is 1mm × the nozzle length is 10 mm).

When the N value of the aromatic polycarbonate compound of the present invention is as low as 1.3 or less, the content ratio of the branched structure is small and the ratio of the linear structure is high. In general, although a polycarbonate resin tends to have a higher fluidity (a higher Q value) when the proportion of the branched structure is increased (when the N value is increased) at the same Mw, a polycarbonate copolymer having a high molecular weight obtained by reacting the aromatic polycarbonate compound of the present invention having such a characteristic with an aliphatic diol compound can realize a high fluidity (a high Q value) while maintaining the low N value.

On the other hand, the aromatic polycarbonate compound of the present invention may have an N value of more than 1.3 depending on the use thereof. That is, an aromatic polycarbonate compound having a branched structure with an N value of more than 1.3, preferably 1.31 to 2.0, more preferably 1.31 to 1.7 can be obtained by introducing a branched structure into the aromatic polycarbonate compound using a predetermined amount of a branching agent.

By using the aromatic polycarbonate compound of the present invention into which a branched structure has been introduced using a predetermined amount of the branching agent as a prepolymer and subjecting a specific aliphatic diol compound to an ester interchange reaction under reduced pressure, a branched aromatic polycarbonate resin having a high molecular weight and a desired degree of branching can be obtained under mild conditions in a short time.

(3) Aromatic polycarbonate prepolymer material

The aromatic polycarbonate compound of the present invention can be used as an aromatic polycarbonate prepolymer used in the production of a high molecular weight aromatic polycarbonate resin, the production of the high molecular weight aromatic polycarbonate resin comprising: and (3) subjecting the aromatic polycarbonate prepolymer and the aliphatic diol compound to an ester interchange reaction in the presence of an ester interchange catalyst under reduced pressure. That is, the aromatic polycarbonate prepolymer material mainly composed of the end-capped aromatic polycarbonate compound (prepolymer) of the present invention is subjected to an ester interchange reaction with an aliphatic diol compound (linking agent) to replace an end-capping terminal group (for example, a terminal phenyl group) derived from a carbonate bond-forming compound present in the prepolymer with an alcoholic hydroxyl group, whereby the linking reaction between the aromatic polycarbonate prepolymers rapidly proceeds, the molecular weight can be increased, and the molecular weight can be rapidly increased under mild conditions.

The prepolymer material for producing a high molecular weight aromatic polycarbonate resin mainly comprising the aromatic polycarbonate prepolymer of the present invention used for such applications preferably has a residual carbonate monomer content of 3000ppm or less, more preferably 2000ppm or less, and particularly preferably 1000ppm or less.

The method for adjusting the amount of the residual carbonate monomer to 3000ppm or less is not particularly limited, and a method of adjusting the amount of the carbonic acid diester to be added during the production (for example, an amount of not more than 1.3 moles, more preferably not more than 1.2 moles based on 1 mole of the total of the aromatic dihydroxy compounds), or selecting an appropriate reaction temperature (for example, 180 ℃ to 320 ℃) and a reduced pressure (for example, 150torr or less) may be employed.

When a material having a structural viscosity index (N value) of 1.25 or less is used as a prepolymer material for producing a high molecular weight aromatic polycarbonate resin, since the prepolymer contains a small proportion of branched structures and has a high proportion of linear structures, when the prepolymer material is reacted with an aliphatic diol compound to increase the molecular weight, an aromatic polycarbonate resin (polycarbonate copolymer) having a high molecular weight and high fluidity (high Q value) can be obtained while maintaining a low N value. The N value (structural viscosity index) of the obtained high molecular weight aromatic polycarbonate resin is preferably 1.3 or less, more preferably 1.28 or less, particularly preferably 1.25 or less, and there is no significant change in the N value with the aromatic polycarbonate compound (prepolymer).

On the other hand, when an aromatic polycarbonate compound having a branched structure in which the N value exceeds 1.25 is introduced is used as the aromatic polycarbonate compound of the present invention, a branched aromatic polycarbonate resin having a high molecular weight and a desired degree of branching corresponding to the amount of the used branching agent can be obtained in a short time under mild conditions by subjecting the aromatic polycarbonate compound to an ester exchange reaction with the aliphatic diol compound. In this case, the degree of branching (N value) of the branched aromatic polycarbonate resin obtained may be in the range of 1.31 to 2.2, more preferably in the range of 1.31 to 2.0, and particularly preferably in the range of 1.31 to 1.9.

Examples

The present invention will be described below with reference to examples, but the present invention is not limited to these examples at all. The measurement values in the examples were measured by the following methods and apparatuses.

1) Polystyrene-reduced weight average molecular weight (Mw): using GPC and chloroform as a developing solvent, a calibration curve was prepared using standard polystyrene having a known molecular weight (molecular weight distribution of 1). Based on the calibration curve, the retention time of GPC was calculated.

2) Glass transition temperature (Tg): the measurement was performed by a Differential Scanning Calorimetry (DSC).

3) Total terminal group amount (number of moles) of polymer): 0.25g of a resin sample was dissolved in 5ml of deuterated chloroform, and the resulting solution was analyzed by a nuclear magnetic resonance analyzer at 23 ℃¹The terminal group was measured by H-NMR (trade name "LA-500" available from Nippon electronics Co., Ltd.) and expressed in terms of the number of moles per 1ton of the polymer.

4) Hydroxyl end concentration (ppm): the determination was carried out by UV/visible light analysis (546 nm) of a complex formed from the polymer and titanium tetrachloride in a dichloromethane solution. Or, by¹As a result of H-NMR analysis, the terminal hydroxyl group was observed and measured.

5) Terminal phenyl concentration (terminal Ph concentration; mole percent): according to¹The analysis result of H-NMR was obtained by the following equation.

6) Resin hue (YI value): a resin sample (6 g) was dissolved in 60ml of methylene chloride, and the YI value was measured with a spectroscopic colorimeter (product of Nippon Denshoku industries Co., Ltd., trade name "SE-2000") in a cuvette having an optical path length of 6 cm.

7) Fluidity (Q value): the Q value is the flow rate (ml/sec) of the molten resin, and is evaluated by the melt flow volume per unit time measured at 280 ℃ under a load of 160kg after drying at 130 ℃ for 5 hours using a high rheometer CFT-500D (manufactured by Shimadzu corporation).

8) The value of N is: the melt flow volume per unit time measured at 280 ℃ under a load of 160kg was defined as Q160 value and the melt flow volume per unit time measured at 280 ℃ under a load of 10kg was defined as Q10 value for the aromatic polycarbonate (sample) dried at 130 ℃ for 5 hours using a rheometer of high viscosity CFT-500D (manufactured by Shimadzu corporation), and these values were determined from the following formula (1).

N value (log (Q160 value) -log (Q10 value))/(log 160-log10) · (1)

9) Ratio of the polymer compound having an i value of 1: the proportion of the polymer compound having a value of i (chain length of structural unit derived from aliphatic diol compound) of 1 in the general formula (III) is determined by the polycarbonate copolymer obtained¹H-NMR analysis results were obtained.

10) Amount of residual carbonate monomer (DPC) and residual phenol (PhOH): quantitation was performed by internal standard method using GPC (UV detector) or GC.

11) Cyclic carbonate content in resin: 10g of the resin sample was dissolved in 100ml of methylene chloride and added dropwise to 1000ml of methanol with stirring. The precipitate was collected by filtration, and the solvent was removed from the filtrate. The obtained solid was analyzed by GC-MS under the following measurement conditions. Wherein the limit value of detection under the measurement conditions was 0.0005 ppm.

GC-MS measurement conditions:

a measuring device: agilent HP6890/5973MSD

Column: capillary column (Capillary Columns) DB-5MS,30m × 0.25mm I.D., film thickness 0.5 μm

Temperature rising conditions are as follows: 50 deg.C (5 min) to 300 deg.C (15 min), 10 deg.C/min

Injection port temperature: 300 ℃, injection amount: 1.0 μ l (split ratio 25)

An ionization method: EI method

Carrier gas: he, 1.0ml/min

Aux temperature: 300 deg.C

Mass scan range: 33-700

Solvent: chloroform for HPLC

Internal standard substance: 1,3, 5-trihydroxymethyl phenol

12) Heat retention test of resin: a test tube was charged with 1g of the sample resin, and dried for 2 hours in a glove box (oxygen concentration 0.0%) substituted with nitrogen using a Heater (Block Heater) set to 120 ℃. Subsequently, the inside of the glove box was heated and retained for 50 minutes by a heater set at 360 ℃. The change amounts of the retention (%) of molecular weight (Mw) and YI value before and after the heat retention test were measured. The test is a test in which the maximum thermal history of the general molding temperature of polycarbonate is given, for example, precision molding in which the melt viscosity of the resin needs to be kept low. The long residence time of 50 minutes is the longest residence time that can be assumed in an actual molding site including a failure of the apparatus and the like.

