KR100676300B1 - Process for producing polyester carbonate resin - Google Patents

Abstract

The present invention relates to a method for producing a high molecular weight polyester carbonate resin, and more particularly, transesterification of an aromatic dihydroxy compound and a carbonic acid diester compound and ester reaction of an aromatic dihydroxy compound and a dicarboxylic acid compound. As a process for producing a high molecular weight polyester carbonate resin comprising a condensation polymerization, crystallization and solid phase polymerization step,

By introducing the condensation polymerization, the molar fraction of allyl carbonates present in the end groups of the reaction by-products less than 3 and the unreacted diaryl carbonate obtained as a result of the transesterification can be maximized to maximize the molecular weight increase of the polyester carbonate after the solid phase polymerization. In addition, it is possible to significantly shorten the time required to prepare the polyester carbonate of the same molecular weight, it is possible to provide a polyester carbonate with improved color and reactivity by using a tin-based catalyst.

Polyester carbonate, transesterification, condensation polymerization, crystallization, solid state polymerization

Description

Method for preparing polyester carbonate resin {Method for preparing poly (carbonate-co-ester) resin}

The present invention provides a low molecular weight polyester carbonate by transesterification of an aromatic dihydroxy compound with a carbonic acid diester compound and an ester reaction of an aromatic dihydroxy compound with a dicarboxylic acid compound to form a low molecular weight polyester carbonate and The present invention relates to a method of preparing a high molecular weight polyester carbonate through a solid phase polymerization after forming a polyester carbonate having a high molecular weight through the condensation polymerization step of the ester carbonate.

Polycarbonate resins are very excellent in heat resistance, impact resistance, mechanical strength, transparency, and the like, and are widely used in the manufacture of compact discs, transparent sheets, packaging materials, automobile bumpers, and sunscreen films, and the demand is rapidly increasing.

However, when exposed to a conventional polycarbonate solvent, there is a problem in that the solvent resistance is poor, such as exhibiting a crazing or cracking phenomenon, and low impact strength at low temperatures. Therefore, various modified polycarbonates have been attempted to improve this problem, and polyester carbonates are particularly useful thermoplastic resins having excellent transparency and high impact resistance.

Conventional production processes in the production of such polyester carbonates include an interfacial polymerization step using phosgene and melt condensation polymerization without phosgene.

Interfacial polymerization processes are disclosed for the reaction of aromatic dihydroxy compounds, such as bisphenol-A, phosgene and dicarboxylic acids, as described in US Pat. No. 4,983,706. Since the method uses harmful chemicals, phosgene, and chlorine-based organic solvents that are harmful to the environment, there is a problem that the risk is very high and accordingly, a huge equipment cost is required.

As an example using a melt polymerization process, the transesterification reaction of an aromatic dihydroxy compound with a carbonic acid diester compound and the ester reaction of an aromatic dihydroxy compound with a dicarboxylic acid compound in US Pat. Disclosed is a method of producing a polyester carbonate by melt polymerization after a step of simultaneously occurring with an ammonium salt catalyst. The method has the advantage of low risk because it does not use toxic materials, but in order to produce a high amount of extruded polyester carbonate, a high-temperature, high-vacuum facility is required when treating high-viscosity reactants, thereby degrading the quality. There is a problem.

Therefore, there is no risk, it is possible to prevent the deterioration of quality, and a situation for further research on a manufacturing method capable of economically manufacturing high molecular weight polyester carbonate in a short time is required.

 In order to solve the above problems, the first technical problem is to introduce a reduced pressure condensation reaction step to shorten the reaction time of the solid phase polymerization reaction step, and to improve the color and reactivity of the polyester carbonate by using a tin-based catalyst It is to provide a manufacturing method.

The second technical problem of the present invention is to provide a polyester carbonate produced by the above method.

In order to achieve the first task,

In the present invention, a) ester reaction of a dicarboxylic acid compound and an aromatic dihydroxy compound and a transesterification reaction of a carbonic acid diester compound and an aromatic dihydroxy compound are simultaneously carried out under a catalyst such that the number average molecular weight is 1,500 to 15,000 g / mol. Preparing a phosphorus low molecular weight amorphous polyester carbonate prepolymer;

b) condensation polymerization of the low molecular weight amorphous polyester carbonate prepolymer of step a) to produce a medium molecular weight amorphous polyester carbonate having a number average molecular weight of 3,000 to 20,000 g / mol;

c) preparing a crystalline polyester carbonate from the medium molecular weight amorphous polyester carbonate of step b); And

d) a process for producing a high molecular weight polyester carbonate resin comprising the step of solid-phase polymerizing the crystalline polyester carbonate of step c) to produce a high molecular weight polyester carbonate having a number average molecular weight of 15,000 to 200,000 g / mol To provide.

In order to achieve the second task,

The present invention provides a polyester carbonate prepared by the above method.

Hereinafter, the present invention will be described in detail.

