KR20040074527A - Preparation of polycarbonate resin - Google Patents

Abstract

PURPOSE: Provided is a method for efficiently producing a high molecular weight polycarbonate resin, which is stable and has excellent reactivity at melt polymerization condition, and can maintain excellent catalytic activity at melt polymerization and solid polymerization processes. CONSTITUTION: The method for preparing the polycarbonate resin comprises the step of polymerizing, more particularly transesterifying a starting material comprising dihydroxy compound and carbonic diester in the presence of polymerization catalyst. The polymerization catalyst is an organic basic compound based on amino group-bonded phosphonium, or a mixture of the organic basic compound and compound comprising alkali metal or alkali earth metal. In the method, solid polymerization can be effected without further adding a catalyst.

Description

Production method of polycarbonate resin {PREPARATION OF POLYCARBONATE RESIN}

The present invention relates to a method for producing a polycarbonate resin, and more particularly, stable and excellent reactivity under melt polymerization conditions, and maintains excellent catalytic activity in the melt polymerization and solid-phase polymerization process to efficiently produce a high molecular weight polycarbonate resin It relates to a method for producing a polycarbonate resin that can be produced.

Polycarbonate resins are widely used in various mechanical parts, optical discs, automotive parts, and other applications because of their excellent mechanical properties such as impact resistance, heat resistance, and transparency.

Conventional polycarbonate resins are prepared by interfacial polycondensation methods for directly reacting bisphenols such as bisphenol A with phosgene, or by melt polymerization or solid phase polymerization methods for transesterifying bisphenols and carbonic acid diesters (for example, diphenyl carbonate). It was.

Since the interfacial polycondensation method polymerizes the polymer while dissolving it in a solvent, the solution viscosity is extremely increased when preparing an aromatic polycarbonate having a high degree of polymerization, and thus a lot of effort and time is required for purification of the polymer such as washing and neutralization. need.

In addition, the transesterification (melting) method has the advantage of being able to produce polycarbonate at a lower cost than the interfacial polycondensation method, and has been attracting special attention in recent years because it is environmentally friendly without using toxic substances such as phosgene or methylene chloride. .

In the method for producing a polycarbonate resin by the melting method, the bisphenol and the carbonic acid diester are reacted under high temperature and reduced pressure in the presence of a specific catalyst.

Currently known catalysts include metal compound catalyst systems and nonmetal compound catalyst systems. As a metal compound catalyst system, U.S. Patent No. 3,153,008 discloses salt compounds such as hydroxides, acetates, alkoxides, carbonates, hydrides, hydroxides, or oxides of alkali or alkaline earth metals and transition metals such as zinc, cadmium, titanium, or lead. An organometallic compound and the like are disclosed. U. S. Patent No. 4,330, 664 also discloses aluminum hydride or borohydride.

In addition, as a non-metal compound catalyst system, a compound represented by the following formula (I) is disclosed in US Pat. No. 3,442,854:

[Formula I]

In the formula (I),

R ₁ , R ₂ , R ₃ , and R ₄ are each independently a hydrocarbon, Z is nitrogen, phosphorus, or arsenium, and X is tetra arylborohydride, bromide, phenolate, or diaryl phosphate.

In addition, US Pat. No. 5,168,112 is a primary, secondary or tertiary amine compound, aromatic compound derivatives including nitrogen such as pyridine, US Pat. No. 5,418,316 is guanidine and its derivatives, US Pat. No. 5,618,906 is a nonmetallic catalyst system. Phage Compounds, US Pat. No. 6,262,219, discloses cyclic compounds containing nitrogen, such as piperidine or morpholine.

When the concentration of the metal compound catalyst system is low, the reactivity is remarkably decreased, and when the concentration is high, irregularly branched polycarbonate resins are formed to reduce the chromaticity of the product and remain in the final polycarbonate resin to reduce the stability of the product. There is a problem. In addition, although the non-metallic compound catalyst system has high reactivity at low temperature, it requires a large amount of catalyst to show the same reactivity as the metal compound catalyst system. There is a problem that the high temperature reactivity is lowered.

Therefore, there is a need for further research on a method for producing polycarbonate resins efficiently and stably under melt polymerization conditions and maintaining excellent catalytic activity in melt polymerization and solid phase polymerization processes.

In order to solve the problems of the prior art as described above, an object of the present invention is to provide a method for producing a polycarbonate resin that can be efficiently produced in a high molecular weight polycarbonate resin is stable and excellent in melt polymerization conditions. .

Another object of the present invention is not only to maintain sufficient catalytic activity from the beginning to the end of the transesterification reaction, it is also possible to proceed with the solid-phase polymerization without the addition of a new catalyst polycarbonate resin that can efficiently produce a high molecular weight polycarbonate resin It is to provide a manufacturing method.

In order to achieve the above object, the present invention is a method for producing a polycarbonate resin,

Starting raw materials containing a dihydroxy compound and a carbonic acid diester,

Polymerizing under a catalyst of a phosphonium-based organic basic compound bonded to an amino group or a mixture of such organic basic compounds and a compound containing an alkali metal or an alkaline earth metal

It provides a method for producing a polycarbonate resin comprising a.

Hereinafter, the present invention will be described in detail.

The inventors of the present invention have studied phosphonium in which a starting material containing a dihydroxy compound and a diester of carbonic acid is combined with an amino group while studying a method for maintaining stable, excellent reactivity and excellent catalytic activity under melt polymerization conditions. The polycarbonate resin was prepared by transesterification under a polymerization catalyst of a series of organic basic compounds alone or a mixture of compounds containing such organic basic compounds and alkali or alkaline earth metals. As a result, the polycarbonate resin was stable and excellent in melt polymerization conditions. Rather, it was confirmed that a high molecular weight polycarbonate resin can be efficiently produced, thereby completing the present invention.

The present invention is characterized by producing a polycarbonate resin using a phosphonium-based organic basic compound bonded to an amino group or a mixture of such organic basic compounds and a compound containing an alkali metal or an alkaline earth metal as a polymerization catalyst.

The polycarbonate resin of the present invention can be produced by two methods, and the first method will be described first.

The present invention includes a dihydroxy compound and a phosphonium-based organic basic compound in which a starting raw material containing carbonic acid diester is combined with an amino group alone, or a mixture of such organic basic compounds and a compound containing an alkali metal or an alkaline earth metal. Provided is a method for producing a polycarbonate resin produced by transesterification under a polymerization catalyst.