13) Resin hue (YI value) before and after heat retention test: a resin sample (1 g) was dissolved in 60ml of methylene chloride, and the YI value was measured using a spectroscopic colorimeter (trade name "SE-2000" manufactured by Nippon Denshoku industries Co., Ltd.) in a cuvette having an optical path length of 6 cm.

The chemical purity of the aliphatic diol compounds used in the following examples and comparative examples was 98 to 99%, the chlorine content was 0.8ppm or less, and the contents of alkali metals, alkaline earth metals, titanium, and heavy metals (iron, nickel, chromium, zinc, copper, manganese, cobalt, molybdenum, and tin) were 1ppm or less, respectively. The chemical purity of the aromatic dihydroxy compound and the carbonic acid diester is 99% or more, the chlorine content is 0.8ppm or less, and the contents of alkali metal, alkaline earth metal, titanium and heavy metal (iron, nickel, chromium, zinc, copper, manganese, cobalt, molybdenum, tin) are 1ppm or less, respectively.

In the following examples, the prepolymer is abbreviated as "PP", the hydroxyl group is abbreviated as "OH group", and the phenyl group is abbreviated as "Ph" in some cases.

< example 1 >

10,000g (43.80 mol) of 2, 2-bis (4-hydroxyphenyl) propane, 10,581g (49.39 mol) of diphenyl carbonate and 1. mu. mol/mol of sodium hydrogencarbonate as a catalyst (the catalyst was calculated in terms of the number of moles based on 2, 2-bis (4-hydroxyphenyl) propane) were charged into a 50L SUS reactor equipped with a stirrer and a distillation apparatus, and the inside of the system was replaced with a nitrogen atmosphere. The reduced pressure was adjusted to 27kPaA (200 torr), and the raw materials were heated and melted at 200 ℃ and stirred for 30 minutes.

Thereafter, phenol distilled out of the reaction system was aggregated in a cooling tube over 4 hours and removed, and the system was kept at 260 ℃ under a reduced pressure of 0.13kPaA (1 torr) or less for 1 hour to conduct an ester exchange reaction.

Next, 396g (0.90 mol) of molten 9, 9-bis [4- (2-hydroxyethoxy) phenyl ] fluorene (hereinafter, abbreviated as "BPEF") was added as an aliphatic diol compound while maintaining the system at 280 ℃ and a reduced pressure of 0.13kPaA (1 torr) or less for 20 minutes, and the mixture was stirred and kneaded for 30 minutes to continue the transesterification reaction. A polycarbonate copolymer having a weight average molecular weight (Mw) of 55,000 was obtained.

Of the polycarbonate copolymer obtained¹The results of H-NMR analysis are shown in FIG. 1 (¹H-NMR spectrum A) and FIG. 2 (¹H-NMR spectrum B). In fig. 1, the peak derived from the aliphatic diol compound (methylene chain portion of BPEF) is enlarged, and the peak derived from the structural unit of the aliphatic diol compound is confirmed. The methylene chain of the BPEF monomer has a signal around 3.9ppm, but is significantly displaced to a different position due to reaction with the aromatic dihydroxy compound. Of these, 4.8ppm is a peak of an aromatic OH group.

From these peaks, it was confirmed that a structure composed of an aromatic polycarbonate chain and an aliphatic diol moiety was obtained. The strongest 2 peaks are the structure in which BPEF is bonded to the aromatic polycarbonate chain, and the adjacent weak 2 peaks represent the structure in which BPEF is bonded to each other by a carbonate bond (block copolymerization).

Further, from fig. 2, the peak of the phenyl moiety of BPEF was confirmed, and thus the structure formed by the aromatic polycarbonate chain and the aliphatic diol moiety was also confirmed.

Namely, it can be seen that: the polycarbonate copolymer obtained here consists essentially of a copolymer having the general formula (II) described aboveI) Wherein the chain length of the structural unit derived from the aliphatic diol compound is 1 (i is 1) (a structure comprising an aromatic polycarbonate chain and 1 structural unit derived from the aliphatic diol compound). From the above¹As a result of H-NMR analysis, the proportion of the polymer compound having a structure in which the i value is 1 was 98 mol% based on the total amount of the polycarbonate copolymer.

In the obtained polycarbonate copolymer, the proportion of the structural unit derived from the aliphatic diol compound (the structural unit represented by the general formula (I)) was 1.7 mol%, and the proportion of the structural unit derived from the aromatic dihydroxy compound (the structural unit represented by the general formula (II)) was 98 mol%. The Q160 value was 0.17 ml/s, and satisfied the formula (2) representing the relationship between Mw and Q value. And the N value (structural viscosity index) was 1.21.

The physical property values of the obtained polycarbonate copolymer are shown in Table 1. The flexural elastic modulus (GPa) and the flexural strength (MPa) are values measured by a bending test according to JIS-K7171, the tensile elastic modulus (GPa), the tensile yield strength (MPa), the tensile yield elongation (%), and the tensile break strength (MPa) are values measured by a tensile test according to JIS-K7113, and the Izod impact strength (kg. cm/cm) is a value measured by a test according to JIS-K7110.

< examples 2 and 3 >

An experiment was carried out in the same manner as in example 1, except that the kind and the amount of the aliphatic diol were changed as shown in table 1. The evaluation results are shown in table 1.

< production example of prepolymer 1; PP-A >

10,000g (43.80 mol) of 2, 2-bis (4-hydroxyphenyl) propane, 10,558g (49.39 mol) of diphenyl carbonate and 1. mu. mol/mol of sodium hydrogencarbonate as a catalyst (the catalyst was calculated in terms of the number of moles based on 2, 2-bis (4-hydroxyphenyl) propane) were charged into a 50L SUS reactor equipped with a stirrer and a distillation apparatus, and the inside of the system was replaced with a nitrogen atmosphere. The reduced pressure was adjusted to 27kPaA (200 torr), and the raw materials were heated and melted at 200 ℃ and stirred for 30 minutes.

Thereafter, phenol distilled out of the reaction system was aggregated in a cooling tube over 4 hours and removed, and the system was subjected to transesterification reaction at 260 ℃ under a reduced pressure of 0.13kPaA (1 torr) or less and further kept for 1 hour. A polycarbonate prepolymer (hereinafter referred to as "PP-A") having ｃA weight average molecular weight (Mw) of 24,000 was obtained.

The OH concentration (ppm) and the phenyl terminal concentration (Ph terminal concentration, mol%) of the polycarbonate prepolymer obtained are shown in Table 2. In Table 2, OH concentration is a value calculated by NMR and represents the concentration of OH groups contained in the whole polymer. The Ph end concentration is a value calculated by NMR and represents the end concentration of all phenylene groups and phenyl groups (including phenyl groups substituted with hydroxyl groups) in the phenyl ends.

< production example 2 of prepolymer; PP-B >

2, 2-bis (4-hydroxyphenyl) propane 9,995g (43.78 mol), diphenyl carbonate 10,321g (48.18 mol) and sodium hydrogencarbonate as a catalyst in an amount of 1. mu. mol/mol (catalyst in terms of moles based on 2, 2-bis (4-hydroxyphenyl) propane) were charged into a 50L SUS reactor equipped with a stirrer and a distillation apparatus, and the inside of the system was replaced with a nitrogen atmosphere. The reduced pressure was adjusted to 27kPaA (200 torr), and the raw materials were heated and melted at 200 ℃ and stirred for 30 minutes.

Thereafter, phenol distilled out of the reaction system was aggregated in a cooling tube over 4 hours and removed, and the system was subjected to transesterification reaction at 260 ℃ under a reduced pressure of 0.13kPaA (1 torr) or less and further kept for 2 hours. A polycarbonate prepolymer ("PP-B") having a weight average molecular weight (Mw) of 33,000 was obtained.

The OH concentration (ppm) and the phenyl terminal concentration (Ph terminal concentration, mol%) of the polycarbonate prepolymer obtained are shown in Table 2. Wherein the Ph end concentration is a value calculated by NMR and represents the concentration of all phenylene groups and phenyl groups at the phenyl ends.