While the present inventors have been studying a method for greatly improving the molecular weight of polyester carbonate within a short time, the polymerization degree obtained as a result of the transesterification reaction by introducing a reaction step of condensation polymerization at a constant reaction temperature under reduced pressure or nitrogen injection, By lowering the mole fraction of the aryl carbonates present in the end groups of the reaction by-products and the unreacted diaryl carbonates, the molecular weight of the polyester carbonates can be maximized after solid phase polymerization, and the time required to prepare polyester carbonates having the same molecular weight The present invention has been completed by discovering that the present invention can be significantly shortened.

First step: transesterification and ester reaction

As the polymerization catalyst used in the transesterification and ester reaction of the present invention, a tin-based catalyst may be used.

The tin-based catalyst is selected from the group consisting of dialkyltin trichloride, dialkyltin dichloride, dialkyltin oxide, dialkyltin dialkoxide, dialkyltin dicarboxylate, and tetraalkyl tin. In this case, the alkyl has 1 to 20 carbon atoms, preferably 1 to 10, more preferably 1 to 6 carbon atoms.                     

Preferred tin catalysts are compounds represented by the following formulas,

Most preferred is dibutyltin oxide.

Particularly, the tin-based catalyst is preferable, and when the tin-based catalyst is used, there are advantages in color, transparency, and reactivity compared to the conventional alkaline earth metal catalyst, quaternary ammonium salt catalyst, and antimony catalyst.

The catalyst is preferably included in the range of 10 ^-1 to 10 ^-6 moles, more preferably 10 ^-2 to 10 ^-5 moles with respect to 1 mole of the dihydroxy compound used as a starting raw material of the transesterification reaction of the present invention. It intended to include, and most preferably comprises 10 ^-3 to 10 ^-4 mol. If the content is less than ^10-6 moles, the catalytic activity can not be sufficiently exhibited at the beginning of the reaction, if the content is larger than ^10-1 mole there is a problem that it is uneconomic.

As the dicarboxylic acid compound which is one of the starting raw materials of the present invention, a compound represented by the following Chemical Formula 1 may be used:

[Formula 1]

HOOC--R ^One --COOH

In Formula 1, R ¹ is a substituted or unsubstituted aryl group having 4 to 30 carbon atoms, an alkyl group having 1 to 10 carbon atoms, or a cycloalkyl group having 5 to 30 carbon atoms.

Examples of the dicarboxylic acid compounds include 1,10-decanedicarboxylic acid, oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, sebacic acid, decandiionic acid, dodecanedioic acid, terephthalic acid and isophthalic acid. And combinations thereof.

Most preferred as the dicarboxylic acid compound is 1,10-decanedicarboxylic acid.

As the aromatic dihydroxy compound, a compound represented by Chemical Formula 2 may be used:

[Formula 2]

In Chemical Formula 2,

R ² and R ³ are each independently a halogen atom or an alkyl group having 1 to 8 carbon atoms; Each independently halogen atom such as fluorine, chlorine, bromine or iodine or methyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, secondary-butyl group, tert-butyl group, pentyl group, An alkyl group having 1 to 8 carbon atoms, such as a hexyl group, a cyclohexyl group, a heptyl group, or an octyl group,

Z is a single bond or an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, -S, -SO-,- SO _2- , -O-, -CO-, a compound represented by the following formula (2) or a compound represented by the following formula (3). At this time, the alkylene group having 1 to 8 carbon atoms or the alkylidene group having 2 to 8 carbon atoms include methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, ethylidine group, isopropylidene group, and the like. , A cycloalkylene group having 5 to 15 carbon atoms or a cycloalkylidene group having 5 to 15 carbon atoms includes a cyclopentyl group, a cyclohexylene group, a cyclopentylidene group, a cyclohexylidene group, and the like:

a and b are each independently an integer of 0 to 4;

 [Formula 3]

[Formula 4]

