KR100878451B1 - Process for producing high molecular weight fluorene-based polycarbonate copolymer by solid phase polymerization - Google Patents

Abstract

The present invention relates to a process for preparing a high molecular weight polycarbonate copolymer resin, wherein the process according to the invention is carried out under a catalyst condition containing a) a tetraarylphosphonium compound catalyst and optionally a promoter. Low molecular weight poly having a number average molecular weight of 1,000 to 10,000 g / mol by melt polymerizing a dihydroxyaromatic mixture and a diaryl carbonate containing a fluorene-based dihydroxyaromatic compound at 180 to 1 mbar and 180 to 240 ° C. An initial step of preparing a copolycarbonate prepolymer; b) converting to semi-crystalline polycarbonate prepolymer by crystallization of the prepolymer, caused by nonsolvent; And c) preparing a high molecular weight polycarbonate copolymer having a weight average molecular weight of 25,000 to 200,000 g / mol by solid phase polymerization of the prepolymer in the presence of a catalyst comprising a tetraaryl phosphonium compound. Include.

Description

TECHNICAL PROCESS OF THE PREPARATION OF HIGH MOLECULAR WEIGHT FLUORENIC COPOLYCARBONATES BY SOLID STATE POLYMERIZATION}

The present invention relates to a process for preparing a high molecular weight polycarbonate copolymer. More specifically, the present invention is substituted or unsubstituted 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene-based compound (e.g., 9,9-bis (4- ( 2-hydroxyethoxy) phenyl) fluorene (bisphenol-HEFL)) or substituted or unsubstituted 9,9-bis (4-hydroxyphenyl) fluorene-based compound (e.g., 9,9-bis (4 -Hydroxyphenyl) fluorene (bisphenol-FL)) and a diol compound of 2,2'-bis (4-hydroxyphenyl) propane (bisphenol-A) by mixing and polymerizing to prepare a polycarbonate copolymer It is about.

Specifically, the solid phase polymerization method is a solvent of a low molecular weight polycarbonate prepolymer using a step of preparing a low molecular weight polycarbonate prepolymer by changing the composition of bisphenol-HEFL or bisphenol-FL and melt polymerizing with bisphenol-A. It characterized in that it comprises a crystallization step by.

An advantage of the present invention is to prepare a high molecular weight polycarbonate copolymer resin having high productivity without containing short crystallization time, excellent color and gel by using a copolymer monomer (comonomer) by a solid phase polymerization method. will be.

There is a strong demand for new materials having excellent processability in the mechanical and optical fields, and one example of the applicable field is the manufacture of optical devices such as optical information storage disks. Much research has been done on several types of polycarbonate resins for this purpose. Polycarbonate resin is a suitable material for optical parts that require characteristics such as proper glass transition temperature, high purity and low water absorption. Especially, aromatic polycarbonate resin has excellent characteristics of transparency, heat resistance and mechanical rigidity. It is used as an engineering plastic having a field.

Generally, aromatic polycarbonate resins are prepared by the reaction of carbonic esters which form compounds such as diphenyl carbonate and phosgene with 2,2'-bis (4-hydroxyphenyl) propane (bisphenol-A).

Aromatic polycarbonate resins prepared using such bisphenol-A as a raw material are widely used for electrical, electronic parts and optical devices because of their excellent transparency, mechanical properties, and processability. Difficulties exist in machining by injection molding, which is limited in speed and amount of information and quality stored on the disc.

Therefore, in recent years, as the demand for reducing the size and weight of electric and electronic products increases, development of aromatic polycarbonate resins having improved heat resistance and mechanical properties without reducing the basic properties of the resins is required.

Therefore, the present invention provides a novel method for producing a high molecular weight polycarbonate which is excellent in heat resistance and mechanical properties, and has no transparency or gel water, and the present invention is also based on a solid-phase polymerization method and using a comonomer Another object of the present invention is to provide a method of manufacturing a polycarbonate copolymer having improved physical properties by changing the structure of the copolymer.

The production method of polycarbonate resin is commercially produced by the method of melt polymerization or interfacial polymerization. A typical melt polymerization process is prepared by combining bisphenol, diaryl carbonate and a suitable catalyst to produce low molecular weight polycarbonate prepolymers with a number average molecular weight ranging from 1,000 to 10,000 g / mol determined by GPC using polystyrene as standard. It is converted into high molecular weight polycarbonate by thermal polymerization which increases the temperature. These polycarbonate prepolymers have an intrinsic viscosity of 0.06 to 0.30 dL / g in chloroform at 30 ° C., typical conditions.

The melt polymerization has several disadvantages, such as a sharp increase in the melt viscosity of the prepolymer at high conversions (> 98%) and very difficult to handle high viscosity melt polymerization mixtures. You lose. This difficulty makes it difficult to mix the prepolymer and causes hot spots along the base wall of the reaction vessel. Another drawback is the need for special devices such as helicon mixers operating at low pressure and in the temperature range of 270-350 ° C., which is expensive and expensive to operate.

In the interfacial polymerization process, polyhydroxy is prepared by reacting a dihydroxy aromatic compound such as bisphenol-A with phosgene in the presence of an appropriate catalyst such as an acid acceptor and an amine in a mixed solution of an aqueous layer / organic layer. However, the interfacial polymerization process uses phosgene, which is a very dangerous substance, and uses a hydrocarbon containing chlorine, such as methylene chloride, as an organic solvent, and thus causes environmental pollution of the solvent. Including residual components of the component has a disadvantage in that it adversely affects the water absorption characteristics and the stability to moisture.

Recently, solid phase polymerization to compensate for these disadvantages has been used as an improved process for producing high molecular weight polycarbonate. The solid phase polymerization provides several advantages over the melt polymerization and the interfacial polymerization. Solid phase polymerization performs the reaction at 180-240 ° C., which is lower than melt polymerization, and does not need to handle melt at high temperatures such as melt polymerization, and does not require special equipment to proceed with the polymerization. Furthermore, since toxic substances such as phosgene and chlorine-containing solvents used in interfacial polymerization are not used and organic solvents are not used, they are also free from environmental pollution by the use of volatile organic solvents. Polycarbonates produced by solid phase polymerization also do not contain sodium and chlorine ions present in interfacial polymerization, thus improving the hydrolytic stability.

In the solid state polymerization process, semi-crystaline polycarbonate prepolymers are heated at temperatures above the glass transition temperature and below the melting point of the prepolymers, and volatile side reactions such as phenol and diphenyl carbonate are used to produce a stream of inert gas. Used or removed under reduced pressure. The process of converting a low molecular weight prepolymer into a high molecular weight polymer proceeds in the solid phase under the above conditions. The melt polymerization process in which a copolymer of a dihydroxy aromatic compound or a composition of a dihydroxy aromatic compound containing a comonomer therewith at a high temperature with a diaryl carbonate to prepare a copolymer is carried out by the comonomer being subjected to a melt reaction. In the case of melt polymerization, thermal deformation may occur due to severe deformation in the case of melt polymerization by using a solid phase polymerization method which can be decomposed under conditions or does not have thermal stability, but can be polymerized by a lower reaction temperature and milder than the melt polymerization reaction. Polycarbonate copolymers containing this reduced unit can be prepared but in solid phase polymerization will be able to produce polymers that can eliminate it. However, many monomers, such as soft block monomers such as polyethylene glycol and polytetrahydrofuran, are likely to be modified even under normal solid state polymerization conditions, so a new method for preparing polycarbonate copolymers by solid phase polymerization is explored. It becomes the target of. Therefore, the method of embedding a copolymer unit in a polymer produced by solid phase polymerization is satisfactory as another alternative.