As the organic basic compound of the phosphonium series bonded to the amino group used in the present invention, it is preferable to use a quaternary phosphonium salt represented by the following formula (1).

[Formula 1]

(In Formula 1,

R ¹ , R ² , R ³ and R ⁴ are each independently or simultaneously an amino group, a linear or branched alkyl group having 1 to 8 carbon atoms, or a cycloalkyl group; An aryl group having or not having a substituent which is a phenyl group, a tolyl group, a naphthyl group, or a biphenyl group; Or an arylalkyl group having or not having a substituent which is a benzyl group, wherein at least one of R ¹ , R ² , R ³ , and R ⁴ is an amino group represented by the following Chemical Formula 2,

[Formula 2]

In the formula (2),

R ⁵ and R ⁶ are each independently or simultaneously a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, or a cycloalkyl group; An aryl group having or not having a substituent which is a phenyl group, a tolyl group, a naphthyl group, or a biphenyl group; Or an arylalkyl group having or without a substituent which is a benzyl group, wherein R ⁵ and R ⁶ may form a ring with each other, and nitrogen at this time may form an amino group by forming a double bond with another nitrogen or phosphorus,

X is a halogen atom, hydroxyl group, alkyloxy group, aryloxy group, alkylcarbonyloxy group, aryl carbonyloxy group, HCO ₃ , CO ₃ , or BR ⁷ ₄ , where R ⁷ is a hydrogen atom, an alkyl group, or aryl Hydrocarbon group)

c is an integer of 1 or 2, wherein X is CO _3, and c is 2, X is not a CO ₃ and c is 1).

The quaternary phosphonium salt represented by the formula (1) may be tetrakis (dimethylamino) phosphonium hydroxide, tetrakis (diethylamino) phosphonium hydroxide, tetrakis (dipropylamino) phosphonium hydroxide, Amino phosphonium hydroxides having alkyl groups such as tetrakis (diphenylamino) phosphonium hydroxide and tetrakis (methylbenzylamino) phosphonium hydroxide, aryl groups, alkylaryl groups, or arylalkyl groups; Tetrakis (diphenylamino) phosphonium borohydrolide, tetrakis (dimethylamino) phosphonium borohydride, tetrakis (diphenylamino) phosphonium tetraphenylborate, or tetrakis (dimethylamino) phosphonium tetraphenylborate Basic ammonium salts such as; Tetrakis (diphenylamino) phosphonium acetate, tetrakis (diphenylamino) phosphonium carbonate, or tetrakis (tris (dimethylamino) phosphoranilideneamino) phosphonium chloride.

The phosphonium-based organic basic compound bonded to the amino group is preferably contained in an amount of 10 ^-1 to 10 ^-6 mol with respect to 1 mol of the dihydroxy compound used as a starting material for the transesterification reaction of the present invention, more preferably. Preferably it is included in 10 ^-2 to 10 ^-5 mol, most preferably in the range of 10 ^-3 to 10 ^-4 mol. When the content of the organic basic compound of the phosphonium-based compound bonded to the amino group is less than 10 ^-6 mol, the catalytic activity cannot be sufficiently exhibited at the beginning of the reaction, and when it exceeds 10 ^-1 mol, the cost increases and it is uneconomical. have.

A mixture of a phosphonium-based organic basic compound bonded to the amino group and a compound containing an alkali metal or an alkaline earth metal is used in an amount corresponding to 1 mol of the dihydroxy compound used as a starting material for the transesterification reaction of the present invention. It is preferably included in 10 ^-1 to 10 ^-8 mol, more preferably in the range of 10 ^-2 to 10 ^-7 mol, most preferably in the range of 10 ^-3 to 10 ^-6 mol. If the total amount of the compound containing organic basic compound of the phosphonium series combination with the amino groups, and alkali metal or alkaline earth metal is less than 10 ^-8 mol, and is impossible to sufficiently exhibit the effect of the catalyst, the 10 ^-1 mol If exceeded, there is a problem in that the cost is increased and the physical properties such as heat resistance and hydrolysis resistance of the final polycarbonate resin may be impaired. The compound containing the alkali metal or alkaline earth metal used in the present invention is not particularly limited, but preferably hydroxides such as lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, It is preferred to use one or more selected from the group consisting of carbonates, acetates, alkoxides, and borohydride compounds.

The compound containing the alkali metal or alkaline earth metal is preferably contained in 10 ^-3 to 10 ^-8 mol with respect to 1 mol of the dihydroxy compound used as the starting raw material of the transesterification reaction of the present invention, more preferably Is included in the range of 10 ^-4 to 10 ^-7 mol, most preferably in the range of 10 ^-5 to 10 ^-6 mol. When the content of the compound containing the alkali metal or alkaline earth metal is less than 10 ^-8 mol can not sufficiently exhibit the catalytic activity in the later stage of the reaction, when the content exceeds 10 ^-3 mol, the cost increases and is uneconomical problem There is this.

The starting raw materials used in the transesterification reaction of the present invention are not particularly limited, but any of various starting raw materials provided for a conventional transesterification reaction can be used. Preferred examples include dihydroxy compounds and carbonic acid diesters, diesters and dicarbonates of dihydroxy compounds, dicarbonate esters of dihydroxy compounds (self-condensation), monocarbonate esters of dihydroxy compounds (magnetic ester exchange) Reaction). Most preferably, the application material is a dihydroxy compound and a carbonic acid diester.

As the dihydroxy compound that can be used as a starting raw material used in the transesterification reaction, it is preferable to use an aromatic dihydroxy compound or an aliphatic dihydroxy compound.