< production example 3 of prepolymer; PP-C >

125.00g (0.548 mol) of 2, 2-bis (4-hydroxyphenyl) propane and 0.3g of sodium dithionite were dissolved in 730 ml of an 8 mass% aqueous solution of sodium hydroxide. 300 ml of methylene chloride was added thereto, and while stirring and maintaining the temperature at 15 ℃, 70.50g (0.713 mol) of phosgene was blown in for 15 minutes.

After the phosgene blowing was completed, 5.16g (0.055 mol) of phenol as a molecular weight modifier was added, and 130 ml of an 8 mass% aqueous solution of sodium hydroxide was added to emulsify the reaction mixture by vigorous stirring, and then 0.60 ml of triethylamine was added and stirred at 20 to 25 ℃ for about 1 hour to polymerize the mixture. After completion of the polymerization, the reaction solution was separated into an aqueous phase and an organic phase, and the organic phase was neutralized with phosphoric acid and then washed with water. The resulting polymer solution was added dropwise to warm water maintained at 50 ℃ to evaporate the solvent and simultaneously crush the solid to obtain a white powdery precipitate. The resulting precipitate was filtered and dried at 120 ℃ for 24 hours to obtain a polymer powder (hereinafter, sometimes referred to as "PP-C").

< example 4 >

10g of an aromatic polycarbonate prepolymer (PP-A obtained in production example 1 of the above prepolymer) was charged into ｃA 300cc four-necked flask equipped with ｃA stirrer and ｃA distillation apparatus, and heated and melted at 280 ℃ under vacuum. Subsequently, 0.33g of 9, 9-bis [4- (2-hydroxyethoxy) phenyl ] fluorene (BPEF) as an aliphatic diol compound was added thereto, and the mixture was kneaded under stirring at a jacket temperature of 280 ℃ and a pressure of 0.04kPaA (0.3 torr) for 60 minutes to effect transesterification. As the catalyst, a polymerization catalyst used in the polymerization of an aromatic polycarbonate prepolymer was used as it is.

Phenol distilled out of the reaction system was agglomerated in a cooling tube and removed from the reaction system, and a polycarbonate copolymer was obtained in which the weight average molecular weight (Mw) was 37,000, the Q value was 0.400, and the proportion of the polymer compound having an i value of 1 (the proportion of the aliphatic diol skeleton having a structure in which an i value was 1) was 96 mol%, and the N value was 1.22. The results are shown in Table 3.

< examples 5 to 15 >

An experiment was carried out in the same manner as in example 4 except that the aromatic polycarbonate prepolymer and the aliphatic diol compound were replaced with those shown in table 3. In the system using PP-C, sodium hydrogencarbonate was added in an amount of 1. mu. mol/mol (the catalyst was calculated as the number of moles per 2, 2-bis (4-hydroxyphenyl) propane unit) as a catalyst. The results are shown in Table 3.

< comparative example 1 >

10,000g (43.80 mol) of 2, 2-bis (4-hydroxyphenyl) propane, 10,000g (46.68 mol) of diphenyl carbonate and 1. mu. mol/mol of sodium hydrogencarbonate as a catalyst (the catalyst was calculated in terms of the number of moles based on 2, 2-bis (4-hydroxyphenyl) propane) were charged into a 50L SUS reactor equipped with a stirrer and a distillation apparatus, and the inside of the system was replaced with a nitrogen atmosphere. The reduced pressure was adjusted to 27kPaA (200 torr), and the raw materials were heated and melted at 200 ℃ and stirred for 30 minutes.

Thereafter, phenol distilled out of the reaction system was aggregated in a cooling tube over 4 hours and removed, and the system was subjected to transesterification reaction at 260 ℃ under a reduced pressure of 0.13kPaA (1 torr) or less, and further kept for 7 hours. About 10kg of an aromatic polycarbonate having a weight average molecular weight (Mw) of 63,000 and a hydroxyl end concentration of 700ppm was obtained. The physical property values of the obtained polycarbonate are shown in Table 1.

< comparative example 2 >

In 40 liters of a 5 mass% aqueous sodium hydroxide solution, 3634g (15.92 moles) of 2, 2-bis (4-hydroxyphenyl) propane and 30g of sodium dithionite were dissolved. To this, 17 liters of methylene chloride was added and stirred, and 2100g (21.23 moles) of phosgene was blown in for 15 minutes while maintaining the temperature at 15 ℃. After the phosgene blowing was completed, 99.91g (0.67 mol) of p-tert-butylphenol as a molecular weight regulator was added, 10L of a 5 mass% aqueous solution of sodium hydroxide and 20L of methylene chloride were added, and the mixture was stirred vigorously to emulsify the reaction mixture, and then 20 mL of triethylamine was added and stirred at 20 to 25 ℃ for about 1 hour to polymerize the mixture. After completion of the polymerization, the reaction solution was separated into an aqueous phase and an organic phase, and the organic phase was neutralized with phosphoric acid and then washed with water. The resulting polymer solution was added dropwise to warm water maintained at 50 ℃ to evaporate the solvent and simultaneously crush the solid to obtain a white powdery precipitate. The resulting precipitate was filtered and dried at 120 ℃ for 24 hours to obtain a polymer powder.

< comparative example 3 >

The procedure of comparative example 2 was repeated, except that the amount of p-tert-butylphenol was changed to 78.86g (0.52 mol). The physical property values of the obtained polycarbonate are shown in Table 1.

< comparative example 4 >

50.96g (0.2232 moles) of 2, 2-bis (4-hydroxyphenyl) propane, 49.04g (0.229 moles) of diphenyl carbonate and 1. mu. mol/mol of sodium hydrogencarbonate as a catalyst (the catalyst was calculated in terms of moles per mole of 2, 2-bis (4-hydroxyphenyl) propane) were charged in a 300cc four-necked flask equipped with a stirrer and a distillation apparatus, heated to 180 ℃ under a nitrogen atmosphere and stirred for 30 minutes.

Then, the pressure was adjusted to 20kPaA (150 torr), and the temperature was raised to 200 ℃ at a rate of 60 ℃/hr, and the temperature was maintained for 40 minutes to carry out the transesterification reaction. Then, the temperature was increased to 225 ℃ at a rate of 75 ℃/hr, and the temperature was maintained for 10 minutes. Subsequently, the temperature was raised to 260 ℃ at a rate of 65 ℃/hr, and the reduced pressure was reduced to 0.13kPaA (1 torr) or less for 1 hour, and the reaction mixture was held for another 6 hours. 30g of an aromatic polycarbonate having a weight average molecular weight (Mw) of 44,000 was obtained. The evaluation results of the physical properties of the obtained polycarbonate are shown in Table 4.

< comparative example 5 >

50.98g (0.2233 moles) of 2, 2-bis (4-hydroxyphenyl) propane, 49.04g (0.229 moles) of diphenyl carbonate and 1. mu. mol/mol of sodium hydrogencarbonate as a catalyst (the catalyst was calculated in terms of moles per mole of 2, 2-bis (4-hydroxyphenyl) propane) were charged into a 300cc four-necked flask equipped with a stirrer and a distillation apparatus, heated to 180 ℃ under a nitrogen atmosphere and stirred for 30 minutes.

Then, the pressure was adjusted to 20kPaA (150 torr), and the temperature was raised to 200 ℃ at a rate of 60 ℃/hr, and the temperature was maintained for 40 minutes to carry out the transesterification reaction. Then, the temperature was increased to 225 ℃ at a rate of 75 ℃/hr, and the temperature was maintained for 10 minutes. Subsequently, the temperature was raised to 260 ℃ at a rate of 65 ℃/hr, and the reduced pressure was maintained at 0.13kPaA (1 torr) or less for 1 hour, and further for 7 hours. 30g of an aromatic polycarbonate having a weight average molecular weight (Mw) of 50,000 was obtained. The evaluation results of the physical properties of the obtained polycarbonate are shown in Table 4.