Solid-state polymerization is available in the temperature range of 80-240 ℃, which is lower than melt polymerization, and it does not need to deal with molten polymer at high temperature, so it can solve the problem of huge scale and complicated equipment, and also does not use toxic materials. Reaction in the solid phase can prevent the degradation of the polymer. Solid phase polymerization is carried out by passing a stream of inert gas through a semicrystalline prepolymer and heating the semicrystalline polycarbonate prepolymer in powder or pellet form with an appropriate catalyst, optionally in a fixed bed or fluidized bed reactor. Can be done.

The reaction temperature and time may vary depending on the chemical structure, molecular weight and the like of the semicrystalline prepolymer. However, the reaction temperature should be at least below the melting point of the prepolymer and above the glass transition temperature, which can prevent the prepolymer from dissolving during the solid phase polymerization. Since the melting point of the semicrystalline prepolymer increases during the polymerization process, it is desirable to gradually increase the reaction temperature as the reaction proceeds. In general, the reaction temperature is preferably 10-50 ° C. or lower than the melting point of the prepolymer, and preferably in the range of 180-240 ° C., and a high molecular weight polycarbonate is obtained when the polymerization is carried out at the above temperature.

The conventional solid phase polymerization process consists of three steps, the first step is to prepare a low molecular weight polycarbonate prepolymer by melt polymerization of bisphenol and diaryl carbonate. Typically mixtures of diaryl carbonates and bisphenols are heated with a transesterification catalyst for 4 to 10 hours at a temperature of 150-300 ° C. with terminal groups having hydroxyl groups and carbonate groups and in the range of number average molecular weights of 1,000 to 10,000 g / mol. Prepolymers are prepared.

In the second step, the crystallization of the linear polycarbonate prepolymer is carried out by (a) dissolving the prepolymer in a solvent and then evaporating the solvent in the presence of a suitable catalyst, (b) diluting the prepolymer and evaporating the diluent from 0 to 10 By refluxing the prepolymer in the presence of a suitable catalyst for a time or (c) heating the prepolymer in the presence of a catalyst at a predetermined temperature (temperature range higher than the glass transition temperature of the prepolymer and below the melting point). Suitable diluents and solvents are aliphatic and aromatic hydrocarbons substituted with aliphatic and aromatic hydrocarbons, ethers, esters, ketones and chlorine. The crystallinity of the resulting prepolymer measured by differential scanning calorimetry (DSC) is 5 to 55%.

In the third stage, volatile side reactants are removed from the reaction system to proceed with the reaction during the solid phase reaction. Inert gas is provided to the solid-state reactor to remove volatile side reactions. Non-volatile gas is generally nitrogen (N2), helium (He), argon (Ar), etc. can be used and the flow rate of the gas provided is It may vary from 0.1 to 5 L / m depending on the particle size and the shape of the reactor. The rate of polymerization may vary depending on the flow rate and type of carrier gas.

Recently, polycarbonate resins are widely used as resins for the production of optical data recording media including optical disks, for example, compact audio disks, and optical storage disks used in computers. The optical requirement of the disc with the ability to read and write requires low birefringence. Reducing birefringence increases the readability of the optics. However, polycarbonates made from bisphenol-A, the most widely used monomers, show high levels of birefringence. The birefringence shows 6,6'-dihydroxy-3,3,3 ', 3'-tetramethyl-1,1'-spirobiindane, 1,1,3-trimethyl-3- ( 4-hydroxyphenyl) -5-hydroxyindan, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2'-bis (4-hydroxyphenyl) adamantane, 1,3-bis By containing a monomer containing a structure of a rigid skeleton such as (4-hydroxyl) adamantane, it can be low enough to be used as an optical component. Birefringence properties of polymer materials are due to a variety of causes, including physical and structural characteristics of the polymer material, thermal deformation of the polymer being processed and the degree of orientation of the molecules in the polymer material. Products molded from polymeric materials are due to defects and orientations of the polymer chains that are made up, for example birefringence in molded optical parts, in part, by filling the polymer into the polymer's molecular structure and the forming mold or during the cooling process. It is determined by the processing conditions such as the applied force. Thermodynamic stresses generated during the fabrication process of molded articles can affect the defects and / or orientation of the polymer chains.

In order to improve the processability of polycarbonates, studies are also underway to introduce flexible block comonomers such as aliphatic compounds such as alkanedionic acid or polyoxyalkylene glycol into the main chain of polycarbonate.

It is an object of the present invention to provide a novel process for preparing high molecular weight polycarbonate copolymer resins.

That is, the present invention is a 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene-based compound substituted or unsubstituted by solid phase polymerization (e.g., 9,9-bis (4- (2-hydride) Hydroxyethoxy) phenyl) fluorene (bisphenol-HEFL)) or substituted or unsubstituted 9,9-bis (4-hydroxyphenyl) fluorene-based compound (e.g., 9,9-bis (4-hydroxy) Phenyl) fluorene (bisphenol-FL)) and a diol compound of 2,2'-bis (4-hydroxyphenyl) propane (bisphenol-A) are polymerized to produce a polycarbonate copolymer. .

More specifically, 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene (bisphenol-HEFL) or 9,9-bis (4-hydroxyphenyl) fluorene (bisphenol by solid phase polymerization -FL) to change the composition and copolymerize with 2,2'-bis (4-hydroxyphenyl) propane (bisphenol-A) to provide a method for producing a high molecular weight polycarbonate copolymer, more specifically The present invention provides a high molecular weight polycarbonate copolymer and a novel method for preparing the same, which have no color discoloration and gel, and which have a good optical property through a short crystallization step.

Another object is to provide a method for producing a high molecular weight polycarbonate copolymer and a low molecular weight polycarbonate prepolymer according to the above production method.

The present invention relates to a bisphenol-based [Formula 1] and a fluorene-gain [Formula 2-1] or [Formula 2-2] in the presence of a catalyst containing (a) a tetraarylphosphonium compound and optionally an alkyl ammonium compound as a promoter To a low molecular weight amorphous polycarbonate prepolymer having a number average molecular weight of 1,000 to 10,000 g / mol by melt polymerization of a dihydroxyaromatic compound comprising a dihydroxy aromatic compound; Making; (b) preparing a low molecular weight polycarbonate prepolymer having a semi-crystalline structure by a non-solvent induced crystallization method of the prepolymer; (c) preparing the semi-crystalline prepolymer into a high molecular weight polycarbonate copolymer having a weight average molecular weight of 25,000 to 200,000 g / mol by solid phase polymerization; to provide.

[Formula 1]

에서 선택되는 관능기를 나타내며, R₂ 및 R₃는 독립적으로 수소원자, C₁-C₂₀의 알킬 그룹, C₄-C₂₀의 시클로알킬 그룹 또는 C₄-C₂₀의 아릴 그룹, 또는 C₄-C₂₀의 융합고리로부터 선택된다.][R ₁ is independently a functional group selected from halogen atom, nitro group, cyano group, C ₁ -C ₂₀ alkyl group, C ₄ -C ₂₀ cycloalkyl group or C ₆ -C ₂₀ aryl group, m and n is independently an integer from 0 to 4, X is an oxygen atom, a sulfur atom, -SO ₂ - in the group, C ₁ -C ₂₀ aliphatic radical, C ₆ -C ₂₀ aromatic radical, C ₆ -C ₂₀ in the Cyclic aliphatic radicals or

R ₂ and R ₃ independently represent a hydrogen atom, an alkyl group of C ₁ -C ₂₀ , a cycloalkyl group of C ₄ -C ₂₀ or an aryl group of C ₄ -C ₂₀ , or C _4- Selected from C ₂₀ fused rings.]