Examples of the aromatic dihydroxy compound represented by Formula 2 include bis (4-hydroxyphenyl) methane, bis (3-methyl-4-hydroxyphenyl) methane and bis (3-chloro-4-hydroxyphenyl) methane , Bis (3,5-dibromo-4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (2-tert-butyl-4-hydroxy -3-methylphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (2 -Methyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 1,1-bis (2-tert-butyl-4-hydroxy-5 -Methylphenyl) propane, 2,2-bis (3-chloro-4-hydroxyphenyl) propane, 2,2-bis (3-fluoro-4-hydroxyphenyl) propane, 2,2-bis (3- Bromo-4-hydroxyphenyl) propane, 2,2-bis (3,5-difluoro-4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl Propane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) prop Ropan, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, 2,2-bis (4-hydroxyphenyl) phenylmethane, 2,2-bis (4-hydroxy-1-methylphenyl) propane, 1,1-bis (4-hydroxy-tert-butylphenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy -3-chlorophenyl) propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane , 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (3-bromo-4-hydroxy-5-chlorophenyl) propane, 2,2- Bis (3-phenyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (3-methyl-4-hydroxyphenyl) butane, 1,1- Bis (2-butyl-4-hydroxy-5-methylphenyl) butane, 1,1-bis (2-tert-butyl-4-hydroxy-5-methylphenyl) butane, 1,1-bis (2-3 Class 4-hydroxy-5-methylphenyl) isobutane, 1,1-bis (2-tert-amyl-4-hydroxy-5-methylphenyl) butane, 2,2-bis (3,5-dichloro-4 -Hydroxyphenyl) butane, 2,2-bis (3,5-dibromo-4-hydrophenyl) butane, 4,4-bis (4-hydroxyphenyl) heptane, 1,1-bis (2- Bis (hydroxyaryl) such as tert-butyl-4-hydroxy-5-methylphenyl) heptane, 2,2-bis (4-hydroxyphenyl) octane, or 1,1- (4-hydroxyphenyl) ethane Alkane; 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (3-methyl-4-hydroxyphenyl) cyclohexane, 1 , 1-bis (3-cyclohexyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (3-phenyl-4-hydroxyphenyl) cyclohexane, or 1,1-bis (4-hydroxyphenyl Bis (hydroxyaryl) cycloalkanes such as) -3,5,5-trimethylcyclohexane; Bis (hydroxyaryl) ethers such as bis (4-hydroxyphenyl) ether or bis (4-hydroxy-3-methylphenyl) ether; Bis (hydroxyaryl) sulfides such as bis (4-hydroxyphenyl) sulfide or bis (3-methyl-4-hydroxyphenyl) sulfide; Bis (hydroxyaryl) sulfoxides such as bis (hydroxyphenyl) sulfoxide, bis (3-methyl-4-hydroxyphenyl) sulfoxide, or bis (3-phenyl-4-hydroxyphenyl) sulfoxide; Bis (hydroxyaryl) sulfones such as bis (4-hydroxyphenyl) sulfone, bis (3-methyl-4-hydroxyphenyl) sulfone, or bis (3-phenyl-4-hydroxyphenyl) sulfone; Or 4,4'-dihydroxyphenyl, 4,4'-dihydroxy-2,2'-dimethylbiphenyl, 4,4'-dihydroxy-3,3'-dimethylbiphenyl, 4, Dihydroxybiphenyl, such as 4'- dihydroxy-3,3'- dicyclohexyl biphenyl or 3, 3- difluoro-4,4'- dihydroxy biphenyl, can be used.

Aromatic dihydroxy compounds usable in addition to the compound represented by Formula 1 include dihydroxybenzene, halogen, or alkyl-substituted dihydroxybenzene, and examples thereof include resorcinol and 3-methylresorci Knoll, 3-Ethyl Resorcinol, 3-Proplysorcinol, 3-butyl Resorcinol, 3-tert-butyl Resorcinol, 3-Phenyl Resorcinol, 3-Cumolesor Sinol, 2,3,4,6-tetrafluororesorcinol, 2,3,4,6-tetrabromoresorcinol, catechol, hydroquinone, 3-methylhydroquinone, 3-ethylhydro Quinone, 3-propylhydroquinone, 3-butylhydroquinone, tert-butylhydroquinone, 3-phenylhydroquinone, 3-cumylhydroquinone, 2,5-dichlorohydroquinone, 2,3,5,6 Tetramethylhydroquinone, 2,3,5,6-tetra-tert-butylhydroquinone, 2,3,5,6-tetrafluorohydroquinone, or 2,3,5,6-tetrabromohydro Quinones and the like.

Bisphenol A is most preferred as an aromatic dihydroxy compound which is a starting material used in the present invention.

As the diaryl carbonate, which is one of the starting raw materials used in the transesterification reaction, a compound represented by the following Chemical Formula 4 or a compound represented by the following Chemical Formula 5 may be used:                     

[Formula 5]

In Chemical Formula 5,

Ar ¹ and Ar ² are each independently an aryl group,

[Formula 6]

In Chemical Formula 6,

Ar ³ and Ar ⁴ are each independently an aryl group,

D ¹ is a residue obtained by removing two hydroxyl groups from the aromatic dihydroxy compound represented by the formula (1).

Examples of the diaryl carbonate represented by Chemical Formula 5 or Chemical Formula 6 include diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, bis (m-cresyl) carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, Or bisphenol A-bisphenol carbonate.

Diphenyl carbonate is most preferred as the diallyl carbonate, which is the starting raw material used in the transesterification reaction of the present invention.

The dicarboxylic acid compound is preferably contained in 1 to (10 ^-4 ) mole with respect to 1 mole of the diaryl carbonate compound. More preferably 0.5 to 10 ^-3 moles, most preferably 0.1 to 0.05 moles. If the content is less than 10 ^-4 mol or greater than 1 mol, it is not possible to secure the physical properties of the differentiated polyester carbonate.

The diaryl carbonate is preferably included in 1.0 to 1.5 moles with respect to 1 mole of the dihydroxy compound. More preferably, it is 1.0-1.3 mol, Most preferably, it is 1.0-1.2 mol. When the content is less than 1.0 mole or larger than 1.5 mole, the degree of polymerization is low by the following formula, which is not preferable.

[Equation 1]

Wherein r is the molar ratio of hydroxy compound groups to carbonate groups, X _n is the degree of polymerization and p is the extent of reaction. In this case, when the reaction degree p has a value of 1.0, Equation 1 can be represented by the following Equation 2, and by adjusting r to a value close to 1.0, the polymerization degree can be maximized within a short time.