As the aromatic dihydroxy compound, a compound represented by Chemical Formula 3 may be used:

[Formula 3]

In the formula (3),

R ⁸ and R ⁹ are each independently or simultaneously a halogen atom such as fluorine, chlorine, bromine or iodine, or a methyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, secondary-butyl An alkyl group having 1 to 8 carbon atoms such as a group, a tert-butyl group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, or an octyl group,

d and e are each independently or simultaneously an integer of 0 to 4,

Z is a single bond, an alkylene group of 1 to 8 carbon atoms, an alkylidene group of 2 to 8 carbon atoms, a cycloalkylene group of 5 to 15 carbon atoms, a cycloalkylidene group of 5 to 15 carbon atoms, -S, -SO-, -SO _2- , -O-, -CO-, a compound represented by the following formula (4), or a compound represented by the following formula (5):

[Formula 4]

[Formula 5]

In Z of Formula 3, the alkylene group having 1 to 8 carbon atoms or the alkylidene group having 2 to 8 carbon atoms may be a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, an ethylidene group, or isopropyl And a dendene group. The cycloalkylene group having 5 to 15 carbon atoms or the cycloalkylidene group having 5 to 15 carbon atoms includes a cyclopentyl group, a cyclohexylene group, a cyclopentylidene group, a cyclohexylidene group, and the like.

Examples of the aromatic dihydroxy compound represented by Chemical Formula 3 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, 1,1-bis (2-tert-butyl-4-hydroxy-3-methylphenyl) ethane, 1-phenyl-1,1-bis (3-fluoro-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) prop Plate, 2,2-bis (3,5-difluoro-4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane, 2,2-bis ( 3,5-dibromo-4-1-hydroxyphenyl) propane, 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-tert-butyl-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-tert-butyl-4-hydroxy-5-methylphenyl Bis (hydroxyaryl) alkanes such as) heptane, 2,2-bis (4-hydroxyphenyl) octane, or 1,1- (4-hydroxyphenyl) ethane; 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, 4,4 Dihydroxybiphenyl, such as' -dihydroxy-3,3'- dicyclohexyl biphenyl or 3, 3- difluoro-4,4'- dihydroxy biphenyl, can be used.

Aromatic dihydroxy compounds other than the compound represented by Formula 3 include dihydroxybenzene, halogen, or alkyl-substituted dihydroxybenzene, and examples thereof include resorcinol, 3-methylresorcinol, 3-ethylresorcinol, 3-propylresorcinol, 3-butylresorcinol, 3-tert-butylresorcinol, 3-phenylresorcinol, 3-cumyl sorsinol , 2,3,4,6-tetrafluororesorcinol, 2,3,4,6-tetrabromoresorcinol, catechol, hydroquinone, 3-methylhydroquinone, 3-ethylhydroquinone, 3-propylhydroquinone, 3-butylhydroquinone, tert-butylhydroquinone, 3-phenylhydroquinone, 3-cumylhydroquinone, 2,5-dichlorohydroquinone, 2,3,5,6-tetra Methylhydroquinone, 2,3,5,6-tetra-tert-butylhydroquinone, 2,3,5,6-tetrafluorohydroquinone, or 2,3,5,6-tetrabromohydroquinone There is this.

The aliphatic dihydroxy compound is butane-1,4-diol, 2,2-dimethylpropane-1,3-diol, hexane-1,6-diol, diethylene glycol, triethylene glycol, tetraethylene glycol, octa Ethylene glycol, dipropylene glycol, N-methyldiethanolamine, cyclohexane-1,3-diol, cyclohexane-1,4-diol, 1,4-dimethylolcyclohexane, p-xylylene glycol, 2, 2-bis (4-hydroxycyclohexyl) propane, dihydric alcohol, dihydric phenol), adduct of ethylene oxide, adduct of propylene oxide and the like can be used.

As mentioned above, it is preferable to use the said dihydroxy compound as a starting raw material used for the transesterification reaction of this invention, It is preferable to use bisphenol A especially.

In addition, the carbonic acid diester that can be used as the starting raw material used in the transesterification reaction may be one selected from the group consisting of carbonates of diaryl compounds, carbonates of dialkyl compounds, and carbonates of alkylaryl compounds. .

As the carbonate of the diaryl compound, a compound represented by the following Chemical Formula 6, or a compound represented by the following Chemical Formula 7, may be used:

[Formula 6]

[Formula 7]

In the formulas (6) and (7),

Ar ¹ , Ar ² , Ar ³ , and Ar ⁴ are each independently or simultaneously an aryl group,

D ¹ is a residue obtained by removing two hydroxyl groups from the aromatic dihydroxy compound described above.

Examples of the diaryl compound carbonate represented by Formula 6 or Formula 7 include diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, bis (m-cresyl) carbonate, dinaphthyl carbonate, and bis (diphenyl) carbonate Or bisphenol A-bisphenol carbonate can be used.

As the carbonate of the dialkyl compound, a compound represented by Formula 8 or a compound represented by Formula 9 may be used:

[Formula 8]

[Formula 9]

In the formulas (8) and (9),

R ¹⁰ , R ¹¹ _, R ¹² , and R ¹³ are each independently or simultaneously an alkyl group having 1 to 6 carbon atoms, or a cycloalkyl group having 4 to 7 carbon atoms,

D ² is a residue obtained by removing two hydroxyl groups from the aromatic dihydroxy compound described above.

As the carbonate of the dialkyl compound represented by Formula 8 or Formula 9, diethyl carbonate, dimethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, or bisphenol A-bis (methyl) carbonate may be used.

As the carbonate of the alkylaryl compound, a compound represented by Formula 10 or a compound represented by Formula 11 may be used:

[Formula 10]

[Formula 11]

In Formula 10 and Formula 11,

Ar ⁵ and Ar ⁶ are each independently or simultaneously an aryl group,

R ¹⁴ and R ¹⁵ are each independently or simultaneously an alkyl group having 1 to 6 carbon atoms, or a cycloalkyl group having 4 to 7 carbon atoms,

D ³ is a residue obtained by removing two hydroxyl groups from the aromatic dihydroxy compound described above.

As the carbonate of the alkylaryl compound represented by Formula 10 or Formula 11, methylphenyl carbonate, ethyl phenyl carbonate, butyl phenyl carbonate, cyclohexyl phenyl carbonate, bisphenol A-methylphenyl carbonate, and the like can be used.

As mentioned above, it is preferable to use the said diester carbonate as a starting raw material used for the transesterification reaction of this invention, and it is especially preferable to use diphenyl carbonate.

Starting raw materials which can be used for the transesterification reaction of the present invention include diacetic acid ester of bisphenol A, dipropionic acid ester of bisphenol A, dibutyric acid ester of bisphenol A, or bisphenol A in addition to the above dihydroxy compound and carbonic acid diester. Diesters of dihydroxy compounds such as dibenzoic acid esters; Bicarbonate esters of dihydroxy compounds such as bismethyl carbonate of bisphenol A, bisethyl carbonate of bisphenol A, or bisphenol carbonate of bisphenol A; Or monocarbonate esters of dihydroxy compounds such as monomethyl carbonate of bisphenol A, monoethyl carbonate of bisphenol A, monopropyl carbonate of bisphenol A, or monophenyl carbonate of bisphenol A.