[Formula 2-1]

[Formula 2-2]

Wherein R ₄ and R ₅ and R ₆ are independently a halogen atom, a nitro group, a cyano group and an alkyl group of C ₁ -C ₂₀ , a cycloalkyl group of C ₄ -C ₂₀ or an aryl group of C ₄ -C ₂₀ M, n, o, p, r and s are independently integers from 0 to 4.

More specifically, the present invention relates to 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene (bisphenol-HEFL) or 9,9-bis (4- (2-hydroxyphenyl) fluorene ( High-molecular-weight polycarbonate by solid phase copolymerization of dihydroxy compound and diaryl carbonate mixed with dihydroxy aromatic compound of bisphenol-HEFL) and 2,2'-bis (4-hydroxyphenyl) propane (bisphenol-A) It is to provide a way to provide.

Numerous terms that may be more readily understood through reference in accordance with the detailed description of embodiments and preferred configurations of the present invention and in the specification, including the claims, may be defined as having the following meanings The terms used in the singular meanings of the following terms include the plural forms unless the context clearly indicates otherwise.

The term 'optional' or 'optionally' means that the events or situations described in succession occur or do not occur, and that the description includes the cases in which the events or situations occur and the cases do not occur.

Polycarbonate copolymers refer to polycarbonates containing structural units obtained from one or more dihydroxy aromatic compounds.

Melt polymerization refers to the preparation of polycarbonate copolymers prepared by transesterification of at least one diaryl carbonate with at least one or more dihydroxy aromatic compounds.

Bisphenol-A is 2,2-bis (4-hydroxyphenyl) propane or 4,4'-isopropylidine diphenol, and bisphenol-HEFL is 9,9-bis (4- (2-hydroxyethoxy) Phenyl) fluorene.

The low molecular weight polycarbonate prepolymer has a number average molecular weight (Mn) of 1,000 to 10,000 g / mol and the high molecular weight polycarbonate copolymer means a number average molecular weight (Mn) of greater than 10,000 g / mol.

An aromatic radical means a radical having at least one valence valence containing at least one aromatic group. Examples of aromatic radicals include phenyl, pyridyl, furanyl, thienyl, naphthyl, phenylene, biphenyl and the like. It may also include groups containing both aromatic and aliphatic compounds, such as benzyl groups, naphthylmethyl groups or phenethyl groups.

Aliphatic radicals represent radicals that are not cyclic and have at least one valence bond, including linear or branched carbon atom arrays. The arrangement can include nitrogen, sulfur, oxygen or heteroatoms which can be made with the exception of carbon and hydrogen. Examples of aliphatic radicals include methyl, methylene, ethyl, ethylene, hexyl, hexamethylene and the like, and cyclic aliphatic radicals represent radicals having at least one or more valence bonds containing an array of atoms which are not aromatic as cyclic. The arrangement may comprise nitrogen, sulfur, oxygen or hetero atoms, which may be made with the exception of carbon and hydrogen. Examples of cyclic aliphatic radicals include cyclopropyl, cyclopentyl, cyclohexyl, tetrahydrofuranyl and the like.

Tetraalkylammonium hydroxide can be used in the present invention in the range of 8x10 ^-8 to 8x10 ^-3 moles per mole of dihydroxy compound as one or more dihydroxy compounds, one or more diarylcarbonates and a catalyst for melt polymerization. Tetraarylphosphonium salts may also be used in the range of 7 × 10 ⁻⁶ to 7 × 10 ⁻² moles per mole of aromatic dihydroxyunsaturated.

According to the method of the present invention, dihydroxy benzenes may be used as the aromatic hydroxy compound. For example, hydroquinone (HQ), 2-methylhydroquinone, resorcinol, 5-methyl resorcinol, and dihydroxy naphthalenes such as 1,4-dihydroxynaphthalene and bisphenol-A and 4,4 Bisphenols, such as' -sulfonyldiphenol, can be used. The aromatic dihydroxy compound according to the present invention includes a mixture of a bisphenol compound represented by the following Chemical Formula 1 and a bisphenol having a structure of Chemical Formula 2-1 or Chemical Formula 2-2, and the substituents are as defined above.

[Formula 1]

[Formula 2-1]

(The substituent is as defined above.)

[Formula 2-2]

(The substituent is as defined above.)

The bisphenols are bisphenol A, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (3-chloro-4-hydroxyphenyl) propane, as described in Formula 1 and Formula 2, 2,2-bis (3-bromo-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxy Hydroxy-3-isopropylphenyl) propane, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9,9-bis (4 -(2-hydroxyethoxy) phenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-methylphenyl) fluorene and the like.

Diaryl carbonate according to the method of the present invention may comprise a compound of formula (3).

[Formula 3]

[R ₇ independently represents halogen atom, nitro group, cyano group, C ₁ -C ₂₀ alkyl group, C ₁ -C ₂₀ alkoxycarbonyl group, C ₄ -C ₂₀ cycloalkyl group or C ₆ -C _Is a functional group selected from an aryl group of ₂₀ , and x and y are integers of 0 to 5, which act independently.]

The compound of formula 3 is diphenyl carbonate, bis (4-methylphenyl) carbonate, bis (2-chlorophenyl) carbonate, bis (4-chlorophenyl) carbonate, bis (4-fluorophenyl) carbonate, bis (2, 4-fluorophenyl) carbonate, bis (2-nitrophenyl) carbonate, bis (4-nitrophenyl) carbonate and bis (methylsalicyl) carbonate, dimethyl carbonate, m-cresyl carbonate, dinaphthyl carbonate, dicyclo Hexyl carbonate and the like.

In the exemplary embodiment of the present invention, the catalyst may be a tetraaryl phosphonium compound represented by the following Chemical Formula 4.

[Formula 4]

[R ₈ -R ₁₁ is independently an aryl radical of C ₄ -C ₂₀ , and X ⁻ is an organic or inorganic anion]

Typically anions X ⁻ may be selected from hydroxyl groups (OH), halogen anions, carboxylic acid group anions, phenoxide groups, sulfonic acid anion groups, sulfites, carbonates, tetraphenyl borates and bicarbonate anion groups. Suitable organic phosphonium compounds include compounds of formula 4, such as tetraphenyl phosphonium hydroxide, tetraphenyl phosphonium acetate, tetraphenyl phosphonium tetraphenylborate and the like. Tetraphenyl phosphonium tetraphenylborate is preferred and the tetraphenylphosphonium compound is used as catalyst in the range of ¹ × 10 ⁻⁹ to 7 × 10 ⁻² moles per mole of dihydroxy aromatic compound.

As a configuration of the present invention, the promoter may be a quaternary ammonium compound represented by the following Chemical Formula 5.

[Formula 5]

[R ₁₂ -R ₁₅ is independently an alkyl radical of C ₁ -C ₂₀ , a cycloalkyl radical of C ₄ -C ₂₀ or an aryl radical of C ₄ -C ₂₀ , and X ⁻ is an organic or inorganic anion. ]

Typically anions X ⁻ are selected from the group consisting of hydroxyl groups (OH), halogen anions, carboxylic acid group anions, sulfonic acid anion groups, sulfites, formic acid anions, carbonates and bicarbonate anions.

Preferred organic phosphonium compounds are compounds comprising Formula 5, such as tetramethyl ammonium hydroxide, tetrabutyl ammonium hydroxide, tetramethyl ammonium acetate, tetramethyl ammonium formate and tetrabutyl ammonium acetate and tetramethyl ammonium hydroxide Is preferred.