 [Equation 2]

In the production of the polycarbonate resin through the transesterification reaction of the present invention, additives such as terminal stoppers and antioxidants may be further used as necessary.

The terminating agent is on-butylphenol, mn-butylphenol, pn-butylphenol, o-isobutylphenol, m-isobutylphenol, p-isobutylphenol, o-tert-butylphenol, m-tertiary Butylphenol, p-tert-butylphenol, on-pentylphenol, mn-pentylphenol, pn-pentylphenol, on-hexylphenol, mn-hexylphenol, pn-hexylphenol, o-cyclohexylphenol, m- Cyclohexylphenol, p-cyclohexylphenol, o-phenylphenol, m-phenylphenol, p-phenylphenol on-nonylphenol, mn-nonylphenol, pn-nonylphenol, o-cumylphenol, m-cumylphenol, p Cumylphenol, o-naphthylphenol, m-naphthylphenol, p-naphthylphenol, 2,6-di-tert-butylphenol, 2,5-di-tert-butylphenol, 2,4- Di-tert-butylphenol, 3,5-di-tert-butylphenol, 3,5-di-cumylphenol, 3,5-dicumylphenol, a compound represented by the following formula (7), represented by the following formula (8) Compound, a compound represented by formula 9, a compound represented by formula 10, a compound represented by formula 11, Compound, or represented by the formula (12) chroman of the formula 13 or formula 14 is one such as the phenol derivatives can be used:

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

In Chemical Formula 9 and Chemical Formula 10,

n is an integer of 7-30.                     

[Formula 11]

[Formula 12]

In Chemical Formulas 11 and 12,

R ¹³ are each independently an alkyl group having 1 to 12 carbon atoms,

k is an integer of 1-3.

[Formula 13]

[Formula 14]

Preferably, the terminator is p-butylphenol, p-cumylphenol, p-phenylphenol, the compound represented by the formula (11), the compound represented by the formula (12), the compound represented by the formula (13) or the It is preferable to use a compound represented by the formula (14).

The terminal stopper is preferably contained in an amount of 0.01 to 10 mol% based on 1 mol of the aromatic dihydroxy compound used as a starting material for the transesterification reaction of the present invention.

All of the terminating agent may be added in advance to the transesterification reaction, or some may be added in advance and the rest may be added as the reaction proceeds. In some cases, after some transesterification of the aromatic dihydroxy compound and the diaryl carbonate is carried out, all of the terminal stoppers may be added.

The antioxidant is preferably to use a phosphorus antioxidant, for example trimethyl phosphite, triethyl phosphite, tributyl phosphite, trioctyl phosphite, trinonyl phosphite, tridecyl phosphite, trioctadecyl phosph Trialkyl phosphites such as fighter, distearyl pentaerythritol diphosphite, tris (2-chloroethyl) phosphite, or tris (2,3-dichloropropyl) phosphite; Tricycloalkyl phosphites such as tricyclohexyl phosphite; Triaryl phosphites such as triphenyl phosphite, tricresyl phosphite, tris (ethylphenyl) phosphite, tris (butylphenyl) phosphite, tris (nonylphenyl) phosphite, or tris (hydroxyphenyl) phosphite ; Monoalkyl diaryl phosphites such as 2-ethylhexyl diphenyl phosphite; Trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tridecyl phosphate, trioctadecyl phosphate distearyl pentaerythritol diphosphate, tris (2-chloroethyl) phosphate, or tris (2,3-dichloropropyl Trialkyl phosphates such as phosphate; Tricycloalkyl phosphates such as tricyclohexyl phosphate; Or triaryl phosphates such as triphenyl phosphate, tricresyl phosphate, tris (nonylphenyl) phosphate, or 2-ethylphenyl diphenyl phosphate.

In the preparation of the polyester carbonate resin of the present invention, the transesterification reaction is carried out in the presence of the polymerization catalyst, the aromatic dihydroxy compound and the diaryl carbonate, wherein further addition of additives such as terminators, branching agents, antioxidants, etc. Can be added.

The end stoppers, branching agents, antioxidants and the like can be added in the form of powders, liquids, gases and the like, and these serve to improve the quality of the obtained polyester carbonate resin.                     

Although the reaction temperature in the transesterification reaction is not particularly limited, it is preferably carried out at a temperature of 100 to 330 ℃, preferably at a temperature of 180 to 300 ℃, more preferably gradually with the progress of the reaction It is advisable to raise the temperature from 180 to 300 ° C. If the reaction temperature is less than 100 ℃ can lower the rate of transesterification, if greater than 330 ℃ there is a problem that can be colored by side reaction or the resulting polyester carbonate resin.

The reaction pressure during the transesterification reaction is not particularly limited, and can be adjusted according to the vapor pressure and the reaction temperature of the monomers used, but in the initial stage of the reaction, it is to be pressurized to an atmospheric pressure (atmospheric pressure) of 1 to 10 atm, and after the reaction In the decompression state to finally be 0.1 to 100 mbar.