The dihydroxy compound and the carbonic acid diester used as starting materials for the transesterification reaction of the present invention preferably contain a carbonic acid diester / dihydroxy compound in a molar ratio of 0.9 to 1.5. More preferably, it is included in the molar ratio of 0.95 to 1.20, most preferably it is included in the molar ratio of 0.98 to 1.20.

In the present invention, in the production of the polycarbonate resin, additives such as terminal stoppers, branching agents, and antioxidants may be further used as necessary.

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 polycarbonate resin obtained.

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 (12), represented by the following formula (13) Compound, a compound represented by Formula 14, a compound represented by Formula 15, a compound represented by Formula 16, Group to compounds of the formula 17 can be used a monovalent phenol derivatives, such as only chroman of the formula 18 or formula 19.

[Formula 12]

[Formula 13]

[Formula 14]

[Formula 15]

In the formula of Formula 14 and Formula 15,

n are each independently or simultaneously an integer of 7 to 30,

[Formula 16]

[Formula 17]

In Formula 16, and Formula 17,

R ¹⁶ are each independently or simultaneously an alkyl group having 1 to 12 carbon atoms,

k is an integer of 1 to 3, each independently or simultaneously.

[Formula 18]

[Formula 19]

Preferably, the terminal stopper is a p-tert-butylphenol, p-cumylphenol, p-phenylphenol, a compound represented by the formula (14), a compound represented by the formula (15), a compound represented by the formula (16) Or a compound represented by the above formula (17) is preferably used.

The terminal stopper is preferably contained in 0.05 to 10 mol with respect to 1 mol of the dihydroxy compound used as the starting raw material of 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 dihydroxy compound and the carbonic acid diester proceeds, it is possible to add all of the terminal stopper.

The branching agent is phloroglucine, trimellitic acid, 1,1,1-tris (4-hydroxyphenyl) ethane, 1- [α-methyl-α- (4'-hydroxyphenyl) ethyl] -4 -[α ', α'-bis (4'-hydroxyphenyl) ethyl] benzene, α, α', α-tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene, or director Tin bis (o-cresol) and the like can be used.

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.

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 carried out at a temperature of 180 to 300 ℃, more preferably 180 gradually depending on the progress of the reaction It is good to raise to 300 degreeC. If the reaction temperature is less than 100 ℃ can lower the rate of transesterification reaction, if it exceeds 330 ℃ there is a problem that the side reaction or the resulting polycarbonate resin can be colored. The reaction pressure during the transesterification reaction is not particularly limited, and can be adjusted according to the vapor pressure of the monomer used, and the reaction temperature, but in the initial stage of the reaction, the reaction pressure is set to an atmospheric pressure (atmospheric pressure) of 1 to 10 atm, and the reaction. Later, the pressure is reduced to finally 0.1 to 100 mbar.

In addition, the reaction time during the transesterification reaction may be carried out until the target molecular weight, preferably 0.2 to 10 hours.

The transesterification reaction is preferably carried out in the absence of an inert solvent, but may be carried out in the presence of 1 to 150% by weight of an inert solvent of the polycarbonate 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. It may also be carried out under an inert gas atmosphere if necessary, wherein the inert gas is a gas such as argon, carbon dioxide, dinitrogen monoxide, nitrogen; Chlorofluoro hydrocarbons, alkanes such as ethane or propane, or alkenes such as ethylene or propylene and the like.

Phenols, alcohols, or esters thereof corresponding to the carbonic acid diester used as the transesterification reaction proceeds under the above conditions; And inert solvent is stripped 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.

In addition, the manufacturing method of the polycarbonate resin of the present invention follows the second method, which will be described in detail.

The present invention includes a dihydroxy compound and a phosphonium-based organic basic compound in which a starting raw material containing carbonic acid diester is combined with an amino group alone, or a mixture of such organic basic compounds and a compound containing an alkali metal or an alkaline earth metal. The present invention provides a method for producing a polycarbonate resin prepared by prepolymerization by a transesterification reaction under a polymerization catalyst to prepare a polycarbonate prepolymer, followed by solid phase polymerization of the polycarbonate prepolymer (second method).

The polycarbonate prepolymer prepared by the pre-polymerization by the transesterification reaction is under a polymerization catalyst comprising a phosphonium-based organic basic compound alone or a mixture of such organic basic compounds and compounds containing alkali or alkaline earth metals bonded to amino groups, As the starting material, the dihydroxy compound and the carbonic acid diester are used, and if necessary, additives such as an end stopper, a branching agent, an antioxidant, and the like are mixed, followed by heating to monohydrate corresponding to the carbonic acid diester. It can be prepared by a transesterification reaction to desorb the oxy compound and the like.

The phosphonium-based organic basic compound, starting raw material, terminal stopper, branching agent, and antioxidant combined with the amino group may use the same kind of compound as described in the first method.

The phosphonium-based organic basic compound bonded to the amino group is preferably contained in an amount of 10 ^-2 to 10 ^-8 mol with respect to 1 mol of the dihydroxy compound used as a starting material, more preferably 10 ^-3 to 10 It should be included as ^-7 mol. If the content is less than 10 ^-8 mol can not fully exhibit the catalytic activity in the early stage of the reaction, if the content exceeds 10 ^-2 mol there is a problem that the cost increases and is uneconomic.

The ratio of use of the starting material dihydroxy compound and the carbonic acid diester may vary depending on the reaction conditions, but the carbonic acid diester is preferably included in 0.9 to 2.5 mol with respect to 1 mol of the dihydroxy compound, more preferably. Preferably 0.98 to 1.5 mol.

The reaction temperature at the time of the prepolymerization may vary depending on the type, content, and other conditions of the raw material or the catalyst, but is preferably carried out at a temperature of 50 to 350 ℃, more preferably 100 to 320 ℃, more preferably Preferably it is carried out at a temperature of 100 to 300 ℃, most preferably 150 to 280 ℃. If the reaction temperature is less than 50 ℃ transesterification reaction does not proceed sufficiently, if it exceeds 350 ℃ is a problem that the starting raw material carbonic acid diester is distilled off from the transesterification system together with the by-product monohydroxy compound. have. In addition, the reaction time is preferably preferably performed for 1 minute to 100 hours, preferably 2 minutes to 10 hours.