The catalyst can be added in various forms according to the method of the present invention. It may be added in solid form and may also be dissolved in a solvent such as alcohol or water. As a configuration of the present invention, the catalyst may be added to the reaction system in the form of an aqueous solution. In the case of dissolving in water, it is common to use an amount of pure water that can dissolve the catalyst component. Since there is no use degree in that those skilled in the art can easily dissolve and use no further description, the pH of the aqueous solution containing the catalyst may vary depending on the type of catalyst used.

Cocatalysts may be added in various forms according to the methods presented herein and quaternary ammonium hydroxides such as tetramethyl ammonium hydroxide may be used. Cocatalysts may be added to increase the activity of the main catalyst and the quaternary ammonium hydroxides present in the constituents of the present invention are in the range of 1 × 10 ⁻⁹ to 8 × 10 ⁻³ moles per mole of aromatic dihydroxy compound used It is preferred to be included.

Melt polymerization according to the process presented herein is preferably carried out in different stages in a typical stirred reactor comprising a reflux tower and a cooler. First, the aromatic dihydroxy compound and the diaryl carbonate are mixed in a molar ratio of 1: 1 to 1: 1.1, the temperature is increased to melt the reactants, and the catalyst and cocatalyst component are added. Charged reactants are continuously removed by-products with increasing temperature and decreasing pressure to produce low molecular weight polycarbonate copolymer oligomers. Typically the reaction temperature for the production of polycarbonate prepolymers ranges from 180 ° C to 240 ° C. In the exemplary embodiment of the present invention, the reaction pressure in the melt polymerization step is preferably in the range of 180 to 1 mbar and the number average molecular weight of the low molecular weight amorphous polycarbonate prepolymer prepared in the step is in the range of 1,000 to 10,000 g / mol. Becomes

The total reaction time is generally 0.1 to 5 hours and may have a total reaction time of 1 to 4 hours as an example of the present invention.

Catalysts and cocatalysts constructed in accordance with the process of the invention can be used in the same or in different stages.

Among the catalyst components, the method according to the present invention has an advantage that a low molecular weight polycarbonate prepolymer can be obtained within a short reaction time by using a tetraarylphosphonium catalyst and a quaternary alkylammonium promoter. When using the same amount of catalyst in the same production conditions, than when using a tetraaryl phosphonium catalyst or a quaternary alkyl ammonium catalyst, when the two components are used at the same time, for example, tetraphenylphosphonium tetraphenyl When a mixed catalyst of borate (TPPTPB) and tetramethylammonium hydroxide tetraphenyl (TMAH) is used, the highest molecular weight is obtained, which means that a low molecular weight polycarbonate prepolymer can be obtained within a short reaction time. It is best to use co-catalysts at the same time.

In the second process according to the method of the present invention, the non-solvent induced semicrystallization step, first, the low molecular weight polycarbonate prepolymer is dissolved in a solvent of a chlorine atom-containing hydrocarbon, and the chlorine-containing hydrocarbons which may be used in the present invention include methylene chloride and chloroform. , 1,2-dichloroethane, chlorobenzene and o-dichlorobenzene can be used. Chloraliphatic hydrocarbons are most preferably methylene chloride or chloroform.

Dissolution of the low molecular weight polycarbonate prepolymer can be at any temperature. Typically from 0 ° C. to the boiling point of the solvent, a temperature range of 20-100 ° C. is preferred. If it is more than a certain amount of solvent for dissolving the polycarbonate prepolymer, the ratio of the solvent is not critically important.

As an example of the step of inducing semicrystallization by the nonsolvent of the present invention, the polycarbonate prepolymer is precipitated from the amorphous polycarbonate copolymer solution by the addition of a mixture of an organic nonsolvent and an organic nonsolvent and water (or alkanol). .

Suitable non-solvents include aliphatic hydrocarbons such as n-hexane, n-heptane and pyrrolium ether aromatic hydrocarbons such as toluene and xylene, hydroxy aliphatic compounds such as ethanol, 2-propanol, ethylene glycol and diethylene glycol, acetone And aliphatic ketones such as methyl ethyl ketone, methyl isobutyl ketone and the like and carboxylic ester compounds such as ethyl acetate and n-butyl acetate. By injecting a non-solvent into the polycarbonate copolymer solution, the polycarbonate copolymer can be precipitated and separated by a filter or by other separation processes described in the above process.

Another semi-crystallization method is a method in which the polycarbonate prepolymer is dissolved in the solvent used in the above constituent examples and the solvent is evaporated to obtain a semicrystalline polycarbonate prepolymer, and also a molten or solid amorphous polycarbonate prepolymer. To swell in a solvent of low solubility such as acetone, toluene, xylene and the like in the gaseous or liquid state can be prepared a semi-crystalline polycarbonate copolymer oligomer.

However, it is preferable to use a non-solvent which can obtain a crystalline polycarbonate copolymer when solid phase polymerization is carried out continuously. The use of the non-solvent is not limited to the amount used as long as the prepolymer is sufficiently crystallized and precipitated into the particles from the solvent, but it is generally economically good to use about 0.5 to 20 volume of the solvent, and as long as it is usually used in excess Has the same effect.

The presence of crystalline components can be found by making polycarbonate copolymer films. The opaque film indicates that the polycarbonate copolymer has some degree of crystallinity.

Non-solvents used in conjunction with chlorinated hydrocarbons and used to prepare crystalline in the present invention are aliphatic ketones, aliphatic hydroxy compounds or mixtures thereof, specifically aliphatic ketones such as acetone, methanol Aliphatic hydroxy compounds such as the like or mixtures of aliphatic ketones and aliphatic hydroxy compounds such as the mixture of acetone and methanol may be used.

The semicrystalline polycarbonate prepolymer contains crystallinity in the range of 10-30%, and in particular, 10-20% crystallinity is most preferable in terms of physical properties and productivity. In general, in the solid phase polymerization, if the crystallinity is high, the polymerization reaction rate is very slow.

The degree of crystallinity was determined from the heat of fusion (ΔHf) obtained by DSC measurement. Sci. Part B: Polym. Phys. The value of 100% crystallized polycarbonate can be calculated based on 109.8 J / g with reference to 25, 1511 (1979).

Crystallization components can also be determined by comparison of fully amorphous polymers with fully crystalline polymers through powder X-ray diffraction. The crystalline ratio of the semicrystalline polycarbonate prepolymer may vary depending on the type and properties of the solvent and nonsolvent used in the present invention.

In particular, certain groups of nonsolvents can greatly affect crystallinity when used with certain solvents. In this case, the use of other solvents does not produce an effect. For example, when chloroform is used as the solvent, methanol is particularly effective as a nonsolvent to improve the crystallinity of the polymer. The selection of suitable nonsolvents for use with the appropriate solvents used in conjunction with the present invention for this purpose and use can be determined by simple experiments.

The low molecular weight semicrystalline polycarbonate prepolymer obtained in the present invention has a number average molecular weight of 1,000 to 10,000 g / mol determined by GPC.

Low molecular weight semicrystalline polycarbonate prepolymers according to the present invention require solid phase polymerization. Solid phase polymerization may be carried out at a temperature range between the glass transition temperature and the melting temperature of the semicrystalline polycarbonate prepolymer, and is often performed at a temperature below 10-50 ° C. below the melting temperature. In general, the temperature is preferably in the range of 150-270 ° C., particularly in the range of 180-250 ° C. for solid phase polymerization.