[ Table 1]

[ Table 2]

	PP-A	PP-B	PP-C
				BPA（_g）	10000	9995.1
BPA（mol）	43.80	43.78
				DPC（g）	10558	10321
DPC（mol）	49.29	48.18
				DPC/BPA molar ratio	1.13	1.10
Mw	24000	33000	22000
				OH concentration (ppm)	181	73	73
Ph end concentration (mol%)	7.3	5.1	7.8

[ Table 3]

[ Table 4]

	Comparative example 4	Comparative example 5
			BPA（g）	50.96	50.98
BPA（mol）	0.2232	0.2233
			DPC（g）	49.04	49.04
DPC（mol）	0.229	0.229
			DPC/BPA molar ratio	1.03	1.03
Connecting agent	－	－
			Formula and amount of bonding agent	－	－
Interlink dosage (g)	－	－
			Interlinking dosage (mol)	－	－
Mw	44000	50000
			Q value [ ml/s]160kg	0.1264	0.0788
Value of N	1.30	1.31

< production example 4 of prepolymer; PP-D >

10,000.6g (43.81 mol) of 2, 2-bis (4-hydroxyphenyl) propane, 10,560.0g (49.30 mol) of diphenyl carbonate and 0.5. mu. mol/mol of cesium carbonate as a catalyst (the catalyst was calculated in terms of the number of moles based on 2, 2-bis (4-hydroxyphenyl) propane) were charged into a 50L SUS reactor equipped with a stirrer and a distillation apparatus, and the inside of the system was replaced with a nitrogen atmosphere. The reduced pressure was adjusted to 27kPaA (200 torr), and the raw materials were heated and melted at 200 ℃ and stirred for 30 minutes.

Thereafter, phenol distilled out of the reaction system was coagulated and removed in a cooling tube for 4 hours, and ester exchange reaction was carried out so that the pressure in the system was 260 ℃ and the reduced pressure was 0.13kPaA (1 torr) or less, and further the system was maintained for 1 hour. A polycarbonate prepolymer (hereinafter referred to as "PP-D") having a weight average molecular weight (Mw) of 22,000 was obtained.

The OH concentration (ppm) and the phenyl terminal concentration (Ph terminal concentration, mol%) of the polycarbonate prepolymer obtained are shown in Table 5. In Table 5, OH concentration is a value calculated by NMR and indicates the concentration of OH groups contained in the whole polymer. The Ph end concentration is a value calculated by NMR and represents the end concentration of all phenylene groups and phenyl groups (including phenyl groups substituted with hydroxyl groups) in the phenyl ends.

< example 16 >

30g of the aromatic polycarbonate prepolymer "PP-D" obtained in production example 4 of the above prepolymer was charged into a 300cc four-necked flask equipped with a stirrer and a distillation apparatus, and heated and melted at 280 ℃ under normal pressure. Next, 0.22g of 1, 4-Cyclohexanedimethanol (CHDM) was added as an aliphatic diol compound, and the mixture was stirred and kneaded at a jacket temperature of 280 ℃ under normal pressure for 1 minute. Then, the mixture was kneaded under stirring at a pressure of 0.04kPaA (0.3 torr) for 45 minutes to effect transesterification. As the catalyst, a polymerization catalyst used in the polymerization of an aromatic polycarbonate prepolymer was used as it is.

Phenol distilled out of the reaction system was agglomerated in a cooling tube and removed from the reaction system, and a polycarbonate copolymer was obtained in which the weight average molecular weight (Mw) was 48,000, the Q value was 0.1294, and the ratio of the polymer compounds having an i value of 1 (the ratio of the aliphatic diol skeleton having a structure having an i value of 1) was 100 mol%, and the N value was 1.22. The results are shown in Table 6.

< example 17 >

30g of an aromatic polycarbonate prepolymer (PP-D obtained in production example 4 of the above prepolymer) was charged into a 300cc four-necked flask equipped with a stirrer and a distillation apparatus, and heated and melted at 300 ℃ under normal pressure. Next, 0.22g of 1, 4-Cyclohexanedimethanol (CHDM) was added as an aliphatic diol compound, and the mixture was kneaded under normal pressure at a jacket temperature of 300 ℃ for 15 minutes. Then, the mixture was kneaded under stirring at a pressure of 0.04kPaA (0.3 torr) for 45 minutes to effect transesterification. As the catalyst, a polymerization catalyst used in the polymerization of an aromatic polycarbonate prepolymer was used as it is.

Phenol distilled out of the reaction system was agglomerated by a cooling tube and removed from the reaction system, and a polycarbonate copolymer was obtained in which the weight average molecular weight (Mw) was 65,000, the Q value was 0.0305, and the proportion of the polymer compound having an i value of 1 (the proportion of the aliphatic diol skeleton having a structure in which an i value is 1) was 100 mol%, and the N value was 1.20. The results are shown in Table 6.

< example 18 >

30g of an aromatic polycarbonate prepolymer (PP-D obtained in production example 4 of the above prepolymer) was charged into a 300cc four-necked flask equipped with a stirrer and a distillation apparatus, and heated and melted at 300 ℃ under normal pressure. Next, 0.30g of decalin-2, 6-dimethanol (DDM) was added as an aliphatic diol compound, and the mixture was kneaded at a jacket temperature of 300 ℃ under normal pressure for 15 minutes. Then, the mixture was kneaded under stirring at a pressure of 0.04kPaA (0.3 torr) for 30 minutes to effect transesterification. As the catalyst, a polymerization catalyst used in the polymerization of an aromatic polycarbonate prepolymer was used as it is.

Phenol distilled out of the reaction system was agglomerated in a cooling tube and removed from the reaction system, and a polycarbonate copolymer was obtained in which the weight average molecular weight (Mw) was 66,000, the Q value was 0.0319, and the ratio of the polymer compounds having an i value of 1 (the ratio of the aliphatic diol skeleton having a structure having an i value of 1) was 100 mol%, and the N value was 1.19. The results are shown in Table 6.

< example 19 >

30g of an aromatic polycarbonate prepolymer (PP-D obtained in production example 4 of the above prepolymer) was charged into a 300cc four-necked flask equipped with a stirrer and a distillation apparatus, and heated and melted at 280 ℃ under normal pressure. Next, 0.30g of decalin-2, 6-dimethanol (DDM) was added as an aliphatic diol compound, and the mixture was kneaded at a jacket temperature of 280 ℃ under normal pressure for 1 minute. Then, the mixture was kneaded under stirring at a pressure of 0.04kPaA (0.3 torr) for 55 minutes to effect transesterification. As the catalyst, a polymerization catalyst used in the polymerization of an aromatic polycarbonate prepolymer was used as it is.

Phenol distilled out of the reaction system was aggregated in a cooling tube and removed from the reaction system, thereby obtaining a polycarbonate copolymer having a weight average molecular weight (Mw) of 61,000, a Q value of 0.0440, and a ratio of a polymer compound having an i value of 1 (a ratio of an aliphatic diol skeleton having a structure having an i value of 1) of 100 mol%, and an N value of 1.17. The results are shown in Table 6.

[ Table 5]

	PP-D
		BPA（g）	10000.6
BPA（mol）	43.81
		DPC（g）	10560
DPC（mol）	49.30
		DPC/BPA molar ratio	1.13
Mw	22000
		OH concentration (ppm)	60
Ph end concentration (mol%)	5.0

[ Table 6]

FIG. 3 is a graph showing the relationship between Mw and Q value (measured at 280 ℃ under a load of 160 kg) of the polycarbonates obtained in the above examples and comparative examples. Therefore, the following steps are carried out: the polycarbonate copolymer of the present invention tends to have higher fluidity than the conventional known polycarbonate resins even when the molecular weight is the same.

In the graph of FIG. 3, the polycarbonate copolymers (examples 1to 19) of the present invention are represented by ■ (black squares). The fluidity was higher than that of the polycarbonate obtained by the interfacial method (comparative examples 2 and 3) (. smallcircle.) and the polycarbonate obtained by the ordinary melt method (comparative examples 1,4, and 5) (. DELTA.) which did not have a structure derived from the aliphatic diol moiety of the aliphatic diol compound.

FIG. 4 is a graph showing the relationship between Mw and N value of the polycarbonates obtained in the above examples and comparative examples. As is clear from the relationship between Mw and N in FIG. 4, the polycarbonate copolymer of the present invention has a significantly low N value and a very small proportion of branched structures even when it is produced by a melt process.

< example 20 >

30.13g of the aromatic polycarbonate prepolymer "PP-D" obtained in production example 4 of the above prepolymer was charged into a 300cc four-necked flask equipped with a stirrer and a distillation apparatus, and heated and melted at 280 ℃. Subsequently, 0.34g of 2-butyl-2-ethylpropane-1, 3-diol (BEPD) as an aliphatic diol compound was added under normal pressure at a jacket temperature of 280 ℃ and kneaded for 3 minutes with stirring.