In addition, during the prepolymerization, the reaction pressure is preferably performed at 0.1 to 100 mbar, more preferably at 1 to 10 mbar. When the reaction pressure is less than 0.1 mbar, the starting raw material carbonic acid diester is distilled off to change the composition in the transesterification reaction system. If the reaction pressure exceeds 100 mbar, the by-product monohydroxy compound is not distilled off. There is a problem that can interfere with the progress of the reaction.

At this time, in order to prevent the polycarbonate prepolymer from coloring in the prepolymerization step of the present invention, it is preferable to perform the prepolymerization reaction at a low temperature as short as possible, in particular a few minutes to several hours at a reaction temperature of 150 to 280 ℃ It is preferable to carry out.

Such a method is preferable for preparing a relatively low molecular weight polycarbonate prepolymer in prepolymerization, and the present invention can easily obtain a colorless transparent polycarbonate prepolymer having the required degree of polymerization.

In the prepolymerization, as the reaction proceeds, a monohydroxy compound corresponding to the carbonic acid diester is produced, and the reaction rate can be increased by removing the by-product outside the reaction system. In addition, a method of removing the monohydroxy compound produced by introducing an inert gas such as nitrogen, argon, helium, carbon dioxide, or a lower hydrocarbon gas into the reaction system while carrying out effective stirring, and a method of carrying out the reaction under reduced pressure , Or a method using both methods together may be preferably used.

The prepolymerization reaction as described above is preferably carried out in a molten state. The solvent which can be used at this time is an inert solvent, such as methylene chloride, chloroform, 1,2-dichloroethane, tetrachloroethane, dicyclobenzene, tetrahydrofuran, diphenylmethane, or diphenyl ether, and is usually melted in the absence of a solvent. It may also be carried out in the state.

The reactor used in the prepolymerization by the transesterification reaction to produce a polycarbonate prepolymer may be a conventional polymerization reactor, in particular a vertical or horizontal reactor equipped with a stirrer controlled by a jacket, an external heat exchanger, etc. Can be used. In addition, the reaction process may consist of one to several stages, and a plurality of reactors may be used in series or in parallel. The reaction may be batchwise, continuous, or a combination thereof, in particular continuous in order to obtain a uniform polycarbonate prepolymer.

In addition, in the method of preparing the polycarbonate prepolymer by prepolymerization by the transesterification reaction of the present invention, it is important to prevent distillation of the carbonic acid diester outside the reaction system. Therefore, the raw material dihydroxy compound and the carbonic acid diester are melted once or several times and supplied to the reactor, or the powder of the raw material is added to the molten dihydroxy compound to obtain a melt of the raw material. It is preferable. In addition, unreacted carbonic acid diesters are more likely to be distilled away at higher temperatures and higher vacuums, that is, they are closely related to temperature and pressure, thereby controlling the temperature and pressure conditions of the reactor to distill off the monodihydroxy compound or polycarbonate prepolymer. It is preferable to calculate the degree of reaction progress from the viscosity of and to control these feedbacks. In addition, distillation of carbonic acid diesters can be reduced by providing a battery or a distillation column between the reactor and the condenser to increase the recovery efficiency of the distilled monohydroxy compound.

The viscosity average molecular weight (Mv) of the polycarbonate prepolymer obtained by the above method is preferably 1,000 to 30,000, more preferably 1,500 to 30,000, most preferably 3,000 to 20,000. When the viscosity average molecular weight of the polycarbonate prepolymer is less than 1,000, it requires a long time in the solid phase polymerization step, there is a problem that it is difficult to hold a solid phase with a low melting point. In addition, when the viscosity average molecular weight exceeds 30,000, it cannot be used as a polycarbonate, and in many cases, it is not necessary to further polymerize to a higher molecular weight. In addition, the terminal ratio (molar ratio) of the polycarbonate prepolymer is preferably 1: 4 to 4: 1 at the end of the carbonate terminal: hydroxyl group, more preferably 1: 1.5 to 1.5: 1, and most preferably 1: 1. To 1.1: 1. If the terminal ratio is not included in the above range, there is a limit to the target final molecular weight, there is a problem that can not produce a high molecular weight polycarbonate resin.

The polycarbonate prepolymer prepolymerized by the transesterification reaction as described above prepares a polycarbonate resin by a method of polymerizing by heating to a solid phase in an inert gas atmosphere or under reduced pressure (solid phase polymerization).

The weight average molecular weight of the polycarbonate prepolymer used in the solid phase polymerization is preferably 2,000 to 20,000, more preferably 2,500 to 15,000, most preferably 4,000 to 12,000. When the polymerization average molecular weight is less than 2,000, there is a problem in that a long time reaction time is required during solid phase polymerization.

In this case, in some cases, the step of crystallizing the polycarbonate prepolymer before the solid phase polymerization may be further performed. The crystallization treatment is carried out in order to raise the melting point of the polycarbonate prepolymer by crystallization and not to cause fusion of the polycarbonate 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, the polycarbonate prepolymer is dissolved in a suitable solvent, the solvent is evaporated, and a non-solvent for the polycarbonate prepolymer is added to precipitate a solid polycarbonate prepolymer, or the solvent has a low solubility in the polycarbonate prepolymer. There is a method in which a polycarbonate prepolymer is contacted with a liquid solvent or solvent vapor to infiltrate the solvent in the polycarbonate prepolymer to crystallize.

Preferred solvents for the solvent treatment of such polycarbonate prepolymers include chloromethane, methylene chloride, chloroform, carbon tetrachloride, chloroethane, dichloroethane (various), trichloroethane (various), trichloroethylene, or tetrachloroethane ( Aliphatic halogen hydrocarbons such as various kinds); 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 polycarbonate prepolymer or the solvent, the degree of crystallization required, the treatment temperature, etc., but is preferably used at 0.05 to 100 times, more preferably 0.1 to 50 times the weight of the polycarbonate prepolymer. It is good to be.