In addition, the reaction time during the transesterification reaction may be carried out until the target weight average molecular weight is usually 1,500 to 15,000 g / mol, it is usually carried out for 0.2 to 10 hours.

The transesterification reaction is usually carried out in the absence of an inert solvent, but may be carried out in the presence of an inert solvent corresponding to 1 to 150% by weight of the polyester carbonate resin obtained as necessary. Examples of the inert solvent include aromatic compounds such as diphenyl ether, halogenated diphenyl ether, benzophenone, polyphenylene ether, dichlorobenzene, and methylnaphthalene; Or cycloalkanes such as tricyclo (5,2,10) decane, cyclooctane, cyclodecane and the like can be used.

In addition, it may be carried out under an inert gas atmosphere if necessary, and examples of the inert gas include gases such as argon, carbon dioxide, dinitrogen monoxide and nitrogen; Chlorofluoro hydrocarbons, alkanes such as ethane or propane, or alkenes such as ethylene or propylene and the like.

As the transesterification reaction proceeds under the above conditions, phenols, their esters, water and inert solvent corresponding to the diallylcarbonate used are desorbed from the reactor. Such detachment may be separated, purified, and regenerated. The transesterification can be carried out batchwise or continuously using any apparatus. At this time, the reaction apparatus of the transesterification reaction can be used as long as it has a normal stirring function, it is good to have a high viscosity type stirring function by increasing the viscosity in the reaction later. Also preferred types of reactors are vessel type or extruder type.

Second step: condensation polymerization reaction step

Dia of the low-molecular-weight polyester carbonate prepolymer having a number average molecular weight of 1,500 to 15,000 g / mol prepared through the transesterification reaction at high temperature or condensation polymerization under nitrogen injection to remain in the unreacted state after the transesterification reaction A low molecular weight reaction by-product, such as ryl carbonate and a low polymerization degree by-product of less than 3, and reaction by-products such as phenol newly generated during the reaction are removed, thereby preparing a high molecular weight amorphous polyester carbonate.

In the condensation reaction, in addition to phenol, which is a reaction byproduct, unreacted diaryl carbonate and a reaction by-product of less than 3 degree of polymerization that are not participating in the reaction are evaporated together with phenol and extracted out of the reactor. In comparison, the solid phase polymerization has the effect of promoting the molecular weight increase of the polyester carbonate.

In addition, in the conventional process, not only the diaryl carbonate, dicarboxylic acid and reaction by-products having a polymerization degree of less than 3 used in the transesterification step are removed through the condensation polymerization step before the solid phase polymerization as in the present invention, As a result, as the molecular weight of the prepolymer increases, the molar difference between the resulting prepolymer-terminated aryl carbonate and aromatic hydroxy becomes large, and thus a long time is required to prepare a high molecular weight polycarbonate in solid phase polymerization.

The condensation polymerization reaction of the present invention can use all of the common condensation reactor, for example a rotating disk reactor (rotating disk reactor) or a rotating cage reactor (rotating cage reactor), in addition to the thin film reactor (Thin film reactor) ) Can be used.

In this case, the reaction temperature is preferably 180 to 330 ° C, more preferably 200 to 300 ° C.

In addition, the condensation polymerization reaction is a reaction product of dialkyl (aryl) carbonate and a reaction by-product of less than polymerization degree 3 and phenol and water, which are newly generated by-products, in the unreacted state after the transesterification reaction and the ester reaction. The removal may be carried out under reduced pressure of 0 to 50 mmHg, more preferably under reduced pressure of 0 to 20 mmHg.

According to one embodiment of the present invention, the reaction by-products may be removed by nitrogen injection instead of the reduced pressure, wherein the amount of nitrogen injected is preferably 0.01 to 1.0 Nm ³ / kg ㅇ h. The reaction time may vary depending on the reaction conditions, but generally 2 to 120 minutes is preferred.

The medium molecular weight amorphous polyester carbonate prepolymer prepared by the above process preferably has a number average molecular weight of 3,000 to 20,000 g / mol.

Phase 3: Crystallization and Solid State Polymerization

A high molecular weight polyester carbonate resin is prepared by solid-phase polymerizing a polyester carbonate having a number average molecular weight of 3,000 to 20,000 g / mol prepared through the condensation polymerization reaction.

The polyester carbonate prepolymer prepolymerized by transesterification, ester reaction and condensation polymerization as described above is prepared by heating to a solid phase in an inert gas atmosphere or under reduced pressure, ie, solid phase polymerization to prepare a high molecular weight polyester carbonate resin. .

The number average molecular weight (Mn) of the medium molecular weight polyester carbonate prepolymer used in the solid phase polymerization is preferably 3,000 to 30,000 g / mol, more preferably 5,000 to 25,000 g / mol. When the number average molecular weight is less than 3,000 g / mol, there is a problem that a long reaction time is required for solid phase polymerization.