Then, the mixture was kneaded under stirring at a jacket temperature of 280 ℃ and a pressure of 0.04kPaA (0.3 torr) for 70 minutes to effect transesterification. As the catalyst, a polymerization catalyst used in the polymerization of an aromatic polycarbonate prepolymer was used as it is.

Phenol distilled out of the reaction system, cyclic carbonate (5-butyl-5-ethyl-1, 3-dioxane-2-one) and unreacted 2-butyl-2-ethylpropane-1, 3-diol (BEPD) were aggregated in a cooling tube and removed from the reaction system to obtain a polycarbonate resin having a weight average molecular weight (Mw) of 56,400 and an N value of 1.19 and containing 154ppm of cyclic carbonate (5-butyl-5-ethyl-1, 3-dioxane-2-one).

1g of the obtained resin was put into a test tube, and dried in a glove box (oxygen concentration 0.0%) substituted with nitrogen for 2 hours with a heater set to 120 ℃. Subsequently, the inside of the glove box was heated and retained for 50 minutes by a heater set at 360 ℃.

As a result, the retention (%) of the molecular weight (Mw) before and after the retention test was 98%, and the variation of YI value was + 5.0.

Adding BEPD, of the mixture at the end of stirring¹The H-NMR spectrum is shown in FIG. 5, and the final polycarbonate resin¹The H-NMR spectrum is shown in FIG. 6. In FIG. 5, the peaks derived from BEPD after the reaction with the aromatic polycarbonate prepolymer and the unreacted BEPD monomer were observedPeak(s). On the other hand, in fig. 6, the peak from BEPD after the reaction and the peak of unreacted BEPD monomer disappeared.

It is understood that the aromatic polycarbonate resin obtained here is a homopolycarbonate having no structural unit derived from the aliphatic diol compound, and the added aliphatic diol is excluded from the reaction system in the form of a cyclic carbonate upon reaction with the aromatic polycarbonate prepolymer.

< examples 21 to 26 >

A polycarbonate resin was obtained in the same manner as in example 20, except that the amount of the aromatic polycarbonate prepolymer added, the aliphatic diol compound used, and the amount added were changed as shown in table 7. The physical properties of the obtained polycarbonate resin are shown in table 7.

< comparative example 6 >

Using the same aromatic polycarbonate prepolymer as in example 20, the reaction was carried out in a short time as in example 20 except that the aliphatic diol compound was not added, and Mw was not increased to 22000 and the molecular weight was not increased.

[ Table 7]

As shown in examples 20 to 26, the proportion (number of moles) of the structural unit derived from the aliphatic diol compound in the finally obtained resin was significantly reduced as compared with the proportion (number of moles) at the end of the addition and kneading of the aliphatic diol compound. According to the method for producing an aliphatic diol compound having a structure represented by the general formulae (g1) to (g4) in the present invention, the proportion (number of moles) of structural units derived from the aliphatic diol compound in the finally obtained resin is 50% or less, preferably 40% or less, more preferably 30% or less, particularly preferably 20% or less, and most preferably 10% or less, relative to the proportion (number of moles) at the end of addition and kneading of the aliphatic diol compound.

From the results of examples 20 to 26 described above, it is clear that: the high molecular weight polycarbonate resin obtained by the method for producing an aliphatic diol compound having a structure represented by the general formulae (g1) to (g4) of the present invention, which is close to a homopolycarbonate resin, has high thermal stability, and has a high retention of molecular weight (Mw) and a low change in YI value before and after a very severe heat retention test of 360 to 50 minutes.

The thermal stability of the polycarbonate copolymers obtained in examples 1to 3 was measured in the same manner, and the results are shown below. In comparison with the results, it is found that: the high-molecular-weight polycarbonate resin obtained by the method for producing the aliphatic diol compound having the structure represented by the general formulae (g1) to (g4) according to the present invention has extremely excellent thermal stability. In addition, when the polycarbonate having a high molecular weight obtained by the conventional melting method of comparative example 1 was used and subjected to the heat retention test in the same manner, gelation occurred, and it was difficult to evaluate various physical properties.

(example 1)

Mw before 360-50 min retention test: 55000

Mw after 360-50 min retention test: 21400

Mw retention (%) after 360-50 min retention test; 39

YI value before 360-50 min retention test; 1.0

YI value after 360-50 minutes retention test; 58.0

The change amount of YI value after the retention test for 360-50 minutes; 57.0

(example 2)

Mw before 360-50 min retention test; 68000

Mw after 360-50 min retention test; 28000

Mw retention (%) after 360-50 min retention test; 41

YI value before 360-50 min retention test; 1.6

YI value after 360-50 minutes retention test; 60.0

The change amount of YI value after the retention test for 360-50 minutes; 58.4

(example 3)

Mw before 360-50 min retention test; 48000

Mw after 360-50 min retention test; 23000

Mw retention (%) after 360-50 min retention test; 48

YI value before 360-50 min retention test; 1.0

YI value after 360-50 minutes retention test; 65.0

The change amount of YI value after the retention test for 360-50 minutes; 64.0

< example 27 >

50.000g (0.219 mol) of 2, 2-bis (4-hydroxyphenyl) propane, 48.091g (0.224 mol) of diphenyl carbonate and 1. mu. mol/mol of sodium hydrogencarbonate as a catalyst (the catalyst was calculated in terms of moles per mole of 2, 2-bis (4-hydroxyphenyl) propane) were charged in a 500cc four-necked flask equipped with a stirrer and a distillation apparatus, heated to 180 ℃ under a nitrogen atmosphere and stirred for 30 minutes.

Then, the pressure was adjusted to 20kPaA (150 torr), and the temperature was raised to 200 ℃ at a rate of 60 ℃/hr, and the temperature was maintained for 40 minutes to carry out the transesterification reaction. Then, the temperature was raised to 225 ℃ at a rate of 75 ℃/hr, and the temperature was maintained at this temperature for 10 minutes. Subsequently, the temperature was raised to 260 ℃ at a rate of 65 ℃/hr, and the reduced pressure was reduced to 0.13kPaA (1 torr) or less for 1 hour, and the reaction mixture was held for 40 minutes. 50g of an aromatic polycarbonate compound (prepolymer for producing an aromatic polycarbonate resin, hereinafter, may be referred to simply as "aromatic polycarbonate prepolymer" or "PP") having a weight average molecular weight (Mw) of 29,000 was obtained.

The aromatic polycarbonate prepolymer thus obtained had a terminal hydroxyl group concentration of 1500ppm, a terminal phenyl group concentration of 3.5 mol% and an N value (structural viscosity index) of 1.23. The results are shown in Table 1.

10g of the above aromatic polycarbonate prepolymer was charged into a 300cc four-necked flask equipped with a stirrer and a distillation apparatus, and heated and melted at 280 ℃ under vacuum. Subsequently, 0.153g of 9, 9-bis [4- (2-hydroxyethoxy) phenyl ] fluorene (BPEF) was added as an aliphatic diol compound, and the mixture was kneaded under stirring at a jacket temperature of 280 ℃ and a pressure of 0.04kPaA (0.3 torr) for 30 minutes to perform a transesterification reaction. As the catalyst, a polymerization catalyst used in the polymerization of an aromatic polycarbonate prepolymer was used as it is.

Phenol distilled out of the reaction system was agglomerated in a cooling tube and removed from the reaction system to obtain a polycarbonate copolymer having a weight average molecular weight (Mw) of 60,000. The results are shown in Table 8. < examples 28 to 31 >

An experiment was carried out in the same manner as in example 27 except that the amounts of 2, 2-bis (4-hydroxyphenyl) propane and diphenyl carbonate used, and the types and amounts of aliphatic diol used were changed as shown in table 1. The results are shown in Table 8.

< example 32 >

10,000g (43.8 mol) of 2, 2-bis (4-hydroxyphenyl) propane, 10,322g (48.2 mol) of diphenyl carbonate and 3. mu. mol/mol of sodium hydrogencarbonate as a catalyst (the catalyst was calculated based on the number of moles of 2, 2-bis (4-hydroxyphenyl) propane) were charged into a 50L SUS reactor equipped with a stirrer and a distillation apparatus, and the inside of the system was replaced with a nitrogen atmosphere. The reduced pressure was adjusted to 27kPaA (200 torr), and the raw materials were heated and melted at 200 ℃ and stirred for 30 minutes.