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

The temperature Tc (° C.) for performing such heat crystallization is preferably in the range from the glass transition temperature (Tg) of the polycarbonate resin to be obtained to the melting temperature Tm (° C.) of the polycarbonate prepolymer. In particular, since the crystallization rate of the polycarbonate prepolymer is lowered at a low temperature, the preferable heat crystallization temperature Tc (° C) is preferably in the range represented by the following formula (1).

[Equation 1]

Tm-50 ≤ Tc ≤ Tm

The heat crystallinity of the polycarbonate prepolymer may be carried out while maintaining a constant temperature in the above formula (1), 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 polycarbonate prepolymer generally increases 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 polycarbonate 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 polycarbonate prepolymer, the presence or absence of a catalyst, the crystallization temperature, the crystallization method, etc., but it is preferably carried out for 1 to 200 hours.

The polycarbonate prepolymer heat-crystallized as described above is solid-phase polymerized to prepare a polycarbonate resin.

In the solid phase polymerization, the catalyst used during the preliminary polymerization may remain so that the polymerization may be carried out without adding a catalyst, and the monohydroxy compound or the carbonic acid diester produced by the solid phase polymerization may be extracted out of the reaction system. Can promote the reaction. As a method for extracting the monohydroxy compound or the carbonic acid diester from the reaction system, an inert gas such as nitrogen, argon, helium, carbon dioxide, a lower hydrocarbon gas, or the like is introduced, and the monohydroxy compound or the carbonic acid diester is introduced into the reaction system. A method of removing with 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, supplied hydrocarbon gas), it is preferable to heat the gas to a temperature near the reaction temperature in advance.

The shape of the polycarbonate prepolymer used for the solid phase polymerization is not particularly limited, but the large bulk polycarbonate prepolymers delay the reaction rate and are difficult to handle, so that the polycarbonate prepolymers such as pellets, beads, granules, and powders desirable. It is also possible to use a solid polycarbonate prepolymer by crushing it to an appropriate size. In particular, the polycarbonate prepolymer crystallized by the solvent treatment after the prepolymerization is usually obtained in the form of porous granules or powders, and the porous polycarbonate prepolymer is a monohydroxy compound or a carbonic acid diester which is a byproduct in the case of solid phase polymerization. It is preferable because extraction is easy.

In addition, the solid phase polymerization may further use additives such as powder, liquid, or gaseous end stoppers, branching agents, antioxidants, etc. of the first method, and these may improve the quality of the polycarbonate resin obtained. It works.

The reaction temperature Tp (° C.) and the reaction time during the solid phase polymerization depend on the type (chemical structure, molecular weight, etc.) or type of the polycarbonate prepolymer, the type or amount of the catalyst, the crystallinity of the polycarbonate prepolymer, or the melting temperature Tm '(° C.). Can vary. In addition, it may vary depending on the degree of polymerization or other reaction conditions of the polycarbonate resin to be obtained, but preferably a temperature at which the polycarbonate prepolymer is not melted from the glass transition temperature (Tg) of the polycarbonate resin to be obtained without melting. It is preferable that it is the range to. More preferably, it is preferably performed for 1 minute to 100 hours, most preferably 0.1 to 50 hours.

[Equation 2]

Tm'-50 ≤ Tc ≤ Tm '

The reaction temperature range of the solid phase polymerization is preferably a solid phase polymerization at 150 to 260 ° C., more preferably at 180 to 230 ° C. when the polycarbonate resin of bisphenol A is prepared.

In order to provide uniform heat to the polymer during the polymerization during the solid phase polymerization, or to facilitate extraction of the by-product monohydroxy compound or carbonic acid diester, a method using a stirring blade or a reactor having a structure in which the reactor itself rotates is used. It is preferable to use a stirring method such as a method of mixing, a method of flowing by heating gas, or the like.

The weight average molecular weight of the polycarbonate resin obtained by the solid state polymerization as described above is 6,000 to 200,000, preferably 10,000 to 50,000, more preferably 15,000 to 40,000. The polycarbonate resin of the present invention having the above weight average molecular weight can be usefully used for industrial purposes.

The shape of the polycarbonate resin obtained by the solid phase polymerization may vary depending on the shape of the polycarbonate prepolymer used, but is usually a powder such as beads, granules, or powder. In addition, the crystallinity of the obtained polycarbonate is usually higher than that of the polycarbonate prepolymer. That is, the polycarbonate resin prepared according to the present invention is a crystalline polycarbonate resin in powder form. In addition, the crystalline polycarbonate 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 polycarbonate resin of the present invention may use a batch type, a flow type, or a combination thereof. In addition, in general, prepolymerization is intended to produce a relatively low molecular weight polycarbonate prepolymer, whereas the present invention, prepolymerization by transesterification reaction is not necessary for the expensive reactor for high viscosity fluid required for high temperature melt polymerization, The crystallization process can be crystallized by solvent or heat treatment of the polycarbonate prepolymer, and no special equipment is required. Solid phase polymerization can also be polymerized with any device that can substantially heat the polycarbonate prepolymer and remove by-product monohydroxy compounds or carbonic acid diesters.

As described above, according to the production method of the present invention, a polycarbonate resin is used under the polymerization catalyst of a phosphonium-based organic basic compound bonded to an amino group alone or a mixture of such organic basic compounds and a compound containing an alkali metal or an alkaline earth metal. It is possible to polymerize at a low temperature, to improve the reaction rate, and to efficiently prepare a high molecular weight polycarbonate resin by preparing a solid phase polymerized polycarbonate prepolymer obtained by preparing or by prepolymerization under the polymerization catalyst. It works.

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

Into a 300 mL glass reactor incorporating a magnetic stirrer was added 85.61 g (0.375 mol) of bisphenol A (BPA) as a dihydroxy compound and 84.35 g (0.394 mol) of diphenyl carbonate as a carbonic acid diester. Tetrakis (tris (dimethylamino) phosphoranylideneamino) phosphonium chloride was charged with a phosphonium-based organic basic compound bonded to an amino group at a concentration of 2.5 × 10 ^-4 to 1 mol of bisphenol A, and then the atmosphere in the reactor Was substituted 5 times with nitrogen. The resulting mixture was heated to 170 ° C. and reacted in a nitrogen atmosphere for 30 minutes. Subsequently, the mixture was heated to 220 ° C., and at this temperature, the degree of vacuum was gradually increased for 30 minutes to reach a vacuum of 10 mbar, and then reacted for 90 minutes to terminate the reaction to obtain a transparent polycarbonate resin.