At this time, if necessary, the step of crystallizing the polyester carbonate prepolymer before the solid phase polymerization is further performed. The crystallization treatment is carried out in order to raise the melting point of the polyester carbonate prepolymer by crystallization and not to cause fusion of the polyester carbonate prepolymer during solid phase polymerization.

There is no restriction | limiting in particular in the said crystallization processing method, Although various methods can be used, it is preferable to carry out especially by a solvent treatment method or a heat crystallization method.

In the solvent treatment method, after dissolving the polyester carbonate prepolymer in a suitable solvent, the solvent is evaporated, a method of precipitating a solid polyester carbonate prepolymer by adding an antisolvent to the polyester carbonate prepolymer, or a polyester carbonate prepolymer. There is a method in which a polyester carbonate prepolymer is contacted with a liquid solvent or solvent vapor having a low solvent solubility to penetrate the solvent in the polyester carbonate prepolymer to crystallize.

Preferred solvents for the solvent treatment of such polyester carbonate prepolymers include chloromethane, methylene chloride, chloroform, carbon tetrachloride, chloroethane, dichloroethane (various), trichloroethane (various), trichloroethylene, or tetrachloroethane Aliphatic halogen hydrocarbons such as (various); Aromatic hydrogenated hydrocarbons such as chlorobenzene or dichlorobenzene; Ether compounds such as tetrahydrofuran or dioxane; Ester compounds such as methyl acetate or ethyl acetate; Ketone compounds such as acetone or methyl ethyl ketone; Aromatic hydrocarbons such as benzene, toluene, or xylene.

The amount of the solvent used for the solvent treatment is different depending on the kind of the polyester carbonate prepolymer or the solvent, the required degree of crystallization, the treatment temperature, etc., but is preferably 0.05 to 100 times the weight of the polyester carbonate prepolymer, more preferably 0.1 to 50 It is good to be used by ship.

On the other hand, the heat crystallization method is a method of crystallizing by heating to a range below the temperature at which the polyester carbonate prepolymer starts to melt above the glass transition temperature of the polyester carbonate resin to obtain the polyester carbonate prepolymer. The method can be crystallized by simply heating the polyester carbonate prepolymer, which is a very easy method.

The temperature T _c (° C.) for performing such heat crystallization is preferably in the range from the glass transition temperature (T _g ) of the polyester carbonate resin to be obtained to the melting temperature T _m (° C.) of the polyester carbonate prepolymer. In particular, since the crystallization rate of the polyester carbonate prepolymer is low at low temperatures, the preferable heat crystallization temperature T _c (° C.) is preferably within the range represented by the following equation (3).

[Equation 3]

T _m -50 ≤ T _c ≤ T _m

The heat crystallinity of the polyester carbonate prepolymer may be carried out while maintaining a constant temperature in the above formula (3), may be carried out while changing the temperature continuously or discontinuously, or may be carried out by mixing them. As the method of changing the temperature, the melting temperature of the polyester carbonate prepolymer generally rises as the heat crystallization progresses. At this time, it is preferable to heat-crystallize while increasing the temperature at the same rate as the rising temperature.

The method of heat crystallization while changing the temperature as described above has the advantage that the crystallization rate of the polyester carbonate prepolymer is faster than the heat crystallization method performed under a constant temperature, and the melting temperature can be increased.

In addition, the time of heat crystallization is different depending on the chemical composition of the polyester carbonate prepolymer, the presence or absence of a catalyst, the crystallization temperature, the crystallization method, etc., but preferably it is performed for 1 to 200 hours.

In the solid phase polymerization, the catalyst used during the prepolymerization remains so that the polymerization can be carried out without adding a catalyst, and the monohydroxy compound, the monocarboxylic acid compound, or the aryl carbonate produced by the solid phase polymerization is a reaction system. The extraction can be accelerated by extraction outside. As a method for extracting the monohydroxy compound, the monocarboxylic acid compound or the aryl carbonate out of the reaction system, an inert gas such as nitrogen, argon, helium, carbon dioxide, a lower hydrocarbon gas, or the like is introduced, and a monohydroxy compound, or aryl A method of removing the carbonate with the gas, a method of carrying out the reaction under reduced pressure, a method of using them in combination, and the like can be used. In addition, when introducing a companion gas (inert gas, lower hydrocarbon gas), it is preferable to heat the gas to a temperature near the reaction temperature in advance.                     

The form of the polyester carbonate prepolymer used in the solid phase polymerization is not particularly limited, but the large lumped polyester carbonate prepolymer is a pellet, bead, granule, powder, or the like because it is difficult to handle and difficult to handle. Carbonate prepolymers are preferred. It is also possible to use a solid polyester carbonate prepolymer crushed to an appropriate size. In particular, the polyester carbonate prepolymer crystallized by solvent treatment after the prepolymerization is usually obtained in the form of a porous granule or powder, and such a porous polyester carbonate prepolymer is a monohydroxy compound, a monocarbye, which is a byproduct in the case of solid phase polymerization. The extraction of the acid compound or the aryl carbonate is preferred since it is easy.

In addition, the solid phase polymerization may further use additives such as powder, liquid, or gaseous end-stopping agents, branching agents, antioxidants, and the like, which serve to improve the quality of the obtained polyester carbonate resin. .