In one embodiment of the present invention, the solid phase polymerization step may be performed in the presence or absence of a catalyst. Suitable catalysts may include basic salts, transition metal oxides, alkoxides, tetraaryl phosphonium compounds, tetraalkyl ammonium and tetraalkyl phosphonium carboxylates, and the like. Tetraphenyl phosphonium tetraphenyl borate is preferred and the proportion of catalyst is usually in the range of ¹ × 10 ⁻⁵ to 5 × 10 ⁻² , based on semicrystalline polycarbonate prepolymer.

Solid-state polymerization is in a mixer that can cause deep gas-solid contact such as stationary bed, fluidized bed, or paddle mixer, while contacting an inert gas such as nitrogen, helium, or argon, which is used as a fluid gas when a fluidized bed is used. It can be performed in. The inert gas may be used for the purpose of fluidizing the mixture or removing volatile by-products such as water or volatile carbonate compounds. The solid phase polymerization is controlled in a stepwise manner under efficient mixing conditions, and is preferably carried out under a reduced pressure of 100 torr or less in order to improve gas-solid contact.

The copolymerization ratio of bisphenol A and other aromatic dihydroxy compounds in the present invention can be selected according to the birefringence, processability and physical properties required by those skilled in the art, but is not particularly limited, but preferably 0.01 to 0.99 mol, preferably 1 mol of bisphenol A. Preferably, the use in the range of 0.02 to 0.50 moles can secure sufficient physical properties.

The polycarbonate copolymer resin produced by the solid phase polymerization according to the present invention shows excellent color tone and can be produced without a gel and also with high productivity.

The following examples illustrate the present invention without limiting the specific details of the polycarbonate copolymer and the preparation method described in the specification to those skilled in the art. Unless otherwise specified, temperature is in degrees Celsius (° C), parts are in weight, weight is in number average molecular weight (Mn) or weight average molecular weight (Mw), and the molecular weight of known polystyrene is standard. Based on the determination at 30 ° C temperature conditions in THF by GPC.

Low molecular weight polycarbonate prepolymers are prepared by melt polymerization with bisphenol-A by varying the composition of bisphenol-HEFL having a number average molecular weight of 1,000 to 10,000 g / mol.

TPPTPB is an abbreviation of Tetraphenylphsphonium tetraphenylbrate and TMAH is an abbreviation of tetramethyl ammonium hydroxide.

Example 1

a) Preparation of Low Molecular Weight Amorphous Polycarbonate Prepolymer

Bisphenol-A (0.95 mol, Kumho Petrochemical), 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene (bisphenol-HEFL) (0.05 mol, Aldrich Chemicals) and diphenyl carbonate ( 1.08 mol, Aceto Co.) is placed in the reactor and the process of purging nitrogen in the reactor to remove oxygen is continued 3-4 times. The reactor was immersed in an oil bath at atmospheric pressure to maintain a temperature range of 180 ° C., and then the stirrer was rotated at a speed of 100 rpm to completely melt the reaction within 15 minutes to obtain a homogeneous mixture. 6.5 x 10 ^-2 mol of TPPTPB and 7.5 x 10 ^-7 mol of TMAH are diluted in deionized water (pure of 18 mohms of resistance) to a concentration of 1 g / 100 ml, and then are continuously added to the reactor and the reaction mixture is stirred at 180 ° C. After reducing the reactor pressure to 150 mbar, the side reaction phenol was distilled off, and after 1 hour, the temperature was adjusted to 210 ° C. and the pressure to 100 mbar.

This condition is the optimum distillation condition of the side reaction phenol and the reactor pressure is reduced to 50 mbar at 210 ° C. after 30 minutes. After 1 hour, increasing the reactor temperature to 240 ° C. and reducing the pressure to 1 mbar yielded a colorless amorphous low molecular weight polycarbonate prepolymer having a number average molecular weight of 7,500 g / mol and a weight average molecular weight of 17,000 g / mol.

b) Preparation of Semicrystalline Polycarbonate Prepolymer

250 g of the low molecular weight amorphous polycarbonate prepolymer prepared through the above process is dissolved in 2.5 L of chloroform at a concentration of 10 wt%. Crystallizing the polycarbonate prepolymer using a mixed nonsolvent of acetone / methanol (50/50) yields a polycarbonate prepolymer of crystalline powder. The obtained crystalline polycarbonate prepolymer had an average particle diameter of 0.2 mm, a glass transition temperature of 133 ° C, a melting point of 208 ° C, a melting point of 183 ° C and a crystallinity of 27%.

c) preparation of high molecular weight polycarbonate copolymers

The powdered semi-crystalline polycarbonate prepolymer obtained in the above process was put into a solid-phase polymerization reactor made of choja without performing an independent grinding process, flowing nitrogen gas at a gas flow rate of 3L per minute, and 160 ° C / 1h, 170 ° C / 1h. , Solid phase polymerization was carried out at 180 ℃ / 1h, 190 ℃ / 2h and 200 ℃ / 4h conditions. After cooling the reaction mixture to room temperature, a colorless polycarbonate copolymer having a number average molecular weight of 24,000 g / mol and a weight average molecular weight of 50,000 g / mol can be obtained. The obtained polycarbonate had a glass transition temperature of 143 占 폚, a melting point of 2790 占 폚, a melting point of 267 占 폚 and a crystallinity of 42%.

Example 2

a) Preparation of Low Molecular Weight Amorphous Polycarbonate Prepolymer

Bisphenol-A (0.90 mol, Kumho Petrochemical), 9,9-bis (4- (2-hydroxy (ethoxy) phenyl) fluorene (bisphenol-HEFL) (0.10 mol, Aldrich Chemicals) and diphenyl carbonate (1.08 mol, Aceto Co.) is placed in the reactor and the process of purging nitrogen in the reactor to remove oxygen is carried out three to four times.The reactor is kept at atmospheric pressure to maintain a temperature range of 180 ° C in an oil bath. After soaking, rotate the stirrer at a speed of 100 rpm to completely melt the reaction within 15 minutes to obtain a uniform mixture of TPPTPB 6.5x10 ^-2 mol and TMAH 7.5x10 ^-7 mol with deionized water (18 mohms). Dilution to 1g / 100ml and then continuously added to the reactor and the reaction mixture is stirred at 180 ° C. After reducing the reactor pressure to 150 mbar, the side reaction phenol is distilled off and the temperature is 210 after 1 hour. ℃, the pressure is adjusted to 100 mbar.

This condition is the optimum distillation condition of the side reaction phenol and the reactor pressure is reduced to 50 mbar at 210 ° C. after 30 minutes. After 1 hour, increasing the reactor temperature to 240 ° C. and decreasing the pressure to 1 mbar yielded a colorless amorphous low molecular weight polycarbonate prepolymer having a number average molecular weight of 5,600 g / mol and a weight average molecular weight of 13,500 g / mol.

b) Preparation of Semicrystalline Polycarbonate Prepolymer

250 g of the low molecular weight amorphous polycarbonate prepolymer prepared through the above process is dissolved in 2.5 L of chloroform at a concentration of 10 wt%. Crystallization of the polycarbonate prepolymer using a mixed nonsolvent of acetone / methanol (50/50) yields a polycarbonate prepolymer of crystalline powder. The obtained crystalline polycarbonate prepolymer had an average particle diameter of 0.2 mm, a glass transition temperature of 128 ° C., a melting point of 188 ° C., a melting point of 173 ° C., and a crystallinity of 22%.

c) preparation of high molecular weight polycarbonate copolymers

The powdered semi-crystalline polycarbonate prepolymer obtained in the above process was put into a solid-phase polymerization reactor made of choja without performing an independent grinding process, flowing nitrogen gas at a gas flow rate of 3L per minute, and 160 ° C / 1h, 170 ° C / 1h. , Solid phase polymerization was carried out at 180 ℃ / 1h, 190 ℃ / 2h and 200 ℃ / 4h conditions. After cooling the reaction mixture to room temperature, a colorless polycarbonate copolymer having a number average molecular weight of 22,000 g / mol and a weight average molecular weight of 47,500 g / mol can be obtained. The obtained polycarbonate had a glass transition temperature of 142 ° C, a melting point of 274 ° C, a starting temperature of melting point of 245 ° C and a crystallinity of 48%.