Thereafter, phenol distilled out of the reaction system was coagulated in a cooling tube for 4 hours to remove it, and ester exchange reaction was carried out so that the pressure in the system was 260 ℃ and the reduced pressure was 0.13kPaA (1 torr) or less, and further held for 1 hour. An aromatic polycarbonate prepolymer having a weight average molecular weight (Mw) of 23,000 was obtained.

The aromatic polycarbonate prepolymer thus obtained had a terminal hydroxyl group concentration of 500ppm, a terminal phenyl group concentration of 6.6 mol% and an N value (structural viscosity index) of 1.20. The results are shown in Table 1. Wherein, in Table 8, the terminal hydroxyl group concentration is based on¹The H-NMR value was calculated and represents the concentration of OH groups contained in the whole polymer. In addition, the concentration of the terminal phenyl group is based on¹The value calculated by H-NMR indicates the concentration of terminal phenyl groups in all phenylene groups and phenyl terminal groups.

10g of the above aromatic polycarbonate prepolymer was charged into a 300cc four-necked flask equipped with a stirrer and a distillation apparatus, and heated and melted at 280 ℃ under vacuum. Subsequently, 0.33g of 9, 9-bis [4- (2-hydroxyethoxy) phenyl ] fluorene (BPEF) was added as an aliphatic diol compound, and the mixture was kneaded under stirring at a jacket temperature of 280 ℃ and a pressure of 0.04kPaA (0.3 torr) for 15 minutes to perform a transesterification reaction. As the catalyst, a polymerization catalyst used in the polymerization of an aromatic polycarbonate prepolymer was used as it is.

Phenol distilled out of the reaction system was agglomerated in a cooling tube and removed from the reaction system to obtain a polycarbonate copolymer having a weight average molecular weight (Mw) of 50,000. The results are shown in Table 8. < examples 33 to 36 >

An experiment was carried out in the same manner as in example 32, except that the amounts of 2, 2-bis (4-hydroxyphenyl) propane and diphenyl carbonate used, and the types and amounts of aliphatic diol used were changed as shown in table 8. The results are shown in Table 8.

Preparation of the aromatic polycarbonate prepolymer obtained in example 34¹The results of H-NMR analysis are shown in FIG. 7. In fig. 7, the peaks of phenyl and phenylene groups from the polycarbonate resin are enlarged. Peaks from the phenyl end groups were identified. The phenylene group of the 2, 2-bis (4-hydroxyphenyl) propane unit has a signal at 7.0 to 7.3ppm and is derived from the phenyl end groupThe peak has a signal around 7.4 ppm. The concentration of the terminal phenyl group was calculated from the signal intensity ratio.

< example 37 >

50.000g (0.219 mol) of 2, 2-bis (4-hydroxyphenyl) propane, 49.000g (0.229 mol) of diphenyl carbonate, 0.210g (0.00069 mol) of 1,1, 1-triphenylphenylethane (hereinafter, sometimes referred to simply as "TPE"), and 3. mu. mol/mol of sodium hydrogencarbonate as a catalyst were charged into a 500cc four-necked flask equipped with a stirrer and a distillation apparatus, heated to 180 ℃ under a nitrogen atmosphere, and stirred for 30 minutes.

Then, the pressure was adjusted to 20kPa (150 torr), and the temperature was raised to 200 ℃ at a rate of 60 ℃/hr, and the temperature was maintained for 40 minutes to carry out the transesterification reaction. Then, the temperature was raised to 225 ℃ at a rate of 75 ℃/hr, and the temperature was maintained at this temperature for 10 minutes. Subsequently, the temperature was raised to 260 ℃ at a rate of 65 ℃/hr, and the reduced pressure was reduced to 0.13kPaA (1 torr) or less over 1 hour. 50g of an aromatic polycarbonate prepolymer having a weight-average molecular weight (Mw) of 27,000 was obtained.

The aromatic polycarbonate prepolymer had a terminal hydroxyl group concentration of 480ppm, a terminal phenyl group concentration of 7.3 mol%, and an N value (structural viscosity index) of 1.31. The results are shown in Table 9. Wherein, in Table 9, the terminal hydroxyl group concentration is based on¹The H-NMR value was calculated and represents the concentration of hydroxyl groups (OH groups) contained in the whole polymer. In addition, the concentration of the terminal phenyl group is based on¹The value calculated by H-NMR indicates the concentration of the terminal phenyl group in all the phenylene groups and the phenyl terminals.

10g of the above aromatic polycarbonate prepolymer was charged into a 300cc four-necked flask equipped with a stirrer and a distillation apparatus, and heated and melted at 290 ℃ under vacuum. Then, 0.328g (2.1 mmol) of 9, 9-bis [4- (2-hydroxyethoxy) phenyl ] fluorene was added thereto, and the mixture was kneaded for 15 minutes with stirring at a jacket temperature of 290 ℃ under a pressure of 0.04kPa (0.3 torr). Phenol distilled out from the reaction system was condensed in a cooling tube and removed from the reaction system. As a result, the weight average molecular weight (Mw) of the obtained aromatic polycarbonate resin was 55,000. The physical property values of the obtained polymer are shown in table 9.

< example 38 >

An experiment was carried out in the same manner as in example 37 except that the amounts of 2, 2-bis (4-hydroxyphenyl) propane, diphenyl carbonate, 1,1, 1-triphenylolethane and the aliphatic diol to be used were changed to those shown in table 9. The results are shown in Table 9.

< comparative example 7 >

An experiment was carried out in the same manner as in example 32, except that the amounts of 2, 2-bis (4-hydroxyphenyl) propane and diphenyl carbonate used, the types of aliphatic diol and the amounts thereof used were changed as shown in table 8. The results are shown in Table 8. Since the concentration of terminal hydroxyl groups in the product is high and the concentration of terminal phenyl groups is low, the aromatic polycarbonate resin has not been sufficiently increased in molecular weight.

< comparative example 8 >

An experiment was carried out in the same manner as in example 37 except that the amounts of 2, 2-bis (4-hydroxyphenyl) propane, 1,1, 1-triphenylolethane, diphenyl carbonate and aliphatic diol to be used were changed as shown in table 9. The results are shown in Table 9. Since the concentration of terminal hydroxyl groups in the product is high and the concentration of terminal phenyl groups is low, the aromatic polycarbonate resin has not been sufficiently increased in molecular weight.

[ Table 8]

[ Table 9]

Wherein the symbols in tables 1to 9 represent the following meanings.

PP: aromatic polycarbonate compound (prepolymer)

BPA: 2, 2-bis (4-hydroxyphenyl) propane

DPC: carbonic acid diphenyl ester

TPE: 1,1, 1-Triphenolethane

And BPEF: 9, 9-bis [4- (2-hydroxyethoxy) phenyl ] fluorene (boiling point: about 625 deg.C)

BPA-2 EO: 2, 2' -bis [4- (2-hydroxyethoxy) phenyl ] propane (boiling point: about 480 ℃ C.)

BP-2 EO: 4,4' -bis (2-hydroxyethoxy) biphenyl (boiling point: about 430 ℃ C.)

PCPDM: pentacyclopentadecane dimethanol (boiling point: about 420 ℃ C.)

FG: fluorene diol (boiling point: about 370 ℃ C.)

CHDM: 1, 4-cyclohexanedimethanol (boiling point: about 283 ℃ C.)

DDM: decalin-2, 6-dimethanol (boiling point: about 341 ℃ C.)

BEPD: 2-butyl-2-ethylpropane-1, 3-diol

DIBPD: 2, 2-diisobutylpropane-1, 3-diol

EMPD: 2-Ethyl-2-methylpropane-1, 3-diol

DEPD: 2, 2-diethylpropane-1, 3-diol

MPPD: 2-methyl-2-propylpropane-1, 3-diol

NPG-DI: bis (3-hydroxy-2, 2-dimethylpropyl) carbonate

1, 2-PD: propane-1, 2-diol

Industrial applicability

The novel polycarbonate copolymer of the present invention has the following characteristics: the physical properties of the polycarbonate by the conventional interfacial method can be maintained without using other resins, additives, etc., and the fluidity is improved despite the high molecular weight. Moreover, the resin composition can be produced by a simple production method without requiring specific production conditions.