The reaction temperature T _p (° C.) and the reaction time during the solid phase polymerization are the type (chemical structure, molecular weight, etc.) or type of the polyester carbonate prepolymer, the type or amount of the catalyst, the crystallinity of the polyester carbonate prepolymer, or the melting temperature T _m '( ℃). In addition, although the degree of polymerization of the polyester carbonate resin to be obtained or other reaction conditions may vary, preferably the polycarbonate prepolymer is not melted from the glass transition temperature (T _g ) of the polyester carbonate resin to be obtained. It is preferable that it is the range to the temperature to hold. More preferably, it is preferably performed for 1 minute to 100 hours, most preferably 0.1 minutes to 50 hours.

[Equation 4]

T _m '-50 ≤ T _p ≤ T _m '

For example, when the polyester carbonate resin of bisphenol A is prepared as the temperature range, solid phase polymerization is preferably performed at 150 to 260 ° C, more preferably at 180 to 230 ° C.

In order to give uniform heat to the polymer during the polymerization during the solid phase polymerization, or to facilitate the extraction of by-product monohydroxy compound, monocarboxylic acid compound or aryl carbonate, the method by stirring blades, the reactor itself is rotated It is preferable to use a stirring method such as a method of using a reactor having a structure, a method of flowing by a heating gas, or the like.

The number average molecular weight (M _n ) of the polyester carbonate resin obtained by the solid state polymerization as described above is 15,000 to 200,000, preferably 15,000 to 100,000. The polyester carbonate resin of the present invention having the above weight average molecular weight can be usefully used for industrial purposes.

The shape of the polyester carbonate resin obtained by the solid phase polymerization may vary depending on the shape of the polyester carbonate prepolymer used, but is usually a powder such as beads, granules, or powder. In addition, the crystallinity of the obtained polyester carbonate is usually higher than that of the polyester carbonate prepolymer. That is, the polyester carbonate resin prepared according to the present invention is a crystalline resin in powder form. In addition, the crystalline resin in the form of powder homogenized to a predetermined molecular weight by solid phase polymerization may be introduced into the compressor as it is, without being cooled, or pelletized, or may be introduced into a molding machine without cooling to be molded.

The reaction apparatus used in the prepolymerization, crystallization, and solid phase polymerization carried out to prepare the polyester carbonate resin of the present invention may use a batch type, a fluidized type, or a combination thereof. In addition, in general, prepolymerization is intended to produce a relatively low molecular weight polyester carbonate prepolymer, whereas the present invention, prepolymerization by transesterification reaction is not necessary for the expensive reactor for high viscosity fluids required for high temperature melt polymerization The crystallization process can be crystallized by solvent or heat treatment of the polyester carbonate prepolymer, and no special equipment is required. Solid phase polymerization can also be polymerized with any device that can substantially heat the polyester carbonate prepolymer and remove by-product monohydroxy compounds, monocarboxylic acid compounds or arylcarbonates.

Hereinafter, preferred examples are provided to help understanding of the present invention, but the following examples are merely to illustrate the present invention, and the scope of the present invention is not limited to the following examples.

Example

Example 1

(Preparation of amorphous polyester carbonate prepolymer)

Nitrogen atmosphere by mixing 1,500 g (6.57 mole), 1,463 g (6.83 mole), and 15.89 g (6.9 × 10 ^-2 mole) of bisphenol-A, diphenyl carbonate, and 1,10-decanedicarboxylic acid, respectively After the injection into the reactor under, dibutyltin oxide was injected into the polymerization catalyst at a molar concentration of 2.5 × 10 ⁻⁴ based on bisphenol-A, and then reacted for 5 minutes at a jacket temperature of 230 ° C. with stirring. Then, a low molecular weight amorphous polyester carbonate prepolymer having a number average molecular weight of 3,589 g / mol was prepared by esterification and transesterification for 30 minutes under a reduced pressure of 1 to 4 mmHg.

(Preparation of amorphous polyester carbonate through condensation polymerization reaction)

Condensation polymerization of the polyester carbonate was carried out by adjusting the low molecular weight amorphous polyester carbonate prepolymer prepared above to a residence time of 30 minutes in a thin film reactor having a temperature of 300 ° C. and a reaction pressure of 1 mmHg or less. To prepare a medium molecular weight amorphous polyester carbonate having a number average molecular weight of 5,269 g / mol.

(Manufacture of crystalline polyester carbonate)

The prepared medium molecular weight amorphous polyester carbonate was dissolved in methylene chloride at a temperature of 0.15 g / mL at room temperature, and 100% methanol was used as a non-solvent to form powdery crystalline polyester carbonate as a precipitate. Obtained.                     

(Manufacture of high molecular weight crystalline polyester carbonate)

The powdery crystalline polyester carbonate prepared above was injected into a solid phase polymerization reactor, and the solid phase polymerization reaction was performed under a reduced pressure of 1 mmHg at an isothermal condition of 200 ° C. The results are shown in Table 1.