Example 3

a) Preparation of Low Molecular Weight Amorphous Polycarbonate Prepolymer

Bisphenol-A (0.85 mol, Kumho Petrochemical), 9,9-bis (4- (2-hydroxy (ethoxy) phenyl) fluorene (bisphenol-HEFL) (0.15 mol, Aldrich Chemicals) and diphenyl carbonate (1.08 mol, Aceto Co.) is placed in the reactor and the process of purging nitrogen in the reactor to remove oxygen is carried out three to four times.The reactor is kept at atmospheric pressure to maintain a temperature range of 180 ° C in an oil bath. After soaking, rotate the stirrer at a speed of 100 rpm to completely melt the reaction within 15 minutes, yielding a uniform mixture of TPPTPB 6.5x10 ^-2 mol and TMAH 7.5x10 ^-7 mol with deionized water (18 mohms of resistance). Pure water), diluted to a concentration of 1g / 100ml and subsequently added to the reactor, and the reaction mixture is stirred at 180 ° C. After reducing the reactor pressure to 150 mbar, the side reaction phenol is distilled off and the temperature is 210 ° C after 1 hour. , Adjust the pressure to 100 mbar.

This condition is the optimum distillation condition of the side reaction phenol and the reactor pressure is reduced to 50 mbar at 210 ° C. after 30 minutes. After 1 hour, increasing the reactor temperature to 240 ° C. and reducing the pressure to 1 mbar yielded a colorless amorphous low molecular weight polycarbonate prepolymer having a number average molecular weight of 7,800 g / mol and a weight average molecular weight of 18,000 g / mol.

b) Preparation of Semicrystalline Polycarbonate Prepolymer

250 g of the low molecular weight amorphous polycarbonate prepolymer prepared through the above process is dissolved in 2.5 L of chloroform at a concentration of 10 wt%. Crystallizing the polycarbonate prepolymer using a mixed nonsolvent of acetone / methanol (50/50) yields a polycarbonate prepolymer of crystalline powder. The average particle diameter of the obtained crystalline polycarbonate prepolymer was 0.2 mm, the glass transition temperature was 132 ° C, the melting point was 185 ° C, the melting point was 172 ° C, and the crystallinity was 20%.

c) preparation of high molecular weight polycarbonate copolymers

The powdered semi-crystalline polycarbonate prepolymer obtained in the above process was put into a solid-phase polymerization reactor made of choja without performing an independent grinding process, flowing nitrogen gas at a gas flow rate of 3L per minute, and 160 ° C / 1h, 170 ° C / 1h. , Solid phase polymerization was carried out at 180 ℃ / 1h, 190 ℃ / 2h and 200 ℃ / 4h conditions. After cooling the reaction mixture to room temperature, a colorless polycarbonate copolymer having a number average molecular weight of 22,700 g / mol and a weight average molecular weight of 50,500 g / mol can be obtained. The obtained polycarbonate had a glass transition temperature of 143 ° C, a melting point of 276 ° C, a melting point of 262 ° C and a crystallinity of 41%.

Example 4

a) Preparation of Low Molecular Weight Amorphous Polycarbonate Prepolymer

Bisphenol-A (0.80 mol, Kumho Petrochemical), 9,9-bis (4- (2-hydroxy (ethoxy) phenyl) fluorene (bisphenol-HEFL) (0.20 mol, Aldrich Chemicals) and diphenyl carbonate (1.08 mol, Aceto Co.) is placed in the reactor and the process of purging nitrogen in the reactor to remove oxygen is carried out three to four times.The reactor is kept at atmospheric pressure to maintain a temperature range of 180 ° C in an oil bath. After soaking, rotate the stirrer at a speed of 100 rpm to completely melt the reaction within 15 minutes, yielding a uniform mixture of TPPTPB 6.5x10 ^-2 mol and TMAH 7.5x10 ^-7 mol with deionized water (18 mohms of resistance). Pure water), diluted to a concentration of 1g / 100ml and subsequently added to the reactor, and the reaction mixture is stirred at 180 ° C. After reducing the reactor pressure to 150 mbar, the side reaction phenol is distilled off and the temperature is 210 ° C after 1 hour. , Adjust the pressure to 100 mbar.

This condition is the optimum distillation condition of the side reaction phenol and the reactor pressure is reduced to 50 mbar at 210 ° C. after 30 minutes. After 1 hour, increasing the reactor temperature to 240 ° C. and decreasing the pressure to 1 mbar yielded a colorless amorphous low molecular weight polycarbonate prepolymer having a number average molecular weight of 6,700 g / mol and a weight average molecular weight of 17,800 g / mol.

b) Preparation of Semicrystalline Polycarbonate Prepolymer

250 g of the low molecular weight amorphous polycarbonate prepolymer prepared through the above process is dissolved in 2.5 L of chloroform at a concentration of 10 wt%. Crystallizing the polycarbonate prepolymer using a mixed nonsolvent of acetone / methanol (50/50) yields a polycarbonate prepolymer of crystalline powder. The obtained crystalline polycarbonate prepolymer had an average particle diameter of 0.2 mm, a glass transition temperature of 110 ° C., a melting point of 178 ° C., a melting point of 162 ° C., and a crystallinity of 18%.

c) preparation of high molecular weight polycarbonate copolymers

The powdered semi-crystalline polycarbonate prepolymer obtained in the above process was put into a solid-phase polymerization reactor made of choja without performing an independent grinding process, flowing nitrogen gas at a gas flow rate of 3L per minute, and 160 ° C / 1h, 170 ° C / 1h. , Solid phase polymerization was carried out at 180 ℃ / 1h, 190 ℃ / 2h and 200 ℃ / 4h conditions. After cooling the reaction mixture to room temperature, a colorless polycarbonate copolymer having a number average molecular weight of 23,500 g / mol and a weight average molecular weight of 53,500 g / mol can be obtained. The obtained polycarbonate had a glass transition temperature of 144 ° C, a melting point of 275 ° C, a melting point of 265 ° C and a crystallinity of 36%.

Example 5

a) Preparation of Low Molecular Weight Amorphous Polycarbonate Prepolymer

Bisphenol-A (0.95 mol, Kumho Petrochemical), 9,9-bis (4-hydroxyphenyl) fluorene (bisphenol-FL) (0.05 mol, Aldrich Chemicals) and diphenyl carbonate (1.08 mol, Aceto Co. ) And purge the nitrogen in the reactor 3-4 times to remove oxygen. The reactor was immersed in an oil bath at atmospheric pressure to maintain a temperature range of 180 ° C., and then the stirrer was rotated at a speed of 100 rpm to completely melt the reaction within 15 minutes to obtain a homogeneous mixture. 6.5 × 10 ⁻² mol of TPPTPB and 7.5 × 10 ⁻⁷ mol of TMAH are diluted to 1g / 100ml with deionized water (18 mohm of pure water) and then added to the reactor continuously and the reaction mixture is stirred at 180 ° C. After reducing the reactor pressure to 150 mbar, the side reaction phenol was distilled off, and after 1 hour, the temperature was adjusted to 210 ° C. and the pressure to 100 mbar.