The high-fluidity polycarbonate copolymer of the present invention has advantages such as a fast molding cycle and a low molding temperature when used as a substitute for conventional general-purpose polycarbonate resins or compositions, and can be preferably used for various applications such as various molded articles, sheets, and films obtained by various injection molding, blow molding, extrusion molding, injection blow molding, rotational molding, compression molding, and the like. Further, since the use of electric power is saved, it is expected to reduce the burden on the natural environment and the production cost of the molded article, and it can be said that the resin is excellent in economy and environmentally friendly to the natural environment.

Further, according to the method for producing a high molecular weight aromatic polycarbonate resin using an aliphatic diol compound having a structure represented by the general formulae (g1) to (g4) of the present invention, a polycarbonate resin having not only a high molecular weight but also high fluidity, excellent quality, a structure similar to that of a product produced by the interfacial method, and good heat resistance can be obtained by removing the cyclic carbonate produced as a by-product from the reaction system.

The high molecular weight aromatic polycarbonate resin of the present invention obtained by the above method has advantages such as a short molding cycle and a low molding temperature when used as a substitute for conventional general-purpose polycarbonate resins or compositions, as with the above polycarbonate copolymer, and can be suitably used for various applications such as various molded articles, sheets, films and the like obtained by various injection molding, blow molding, extrusion molding, injection blow molding, rotational molding, compression molding and the like. Further, since the use of electric power is saved, it is expected to reduce the burden on the natural environment and the production cost of the molded article, and it can be said that the resin is excellent in economy and environmentally friendly to the natural environment. In particular, even when the polycarbonate is subjected to the maximum thermal history at a usual molding temperature for a long time, it shows extremely excellent thermal stability such as a high retention of molecular weight (Mw) (for example, 70% or more) and a small change in YI value (for example, + 25 or less). Therefore, it is particularly preferable for precision molding or the like which requires a low melt viscosity of the resin.

The novel aromatic polycarbonate compound of the present invention has specific terminal physical properties, and is particularly suitable as a prepolymer material for producing a polycarbonate resin by an ester exchange reaction with a specific aliphatic diol compound having an aliphatic hydrocarbon group bonded to a terminal hydroxyl group.

By subjecting the aromatic polycarbonate compound of the present invention and a specific aliphatic diol compound to an ester interchange reaction, it is possible to achieve a sufficient high molecular weight of the aromatic polycarbonate resin by a simple method while maintaining good quality of the aromatic polycarbonate resin. In particular, a polycarbonate copolymer having a high molecular weight, but high fluidity, and containing no branched structure can be produced without using an additive or the like. On the other hand, if a branching structure is introduced into the aromatic polycarbonate compound by using a predetermined amount of the branching agent, an aromatic polycarbonate resin having a desired branching degree can be easily produced.

Claims

1. A high flow polycarbonate copolymer characterized by:

substantially comprises a structural unit represented by the following general formula (I) and a structural unit represented by the following general formula (II), wherein the structural unit represented by the following general formula (I) is derived from an aliphatic diol compound having an aliphatic hydrocarbon group bonded to a terminal hydroxyl group,

the high-fluidity polycarbonate copolymer satisfies the following conditions (a) to (d),

in the general formula (I), Q represents a hydrocarbon group having 3 or more carbon atoms which may contain a hetero atom, and R₁～R₄Each independently represents a group selected from a hydrogen atom, an aliphatic hydrocarbon group having 1to 30 carbon atoms and an aromatic hydrocarbon group having 1to 30 carbon atoms, n and m each independently represents an integer of 0to 10, wherein in the case where Q does not include an aliphatic hydrocarbon group bonded to a terminal hydroxyl group, n and m each independently represent an integer of 1to 10, and R₁And R₂And R₃And R₄At least one of which is independently selected from a hydrogen atom and an aliphatic hydrocarbon group,

in the general formula (II), R₁And R₂Independently represents a halogen atom, an alkyl group having 1to 20 carbon atoms, an alkoxy group having 1to 20 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms or an aryloxy group having 6 to 20 carbon atoms, p and q represent an integer of 0to 4, X represents only a valence bond or a group selected from divalent organic groups represented by the following general formula (II'),

in the formula (II'), R₃And R₄Each independently represents a hydrogen atom, an alkyl group having 1to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, R₃And R₄Can be combined to form an aliphatic ring,

(a) has a structure represented by the following general formula (III),

in the general formula (III), k represents an integer of 4 or more, i represents an integer of 1 or more, l represents an integer of 1 or more, k' represents an integer of 0 or 1, R represents a linear or branched hydrocarbon group, a phenyl group which may contain fluorine, or a hydrogen atom, wherein 70% by weight or more of the total amount of the copolymer is i ═ 1,

(b) the proportion of the structural unit represented by the general formula (I) is 1to 30 mol%, the proportion of the structural unit represented by the general formula (II) is 99 to 70 mol%, based on the total amount of the structural units constituting the polycarbonate copolymer,

(c) the index of fluidity is 0.02 to 1.0ml/s in Q value measured at 280 ℃ under a load of 160kg,

(d) the weight average molecular weight (Mw) is 30,000-100,000.

2. The high flow polycarbonate copolymer of claim 1, wherein:

an N value representing a structural viscosity index represented by the following numerical formula (1) is 1.25 or less, wherein N is (log (Q160 value) -log (Q10 value))/(log 160-log 10.· (1)),

in the above formula (1), Q160 value represents the melt flow volume ml/sec per unit time measured at 280 ℃ under a load of 160kg, and Q10 value represents the melt flow volume ml/sec per unit time measured at 280 ℃ under a load of 10 kg.

3. The high flow polycarbonate copolymer of claim 1, wherein: the Mw and Q values satisfy the following formula (2),

4.61×EXP(－0.0000785×Mw)<Q(ml/s)···(2)。

4. the high flow polycarbonate copolymer of claim 1, wherein:

the Mw and Q values satisfy the following formula (3),

4.61×EXP(－0.0000785×Mw)<Q(ml/s)<2.30×EXP(－0.0000310×Mw)···(3)。

5. the high flow polycarbonate copolymer of claim 1, wherein:

the aliphatic diol compound from which the structural unit represented by the general formula (I) is derived is a compound represented by the following general formula (A),

HO－(CR₁R₂)_n－Q－(CR₃R₄)_m－OH···(A)

in the general formula (A), Q represents a hydrocarbon group having 3 or more carbon atoms which may contain a hetero atom, and R₁、R₂、R₃And R₄Each independently represents a group selected from a hydrogen atom, an aliphatic hydrocarbon group having 1to 30 carbon atoms and an aromatic hydrocarbon group having 6 to 20 carbon atoms, n and m each independently represents an integer of 0to 10, wherein in the case where Q does not include an aliphatic hydrocarbon group bonded to a terminal hydroxyl group, n and m each independently represent an integer of 1to 10, and R₁And R₂And R₃And R₄At least one of which is independently selected from a hydrogen atom and an aliphatic hydrocarbon group.

6. The high flow polycarbonate copolymer of claim 5, wherein:

the aliphatic diol compound is a compound shown in the following general formula (i),

HO－(CR₁R₂)_n1－Q₁－(CR₃R₄)_m1－OH···(i)

in the general formula (i), Q₁Represents a C6-40 hydrocarbon group containing an aromatic ring, R₁、R₂、R₃And R₄Each independently represents a group selected from a hydrogen atom, an aliphatic hydrocarbon group having 1to 30 carbon atoms, and an aromatic hydrocarbon group having 6 to 20 carbon atoms, and n1 and m1 each independently represents an integer of 1to 10.

7. The high flow polycarbonate copolymer of claim 6, wherein:

the aliphatic diol compound is selected from 4,4 '-bis (2-hydroxyethoxy) biphenyl, 2' -bis [ (2-hydroxyethoxy) phenyl ] propane, 9-bis [4- (2-hydroxyethoxy) phenyl ] fluorene, 9-bis (hydroxymethyl) fluorene and 9, 9-bis (hydroxyethyl) fluorene.

8. The high flow polycarbonate copolymer of claim 5, wherein:

the aliphatic diol compound is a compound represented by the following general formula (ii),

HO－(CR₁R₂)_n2－Q₂－(CR₃R₄)_m2－OH···(ii)

in the general formula (ii), Q₂Represents a straight-chain or branched-chain hydrocarbon group having 3to 40 carbon atoms which may contain a heterocycle, R₁、R₂、R₃And R₄Each independently represents a group selected from a hydrogen atom, an aliphatic hydrocarbon group having 1to 30 carbon atoms, and an aromatic hydrocarbon group having 6 to 20 carbon atoms, and n2 and m2 each independently represents an integer of 0to 10.