Comparative Example 1

A polycarbonate resin was prepared in the same manner as in Example 1, except that tetramethylammonium hydroxide was used as a polymerization catalyst in Example 1 at a concentration of 2.5 × 10 ^{−4 based} on 1 mol of bisphenol A. It was.

Comparative Example 2

A polycarbonate resin was prepared in the same manner as in Example 1, except that tetrabutylphosphonium hydroxide was used as a polymerization catalyst in Example 1 at a concentration of 2.5 × 10 ^{−4 based} on 1 mol of bisphenol A. Prepared.

The mass average molecular weights of the polycarbonate resins prepared in Example 1 and Comparative Examples 1 and 2 were measured using GPC, and the results are shown in Table 1 below.

division Polymerization Catalyst density Mass average molecular weight (Mw) Example 1 Tetrakis (tris (dimethylamino) phosphoranylideneamino) phosphonium chloride 2.5 × 10 ^-4 7,181 Comparative Example 1 Tetramethylammonium hydroxide 2.5 × 10 ^-4 3,400 Comparative Example 2 Tetrabutylphosphonium hydroxide 2.5 × 10 ^-4 6,740

As can be seen from the results of Table 1, in Example 1 of the present invention, a high molecular weight polycarbonate resin was efficiently used in comparison with Comparative Examples 1 and 2, using a phosphonium-based organic basic compound bonded to an amino group as a polymerization catalyst. Could be prepared as.

Example 2

Into a 300 mL glass reactor incorporating a magnetic stirrer was added 85.61 g (0.375 mol) of bisphenol A (BPA) as a dihydroxy compound and 84.35 g (0.394 mol) of diphenyl carbonate as a carbonic acid diester. Tetrakis (tris (dimethylamino) phosphoranylideneamino) phosphonium chloride was charged with a phosphonium-based organic basic compound bonded to an amino group at a concentration of 2.5 × 10 ^-4 to 1 mol of bisphenol A, and then the atmosphere in the reactor Was substituted 5 times with nitrogen. The resulting mixture was heated to 170 ° C. and reacted in a nitrogen atmosphere for 30 minutes. The mixture was then heated to 220 ° C. at which temperature the vacuum was gradually raised for 30 minutes to reach a vacuum of 10 mbar and then reacted for 90 minutes.

After completion of the reaction, the pressure in the reactor was restored to atmospheric pressure using nitrogen, and the polycarbonate prepolymer as the contents was extracted and ground. At this time, the mass average molecular weight of the polycarbonate prepolymer measured using GPC was 7,181 g / mole. The obtained polycarbonate prepolymer was dissolved in chloroform, added to methanol to deposit the powder, concentrated to dryness and vacuum dried to prepare a powdery polycarbonate prepolymer. 10 g of polycarbonate prepolymer was supplied to a 10 mm diameter × 200 mm length stainless steel pipe, and nitrogen was passed through at a rate of 3 L / min at 200 ° C. to give a solid phase polymerization reaction over time to prepare a polycarbonate resin. .

Comparative Example 3

In Example 2, a polycarbonate prepolymer having a mass average molecular weight of 8,548 g / mol was prepared using sodium acetate at a concentration of 3.0 × 10 ⁻⁵ relative to bisphenol A as a polymerization catalyst, and the same method as in Example 1 was used. Solid phase polymerization produced a polycarbonate resin.

Comparative Example 4

Tetramethylammonium hydroxide was used as a polymerization catalyst in Example 2 at a concentration of 2.5 × 10 ^-4 compared to bisphenol A, and the polymerization reaction was performed four times longer to obtain a polycarbonate prepolymer having a mass average molecular weight of 9,094 g / mol. To prepare a polycarbonate resin by solid phase polymerization in the same manner as in Example 1.

Comparative Example 5

Using tetrabutyl phosphonium hydroxide as a polymerization catalyst in Example 2 in a concentration of 2.5 × 10 ^-4 compared to bisphenol A to prepare a polycarbonate prepolymer having a mass average molecular weight of 6,740 g / mol, using the Example Solid phase polymerization in the same manner as in 1 to prepare a polycarbonate resin.

The mass average molecular weight of the polycarbonate resin prepared in Example 2 and Comparative Examples 3 to 5 was measured according to the solid state polymerization reaction time (5 hours, 10 hours, 15 hours), and the results are shown in Table 2 below. .

division Mass average molecular weight (Mw) Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 0 hours 7,181 8,548 9,094 6,740 5 hours 20,910 18,218 16,777 20,547 10 hours 27,924 21,207 24,810 27,017 15 hours 36,244 22,063 29,230 28,162

In the results of Table 2, Example 2 of the present invention is compared with Comparative Examples 3 to 5 by using a phosphonium-based organic basic compound bonded to an amino group as a polymerization catalyst, the higher the molecular weight It can be seen that the polycarbonate resin can be efficiently produced.

As described above, the production method of the polycarbonate resin of the present invention is stable and excellent in the melt polymerization conditions, it is possible to efficiently produce a high molecular weight polycarbonate resin, and from the beginning to the end of the transesterification reaction In addition to maintaining sufficient catalytic activity, there is an effect that can proceed with the solid-phase polymerization without the addition of a new catalyst.

Claims (22)