This condition is the optimum distillation condition of the side reaction phenol and the reactor pressure is reduced to 50 mbar at 210 ° C. after 30 minutes. After 1 hour, increasing the reactor temperature to 240 ° C. and decreasing the pressure to 1 mbar yielded a colorless amorphous low molecular weight polycarbonate prepolymer having a number average molecular weight of 4,700 g / mol and a weight average molecular weight of 10,500 g / mol.

b) Preparation of Semicrystalline Polycarbonate Prepolymer

250 g of the low molecular weight amorphous polycarbonate prepolymer prepared through the above process is dissolved in 2.5 L of chloroform at a concentration of 10 wt%. Crystallizing the polycarbonate prepolymer using a mixed nonsolvent of acetone / methanol (50/50) yields a polycarbonate prepolymer of crystalline powder. The obtained crystalline polycarbonate prepolymer had an average particle diameter of 0.2 mm, a glass transition temperature of 133 ° C, a melting point of 217 ° C, a melting point of 176 ° C and a crystallinity of 26%.

c) preparation of high molecular weight polycarbonate copolymers

The powdered semi-crystalline polycarbonate prepolymer obtained in the above process was put into a solid-phase polymerization reactor made of choja without performing an independent grinding process, flowing nitrogen gas at a gas flow rate of 3L per minute, and 160 ° C / 1h, 170 ° C / 1h. , Solid phase polymerization was carried out at 180 ℃ / 1h, 190 ℃ / 2h and 200 ℃ / 4h conditions. After cooling the reaction mixture to room temperature, a colorless polycarbonate copolymer having a number average molecular weight of 24,000 g / mol and a weight average molecular weight of 60,000 g / mol can be obtained. The obtained polycarbonate had a glass transition temperature of 149 ° C, a melting point of 280 ° C, a starting temperature of melting point of 269 ° C and a crystallinity of 55%.

Example 6

a) Preparation of Low Molecular Weight Amorphous Polycarbonate Prepolymer

Bisphenol-A (0.90 mol, Kumho Petrochemical), 9,9-bis (4-hydroxyphenyl) fluorene (bisphenol-FL) (0.10 mol, Aldrich Chemicals) and diphenyl carbonate (1.08 mol, Aceto Co. ) And purge the nitrogen in the reactor 3-4 times to remove oxygen. The reactor was immersed in an oil bath at atmospheric pressure to maintain a temperature range of 180 ° C., and then the stirrer was rotated at a speed of 100 rpm to completely melt the reaction within 15 minutes to obtain a homogeneous mixture. 6.5 × 10 ⁻² mol of TPPTPB and 7.5 × 10 ⁻⁷ mol of TMAH are diluted to decent concentration with deionized water (18 mohm pure water resistance) and then added to the reactor continuously and the reaction mixture is stirred at 180 ° C. After reducing the reactor pressure to 150 mbar, the side reaction phenol was distilled off, and after 1 hour, the temperature was adjusted to 210 ° C. and the pressure to 100 mbar.

This condition is the optimum distillation condition of the side reaction phenol and the reactor pressure is reduced to 50 mbar at 210 ° C. after 30 minutes. After 1 hour, increasing the reactor temperature to 240 ° C. and decreasing the pressure to 1 mbar yielded a colorless amorphous low molecular weight polycarbonate prepolymer having a number average molecular weight of 4,600 g / mol and a weight average molecular weight of 10,400 g / mol.

b) Preparation of Semicrystalline Polycarbonate Prepolymer

250 g of the low molecular weight amorphous polycarbonate prepolymer prepared through the above process is dissolved in 2.5 L of chloroform at a concentration of 10 wt%. Crystallizing the polycarbonate prepolymer using a mixed nonsolvent of acetone / methanol (50/50) yields a polycarbonate prepolymer of crystalline powder. The average particle diameter of the obtained crystalline polycarbonate prepolymer was 0.2 mm, the glass transition temperature was 136 ° C, the melting point was 195 ° C, the melting point was 168 ° C, and the crystallinity was 21%.

c) preparation of high molecular weight polycarbonate copolymers

The powdered semi-crystalline polycarbonate prepolymer obtained in the above process was put into a solid-phase polymerization reactor made of choja without performing an independent grinding process, flowing nitrogen gas at a gas flow rate of 3L per minute, and 160 ° C / 1h, 170 ° C / 1h. , Solid phase polymerization was carried out at 180 ℃ / 1h, 190 ℃ / 2h and 200 ℃ / 4h conditions. After cooling the reaction mixture to room temperature, a colorless polycarbonate copolymer having a number average molecular weight of 27,000 g / mol and a weight average molecular weight of 65,000 g / mol can be obtained. The obtained polycarbonate had a glass transition temperature of 155 占 폚, a melting point of 257 占 폚, a melting point of 245 占 폚 and a crystallinity of 35%.

Example 7

a) Preparation of Low Molecular Weight Amorphous Polycarbonate Prepolymer

Bisphenol-A (0.85 mol, Kumho Petrochemical), 9,9-bis (4-hydroxyphenyl) fluorene (bisphenol-FL) (0.15 mol, Aldrich Chemicals) and diphenyl carbonate (1.08 mol, Aceto Co. ) And purge the nitrogen in the reactor 3-4 times to remove oxygen. The reactor was immersed in an oil bath at atmospheric pressure to maintain a temperature range of 180 ° C., and then the stirrer was rotated at a speed of 100 rpm to completely melt the reaction within 15 minutes to obtain a homogeneous mixture. 6.5 x 10 ^-2 mol of TPPTPB (Tetraphenylphsphonium tetraphenylborate, TCI acid) and 7.5 x 10 ^-7 mol of TMAH (tetramethylammonium hydroxide, Aldrich) were diluted with deionized water (pure water of 18 mohm) and continuously And the reaction mixture is stirred at 180 ° C. After reducing the reactor pressure to 150 mbar, the side reaction phenol was distilled off, and after 1 hour, the temperature was adjusted to 210 ° C. and the pressure to 100 mbar.

This condition is the optimum distillation condition of the side reaction phenol and the reactor pressure is reduced to 50 mbar at 210 ° C. after 30 minutes. After 1 hour, increasing the reactor temperature to 240 ° C. and decreasing the pressure to 1 mbar yielded a colorless amorphous low molecular weight polycarbonate prepolymer having a number average molecular weight of 4,700 g / mol and a weight average molecular weight of 10,500 g / mol.

b) Preparation of Semicrystalline Polycarbonate Prepolymer

250 g of the low molecular weight amorphous polycarbonate prepolymer prepared through the above process is dissolved in 2.5 L of chloroform at a concentration of 10 wt%. Crystallization of the polycarbonate prepolymer using a mixed nonsolvent of acetone / methanol (50/50) yields a polycarbonate prepolymer of crystalline powder. The obtained crystalline polycarbonate prepolymer had an average particle diameter of 0.2 mm, a glass transition temperature of 143 ° C., a melting point of 182 ° C., a melting point of 170 ° C., and a crystallinity of 18%.

c) preparation of high molecular weight polycarbonate copolymers

The powdered semi-crystalline polycarbonate prepolymer obtained in the above process was put into a solid-phase polymerization reactor made of choja without performing an independent grinding process, flowing nitrogen gas at a gas flow rate of 3L per minute, and 160 ° C / 1h, 170 ° C / 1h. , Solid phase polymerization was carried out at 180 ℃ / 1h, 190 ℃ / 2h and 200 ℃ / 4h conditions. After cooling the reaction mixture to room temperature, a colorless polycarbonate copolymer having a number average molecular weight of 30,000 g / mol and a weight average molecular weight of 74,000 g / mol can be obtained. The polycarbonate obtained had a glass transition temperature of 157 ° C, a melting point of 255 ° C, a starting temperature of melting point of 242 ° C and a crystallinity of 32%.