9. The high flow polycarbonate copolymer of claim 8, wherein:

said Q₂Represents a C6-40 chain aliphatic hydrocarbon group having a branched chain without a heterocyclic ring.

10. The high flow polycarbonate copolymer of claim 9, wherein:

the aliphatic diol compound is selected from 2-butyl-2-ethyl propane-1, 3-diol, 2-diisobutyl propane-1, 3-diol, 2-ethyl-2-methyl propane-1, 3-diol, 2-diethyl propane-1, 3-diol and 2-methyl-2-propyl propane-1, 3-diol.

11. The high flow polycarbonate copolymer of claim 5, wherein:

the aliphatic diol compound is a compound represented by the following general formula (iii),

HO－(CR₁R₂)_n3－Q₃－(CR₃R₄)_m3－OH···(iii)

in the general formula (iii), Q₃R represents a cyclic hydrocarbon group having 6 to 40 carbon atoms₁、R₂、R₃And R₄Each independently represents a group selected from a hydrogen atom, an aliphatic hydrocarbon group having 1to 30 carbon atoms, and an aromatic hydrocarbon group having 6 to 20 carbon atoms, and n3 and m3 each independently represents an integer of 0to 10.

12. The high flow polycarbonate copolymer of claim 11, wherein:

the aliphatic diol compound is at least one compound selected from pentacyclopentadecane dimethanol, 1, 4-cyclohexane dimethanol, 1, 3-adamantane dimethanol, decalin-2, 6-dimethanol and tricyclodecane dimethanol.

13. The high flow polycarbonate copolymer of any of claims 5-12, wherein:

the boiling point of the aliphatic diol compound is 240 ℃ or higher.

14. A molded body, characterized in that:

the polycarbonate copolymer of claim 1, which is molded by a molding method selected from the group consisting of injection molding, blow molding, extrusion molding, injection blow molding, rotational molding and compression molding.

15. A molded body, characterized in that:

selected from the group consisting of sheets and films comprising the polycarbonate copolymer of claim 1.

16. A method for producing an aromatic polycarbonate resin having a high molecular weight, comprising:

comprises a step of increasing the molecular weight of an aromatic polycarbonate by transesterification with an aliphatic diol compound represented by the general formula (g1) in the presence of a transesterification catalyst,

in the general formula (g1), Ra and Rb each independently represent a hydrogen atom, a linear or branched alkyl group having 1to 12 carbon atoms, or a phenyl group, and m represents an integer of 1to 30.

17. The manufacturing method according to claim 16, wherein:

m in the general formula (g1) is an integer of 2-8.

18. The manufacturing method according to claim 16, wherein:

the aliphatic diol compound represented by the general formula (g1) is a compound represented by the general formula (g2),

in the general formula (g2), Ra and Rb each independently represent a hydrogen atom, a linear or branched alkyl group having 1to 12 carbon atoms, or a phenyl group, and n represents an integer of 1to 28.

19. The manufacturing method according to claim 18, wherein:

n in the general formula (g2) is an integer of 1to 6.

20. The manufacturing method according to claim 18, wherein:

the aliphatic diol compound represented by the general formula (g2) is a compound represented by the general formula (g3),

in the general formula (g3), Ra and Rb each independently represent a hydrogen atom, a linear or branched alkyl group having 1to 12 carbon atoms, or a phenyl group.

21. The manufacturing method according to claim 20, wherein:

in the general formula (g3), Ra and Rb each independently represent a hydrogen atom or a linear or branched alkyl group having 1to 5 carbon atoms.

22. The manufacturing method according to claim 20, wherein:

in the general formula (g3), Ra and Rb each independently represent a linear or branched alkyl group having 1to 4 carbon atoms.

23. The method for producing a high molecular weight aromatic polycarbonate resin according to claim 22, wherein:

24. A method for producing an aromatic polycarbonate resin having a high molecular weight, comprising:

comprises a step of increasing the molecular weight of an aromatic polycarbonate by transesterification with an aliphatic diol compound represented by the general formula (g4) in the presence of a transesterification catalyst,

in the general formula (g4), R represents a divalent hydrocarbon group selected from the structures represented by the following formulas, n represents an integer of 1to 20,

25. the manufacturing method according to claim 24, wherein:

in the general formula (g4), R is- (CH)₂)_mA divalent hydrocarbon group represented by-or-CH₂－C(CH₃)₂－CH₂Wherein m is an integer of 3to 20, and n is 1to 3.

26. The manufacturing method according to claim 16 or 24, comprising:

a high molecular weight increasing step of reacting an aromatic polycarbonate with an aliphatic diol compound in the presence of an ester exchange catalyst to increase the molecular weight; and

a cyclic carbonate removal step of removing at least a part of the cyclic carbonate produced as a by-product in the high molecular weight increasing step from the reaction system.

27. The method of manufacturing of claim 26, wherein:

the cyclic carbonate is a compound represented by the following general formula (h1)

In the general formula (h1), Ra and Rb each independently represent a hydrogen atom, a linear or branched alkyl group having 1to 12 carbon atoms, or a phenyl group, and m represents an integer of 1to 30.

28. The method of manufacturing of claim 27, wherein:

m in the general formula (h1) is an integer of 2-8.

29. The method of manufacturing of claim 27, wherein:

the cyclic carbonate represented by the general formula (h1) is a compound represented by the following general formula (h2),

in the general formula (h2), Ra and Rb each independently represent a hydrogen atom, a linear or branched alkyl group having 1to 12 carbon atoms, or a phenyl group, and n represents an integer of 1to 28.

30. The method of manufacturing of claim 29, wherein:

n in the general formula (h2) is an integer of 1-6.

31. The method of manufacturing of claim 29, wherein:

the cyclic carbonate represented by the general formula (h2) is a compound represented by the following general formula (h3),

in the general formula (h3), Ra and Rb each independently represent a hydrogen atom, a linear or branched alkyl group having 1to 12 carbon atoms, or a phenyl group.

32. The method of manufacturing of claim 31, wherein:

in the general formula (h3), Ra and Rb each independently represent a hydrogen atom or a linear alkyl group having 1to 5 carbon atoms.

33. The manufacturing method according to claim 16 or 24, wherein:

the amount of the aliphatic diol compound used is 0.01 to 1.0 mole per 1 mole of the total amount of the terminal ends of the aromatic polycarbonate before the reaction in the step of increasing the molecular weight.

34. The manufacturing method according to claim 16 or 24, wherein:

at least a part of the aromatic polycarbonate before the reaction in the step of increasing the molecular weight is capped.

35. The manufacturing method according to claim 16 or 24, wherein:

the aromatic polycarbonate before the reaction in the high molecular weight increasing step is an end-capped prepolymer obtained by a reaction of an aromatic dihydroxy compound and a carbonic acid diester.

36. The manufacturing method according to claim 16 or 24, wherein:

the concentration of the hydroxyl terminal groups of the aromatic polycarbonate before the reaction in the step of increasing the molecular weight is 1,500ppm or less.

37. The manufacturing method according to claim 16 or 24, wherein:

the weight average molecular weight Mw of the aromatic polycarbonate resin having undergone the high molecular weight after the reaction in the high molecular weight increasing step is higher than the weight average molecular weight Mw of the aromatic polycarbonate resin before the reaction in the high molecular weight increasing step by 5,000 or more.

38. The manufacturing method according to claim 16 or 24, wherein:

the weight average molecular weight Mw of the aromatic polycarbonate before the reaction in the step of increasing the molecular weight is 5,000 to 60,000.

39. A polycarbonate resin composition characterized by:

which mainly comprises the aromatic polycarbonate resin having a high molecular weight produced by the production method according to claim 16 or 24 and which contains 3000ppm or less of a cyclic carbonate represented by the following general formula (h1),

40. The polycarbonate resin composition of claim 39, wherein:

m in the general formula (h1) is an integer of 2-8.

41. The polycarbonate resin composition of claim 39, wherein:

42. The polycarbonate resin composition of claim 41, wherein:

n in the general formula (h2) is an integer of 1-6.

43. The polycarbonate resin composition of claim 41, wherein:

44. The polycarbonate resin composition of claim 43, wherein:

45. The polycarbonate resin composition of claim 39, wherein:

the aromatic polycarbonate resin having a high molecular weight has an N value of 1.25 or less which is represented by the following formula (1),

n value (log (Q160 value) -log (Q10 value))/(log 160-log10) · (1),