Comparative Example 1

(Manufacture of crystalline polyester carbonate)

A powdery crystalline polyester carbonate was prepared in the same manner as in Example 1, except that the condensation polymerization step was not performed in Example 1.

(Manufacture of high molecular weight crystalline polyester carbonate resin)

Solid phase polymerization of the powdered crystalline siloxane copolycarbonate prepared in the same manner as in Example 1 is shown in Table 1 and Table 1.

Solid State Polymerization Time Example 1 Comparative Example 1 0 5,269 3,589 2 11,817 10,551 4 15,463 12,019 6 16,548 12,285 8 17,808 12,660 10 19,663 12,966 12 20,265 12,743

Comparative Example 2

Except for sodium acetate and tetrabutyl phosphonium hydroxide as a polymerization catalyst in Example 1, except that the molar concentration of 1 x 10 ^-6 and 2.5 x 10 ^-4 based on bisphenol-A, respectively In the same manner as in 1 to prepare an amorphous polyester carbonate.

At this time, the number average molecular weight was 2,479 and the color was inferior.

Comparative Example 3

An amorphous polyester carbonate was prepared in the same manner as in Example 1, except that antimony oxide was used as a polymerization catalyst as a polymerization catalyst in Example 1 to a molar concentration of 2.5 × 10 ⁻⁴ based on bisphenol-A.

At this time, the number average molecular weight was 2,117 and the chromaticity and transparency were inferior.

The method for preparing polyester carbonate of the present invention shortens the reaction time by introducing a condensation polymerization step between a transesterification step and a solid phase polymerization step, and improves color and reactivity by using a tin-based catalyst. Can be prepared.

Claims (12)

a) Ester reaction of the dicarboxylic acid compound with the aromatic dihydroxy compound and transesterification reaction of the carbonic acid diester compound with the aromatic dihydroxy compound proceed simultaneously under the catalyst so that the number average molecular weight (M _n ) is 1,500 to 15,000 g / preparing a low molecular weight amorphous polyester carbonate prepolymer that is mol; b) condensation polymerization of the low molecular weight amorphous polyester carbonate prepolymer of step a) to produce a medium molecular weight amorphous polyester carbonate having a number average molecular weight of 3,000 to 20,000 g / mol; c) preparing a crystalline polyester carbonate from the medium molecular weight amorphous polyester carbonate of step b); And d) a method of preparing a polyester carbonate resin comprising solid phase polymerizing the crystalline polyester carbonate of step c) to produce a polyester carbonate having a number average molecular weight of 15,000 to 200,000 g / mol. The method for producing a polyester carbonate resin according to claim 1, wherein the catalyst is a tin-based catalyst. 3. The tin-based catalyst of claim 2 wherein the tin-based catalyst is selected from the group consisting of dialkyltin trichloride, dialkyltin dichloride, dialkyltin oxide, dialkyltin dialkoxide, dialkyltin dicarboxylate, and tetraalkyl tin Selected method. The method according to claim 2, wherein the tin catalyst is selected from the compounds represented by the following formulas.

The method of claim 1, wherein the catalyst is contained in an amount of 10 ^-1 to 10 ^-6 moles per mole of the aromatic dihydroxy compound. The method of claim 1, wherein the dicarboxylic acid compound used in step a) is a compound represented by the following formula (1): [Formula 1] HOOC--R ^One --COOH (In Formula 1, R ¹ is a substituted or unsubstituted aryl group having 4 to 30 carbon atoms, an alkyl group having 1 to 10 carbon atoms, or a cycloalkyl group having 5 to 30 carbon atoms). The method of claim 1, wherein the aromatic dihydroxy compound used in step a) is a compound represented by the following formula (1). [Formula 2]

(In Formula 2, R ² and R ³ are each independently a halogen atom or an alkyl group having 1 to 8 carbon atoms; a and b are each independently an integer of 0 to 4; Z is an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, -S, -SO-, -SO _2- , -O-, -CO-, a compound represented by the following formula (3) or a compound represented by the following formula (4) [Formula 3]

[Formula 4]

The method of claim 1, wherein the diaryl carbonate used in step a) is a compound represented by Formula 5 or a compound represented by Formula 6 below. [Formula 5]

(In Chemical Formula 5, Ar ¹ and Ar ² are each independently an aryl group) [Formula 6]

(In Chemical Formula 6, Ar ³ and Ar ⁴ are each independently an aryl group, D ¹ is two from the aromatic dihydroxy compound represented by the formula (1) Residues obtained by removing hydroxyl groups). The method for producing a polyester carbonate resin according to claim 1, wherein the dicarboxylic acid compound is 1 to 10 ^-4 moles per 1 mole of the diaryl carbonate compound. The method for producing a polyester carbonate resin according to claim 1, wherein the diaryl carbonate is 1.0 to 1.5 moles with respect to 1 mole of the dihydroxy compound. The method of claim 1, wherein the step b) is performed in a reactor selected from the group consisting of a rotating disk reactor, a rotating cage reactor and a thin film reactor. The manufacturing method of polyester carbonate resin made into. The polyester carbonate resin manufactured by the method of any one of Claims 1-11.