Example 8

a) Preparation of Low Molecular Weight Amorphous Polycarbonate Prepolymer

Bisphenol-A (0.80 mol, Kumho Petrochemical), 9,9-bis (4-hydroxyphenyl) fluorene (bisphenol-FL) (0.20 mol, Aldrich Chemicals) and diphenyl carbonate (1.08 mol, Aceto Co. ) And purge the nitrogen in the reactor 3-4 times to remove oxygen. The reactor was immersed in an oil bath at atmospheric pressure to maintain a temperature range of 180 ° C., and then the stirrer was rotated at a speed of 100 rpm to completely melt the reaction within 15 minutes to obtain a homogeneous mixture. 6.5 × 10 ⁻² mol of TPPTPB and 7.5 × 10 ⁻⁷ mol of TMAH are diluted to 1g / 100ml with deionized water (18 mohm of pure water) and then added to the reactor continuously and the reaction mixture is stirred at 180 ° C. After reducing the reactor pressure to 150 mbar, the side reaction phenol was distilled off, and after 1 hour, the temperature was adjusted to 210 ° C. and the pressure to 100 mbar.

This condition is the optimum distillation condition of the side reaction phenol and the reactor pressure is reduced to 50 mbar at 210 ° C. after 30 minutes. After 1 hour, increasing the reactor temperature to 240 ° C. and reducing the pressure to 1 mbar yielded a colorless amorphous low molecular weight polycarbonate prepolymer having a number average molecular weight of 5,800 g / mol and a weight average molecular weight of 13,700 g / mol.

b) Preparation of Semicrystalline Polycarbonate Prepolymer

250 g of the low molecular weight amorphous polycarbonate prepolymer prepared through the above process is dissolved in 2.5 L of chloroform at a concentration of 10 wt%. Crystallization of the polycarbonate prepolymer using a mixed nonsolvent of acetone / methanol (50/50) yields a polycarbonate prepolymer of crystalline powder. The obtained crystalline polycarbonate prepolymer had an average particle diameter of 0.2 mm, a glass transition temperature of 150 ° C, a melting point of 195 ° C, a melting point of 180 ° C, and a crystallinity of 15%.

c) preparation of high molecular weight polycarbonate copolymers

The powdered semi-crystalline polycarbonate prepolymer obtained in the above process was put into a solid-phase polymerization reactor made of choja without performing an independent grinding process, flowing nitrogen gas at a gas flow rate of 3L per minute, and 160 ° C / 1h, 170 ° C / 1h. , Solid phase polymerization was carried out at 180 ℃ / 1h, 190 ℃ / 2h and 200 ℃ / 4h conditions. After cooling the reaction mixture to room temperature, a colorless polycarbonate copolymer having a number average molecular weight of 27,000 g / mol and a weight average molecular weight of 72,000 g / mol can be obtained. The obtained polycarbonate had a glass transition temperature of 159 ° C, a melting point of 250 ° C, a starting temperature of 239 ° C and a crystallinity of 34%.

Claims (9)

a) a low molecular weight amorphous polycarbonate prepolymer having a number average molecular weight of 1,000 to 10,000 g / mol by melt polymerization of a dihydroxy aromatic mixture comprising a dihydroxyaromatic compound containing a fluorene group and a diarylcarbonate; preparing a prepolymer); b) converting the low molecular weight amorphous polycarbonate prepolymer into a semi-crystalline prepolymer having a crystallinity of 10-30% by non-solvent induced crystallization; And c) preparing a high molecular weight polycarbonate copolymer having a weight average molecular weight of semi-crystalline prepolymer in the range of 25,000 to 200,000 g / mol by solid phase polymerization; Method of producing a high molecular weight polycarbonate copolymer resin comprising a. The method of claim 1, The dihydroxy aromatic compound may be represented by the following Chemical Formula 1; And a compound selected from Formula 2-1 or 2-2; Method for producing a high molecular weight polycarbonate copolymer resin, characterized in that a mixture of. [Formula 1]

[R ₁ is independently a functional group selected from halogen atom, nitro group, cyano group, C ₁ -C ₂₀ alkyl group, C ₄ -C ₂₀ cycloalkyl group or C ₆ -C ₂₀ aryl group, m and n is independently an integer of 0 to 4, X is an oxygen atom, a sulfur atom, -SO ₂ - group, an aliphatic radical of _{C 1 -C 20, C 6 -C} 20 aromatic radical, C ₆ -C ₂₀ of the annular Aliphatic radicals or

R ₂ and R ₃ are independently a hydrogen atom, an alkyl group of C ₁ -C ₂₀ , a cycloalkyl group of C ₄ -C ₂₀ or an aryl group of C ₄ -C ₂₀ , or Selected from fused rings of C ₄ -C _20. ] [Formula 2-1]

[Formula 2-2]

[In the formula, R ₄ to R ₆ independently represent a halogen atom, a nitro group, a cyano group and an alkyl group of C ₁ -C ₂₀ , a cycloalkyl group of C ₄ -C ₂₀ or an aryl group of C ₄ -C ₂₀ . , m, n, o, p, r and s are independently integers from 0 to 4.] The method of claim 2, The dihydroxy aromatic compound may be 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene (bisphenol-HEFL) or 9,9-bis (4- (2-hydroxyphenyl) fluorene It is a mixed dihydroxy aromatic compound of (bisphenol-FL) and 2,2'-bis (4-hydroxyphenyl) propane (bisphenol-A), The manufacturing method of the high molecular weight polycarbonate copolymer resin characterized by the above-mentioned. The method of claim 1, The diaryl carbonate is a method for producing a high molecular weight polycarbonate copolymer resin, characterized in that the compound of formula (3). [Formula 3]

[R ₇ independently represents halogen atom, nitro group, cyano group, C ₁ -C ₂₀ alkyl group, C ₁ -C ₂₀ alkoxycarbonyl group, C ₄ -C ₂₀ cycloalkyl group or C ₆ -C _Is a functional group selected from an aryl group of ₂₀ , and x and y are integers of 0 to 5, which act independently.] The method of claim 4, wherein The diaryl carbonates are diphenyl carbonate, bis (4-methylphenyl) carbonate, bis (4-chlorophenyl) carbonate, bis (4-fluorophenyl) carbonate, bis (4-nitrophenyl) carbonate, bis (2-nitro A method for producing a high molecular weight polycarbonate copolymer resin, characterized in that it is selected from phenyl) carbonate or bis (methyl salicylic) carbonate. The method of claim 1, The diaryl carbonate is diphenyl carbonate and the dihydroxy aromatic compound is a bisphenol-HEFL or a mixture of bisphenol-FL and bisphenol-A method for producing a high molecular weight polycarbonate copolymer resin The method of claim 1, The non-solvent may be an aliphatic hydrocarbon such as n-hexane, n-heptane or pyrrolium ether, an aromatic hydrocarbon such as toluene or xylene, a hydroxy aliphatic compound such as methanol, ethanol, 2-propanol, ethylene glycol or diethylene glycol, A method for producing a high molecular weight polycarbonate resin, characterized in that it is at least one selected from aliphatic ketones such as acetone, methyl ethyl ketone or methyl isobutyl ketone, and carboxylic ester compounds such as ethyl acetate and n-butyl acetate. delete A high molecular weight polycarbonate resin having a crystallinity of 10 to 60% prepared by the process according to any one of claims 1 to 7.