In the method for producing a polycarbonate resin, Starting material containing a dihydroxy compound and a carbonic acid diester Polymerizing under a catalyst of a phosphonium-based organic basic compound bonded to an amino group or a mixture of such organic basic compounds and a compound containing an alkali metal or an alkaline earth metal Method for producing a polycarbonate resin comprising a. The method of claim 1, a) starting raw materials containing a dihydroxy compound and a carbonic acid diester; Iii) phosphonium-based organic basic compounds bonded to amino groups; or Ii) a) phosphonium-based organic basic compounds bonded to amino groups; And B) compounds containing alkali or alkaline earth metals Mixture of Transesterification under a polymerization catalyst comprising a Method for producing a polycarbonate resin comprising a. The method according to claim 1 or 2, Method for producing a polycarbonate resin is a phosphonium-based organic basic compound bonded to the amino group is a quaternary phosphonium salt represented by the following formula (1): [Formula 1] In the formula of Formula 1, R ¹ , R ² , R ³ and R ⁴ are each independently or simultaneously an amino group, a linear or branched alkyl group having 1 to 8 carbon atoms, or a cycloalkyl group; An aryl group having or not having a substituent which is a phenyl group, a tolyl group, a naphthyl group, or a biphenyl group; Or an arylalkyl group having or not having a substituent which is a benzyl group, wherein at least one of R ¹ , R ² , R ³ , and R ⁴ is an amino group represented by the following Chemical Formula 2, [Formula 2] In the formula (2), R ⁵ and R ⁶ are each independently or simultaneously a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, or a cycloalkyl group; An aryl group having or not having a substituent which is a phenyl group, a tolyl group, a naphthyl group, or a biphenyl group; Or an arylalkyl group having or without a substituent which is a benzyl group, wherein R ⁵ and R ⁶ may form a ring with each other, and nitrogen at this time may form an amino group by forming a double bond with another nitrogen or phosphorus, X is a halogen atom, a hydroxyl group, an alkyloxy group, an aryloxy group, an alkylcarbonyloxy group, an aryl carbonyloxy group, HCO ₃ , CO ₃ , or BR ⁷ ₄ , where R ⁷ is a hydrogen atom, an alkyl group or an aryl group Hydrocarbons), c is an integer of 1 or 2, wherein X is CO _3, and c is 2, X is not a CO ₃ and c is 1. The method of claim 3, The quaternary phosphonium salt represented by the formula (1) may be tetrakis (dimethylamino) phosphonium hydroxide, tetrakis (diethylamino) phosphonium hydroxide, tetrakis (dipropylamino) phosphonium hydroxide, Amino phosphonium hydroxides having an alkyl group, an aryl group, an alkylaryl group, or an arylalkyl group, including tetrakis (diphenylamino) phosphonium hydroxide or tetrakis (methylbenzylamino) phosphonium hydroxide; Tetrakis (diphenylamino) phosphonium borohydrolide, tetrakis (dimethylamino) phosphonium borohydride, tetrakis (diphenylamino) phosphonium tetraphenylborate, or tetrakis (dimethylamino) phosphonium tetraphenylborate Basic ammonium salt containing; Tetrakis (diphenylamino) phosphonium acetate; Tetrakis (diphenylamino) phosphonium carbonate; And tetrakis (tris (dimethylamino) phosphoranylideneamino) phosphonium chloride. The method according to claim 1 or 2, A method for producing a polycarbonate resin comprising 10 ^-1 to 10 ^-6 mol of the phosphonium-based organic basic compound bonded to the amino group with respect to 1 mol of the dihydroxy compound as the starting material. The method according to claim 1 or 2, The compound containing the alkali metal or alkaline earth metal is selected from the group consisting of hydroxides, carbonates, acetates, alkoxides, and borohydrides of lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, or barium. The manufacturing method of polycarbonate resin chosen by 1 or more types. The method according to claim 1 or 2, A mixture of a phosphonium-based organic basic compound bonded to the amino group and a compound containing an alkali metal or an alkaline earth metal is 10 ^-1 to 10 ^-8 mol based on 1 mol of the dihydroxy compound as a starting material Manufacturing method. The method according to claim 1 or 2, A method for producing a polycarbonate resin, wherein the compound containing the alkali metal or the alkaline earth metal is contained in an amount of 10 ^-3 to 10 ^-8 mol based on 1 mol of the dihydroxy compound as a starting material. The method according to claim 1 or 2, A method for producing a polycarbonate resin wherein the dihydroxy compound is an aromatic dihydroxy compound or an aliphatic dihydroxy compound. The method according to claim 1 or 2, The method for producing a polycarbonate resin, wherein the carbonic acid diester is selected from the group consisting of carbonates of diaryl compounds, carbonates of dialkyl compounds, and carbonates of alkylaryl compounds. The method according to claim 1 or 2, Method for producing a polycarbonate resin containing the carbonic acid diester / dihydroxy compound in a molar ratio of 0.9 to 1.5. The method according to claim 1 or 2, A method for producing a polycarbonate resin further comprising at least one additive selected from the group consisting of terminal terminators, branching agents, and antioxidants. The method of claim 12, Method for producing a polycarbonate resin containing the terminal stopper is 0.05 to 10 mol with respect to 1 mol of the dihydroxy compound which is the starting raw material. The method of claim 2, The transesterification reaction is a reaction temperature of 100 to 330 ℃, the initial pressure of the reaction of 1 to 10 atm, the reaction pressure of 0.1 to 100 mbar, the reaction time is produced in the polycarbonate resin is carried out under the conditions of 0.2 to 10 hours Way. The method of claim 1, a) starting raw material containing a dihydroxy compound and a carbonic acid diester; Iii) phosphonium-based organic basic compounds bonded to amino groups; or Ii) a) phosphonium-based organic basic compounds bonded to amino groups; And B) compounds containing alkali or alkaline earth metals Mixture of Preparing a polycarbonate prepolymer by prepolymerization by transesterification under a polymerization catalyst comprising a; And b) solid-phase polymerization of the polycarbonate prepolymer of step a) Method for producing a polycarbonate resin comprising a. The method of claim 15, A method of preparing a polycarbonate resin, wherein the organic basic compound of the phosphonium-based compound including the amino group of step a) is contained in an amount of 10 ^-2 to 10 ^-8 mol based on 1 mol of the dihydroxy compound as a starting material. The method of claim 15, Method for producing a polycarbonate resin containing the carbonic acid diester of step a) is 0.9 to 2.5 mol with respect to 1 mol of the dihydroxy compound. The method of claim 15, The prepolymerization of step a) is a reaction temperature of 50 to 350 ℃, the reaction pressure is 0.1 mbar to 100 mbar, the reaction time is a method of producing a polycarbonate resin 1 minute to 100 hours. The method of claim 15, The polycarbonate prepolymer of step a) is a method of producing a polycarbonate resin having a viscosity average molecular weight (Mv) of 1,000 to 30,000. The method of claim 15, c) A method of producing a polycarbonate resin further comprising the step of crystallizing the polycarbonate prepolymer of step a). The method of claim 15, A method for producing a polycarbonate resin, wherein the crystallization treatment is a solvent treatment method or a heat crystallization method. The method of claim 15, The polycarbonate resin of step b) has a weight average molecular weight of 6,000 to 200,000.