WO1994022938A1

WO1994022938A1 - Process for producing polycarbonate

Info

Publication number: WO1994022938A1
Application number: PCT/JP1994/000522
Authority: WO
Inventors: Toru Bando; Kenji Tanaka
Original assignee: Idemitsu Kosan Co., Ltd.
Priority date: 1993-03-31
Filing date: 1994-03-30
Publication date: 1994-10-13

Abstract

A process for producing a polycarbonate with excellent quality efficiently through transesterification using a reduced amount of a transesterification catalyst, which process comprises adding to the reaction system 10-6-10-1 mol, per mole of a dihydroxy compound as the main starting material, of a phenol selected from the group consisting of monohydric and dihydric phenols and mixtures thereof and having an acidity higher than that of the dihydroxy compound.

Description

Specification

Manufacturing method of polycarbonate

The present invention relates to a method for producing a polycarbonate used in the fields of electric and electronics and automobile. More specifically, the present invention relates to a method for producing polycarbonate capable of providing high-quality polycarbonate with high productivity. Technology background

Polycarbonate is an engineering plastic with excellent transparency, heat resistance and impact resistance, and is a resin widely used in the industrial field today. However, in the interface polycondensation method, there is a problem in that toxic phosgene gas and chlorine iodine methylene as a source of chlorine impurities are used in the production process, and improvement of the production method has been desired. . In order to solve this problem, recently, various improvements in the so-called melt polymerization method utilizing the transesterification reaction between carbonic acid diester and divalent phenol have been proposed.

In the production of polycarbonate by a transesterification reaction, a basic catalyst such as an alkali metal or alkaline earth metal carbonate, acetate or hydroxide is used as a reaction catalyst. Also, recently, for example, a method using a barium compound and a borate ester as a catalyst described in Japanese Patent Application Laid-Open No. 3-209392, and a method described in Japanese Patent Application Laid-Open No. 5-11445 have been described. Research on new catalyst systems such as a method using an electron donating amine compound and a compound containing the elements IIb, IVb, and Vb as catalysts is also being actively conducted. However, these catalysts inherently reduce the chemical stability of the carbonate bond, and therefore, if these catalysts remain in the final product, polycarbonate, they will have poor thermal stability and water resistance. This leads to deterioration of physical properties such as decomposability.

In order to prevent the deterioration of the physical properties of these final products, there is a method of reducing the amount of the above catalyst.However, this method slows down the polymerization rate and requires a long time for production. There is a problem that the cost is reduced, and as a result, the product cost is increased. Therefore, how to reduce the amount of catalyst to be added while maintaining productivity is an important study item in the production of polycarbonate using transesterification.

Also, Japanese Patent Application Laid-Open No. 4-296325 discloses a method in which an electron-donating amine compound is used as a catalyst, but this method is not always sufficient. Disclosure of the invention

The present invention has been used in the past by producing a polycarbonate by a transesterification method by adding a monovalent or divalent phenol having higher acidity than a dihydroxy compound as a main raw material to a reaction system as a cocatalyst. It is an object of the present invention to provide a method for producing a polycarbonate capable of reducing the amount of a transesterification catalyst added and producing a high-quality polycarbonate with high productivity.

That is, in the present invention, when a polycarbonate is produced by a transesterification reaction, the reaction system is selected from the group consisting of monovalent phenol, divalent phenol and a mixture thereof, and has a higher acidity than the dihydroxy compound as the main raw material. high Fuwenoru acids, relative to the dihydroxy compound to 1 mol of the main raw material, 1 0- ^6-1 0- ¹ mol is added, to provide a process for the preparation of polycarbonate which comprises reacting the presence of S. ether interchange catalyst Things.

According to the production method of the present invention, the transesterification reaction proceeds sufficiently even if the amount of the transesterification catalyst is reduced, and a polycarbonate having a large molecular weight can be obtained. Although the reaction route in the method of the present invention is not clear at present, for example, when a diester carbonate is used as the carbonate-forming compound, an active reaction intermediate is obtained by a reaction between the phenol having a high acidity and the diester carbonate. Is thought to be formed. Thus, at this stage, the mechanism of action of phenols with high acidity, that is, phenols selected from the group consisting of the above-mentioned monovalent phenols, divalent phenols and mixtures thereof, is not clear, but a small amount of Since the addition has the effect of promoting the ester exchange reaction, the following description will be used in the present specification in order to distinguish it from the raw material dihydroxy compound, particularly the aromatic dihydroxy compound. Sometimes referred to as a catalyst. BEST MODE FOR CARRYING OUT THE INVENTION

Examples of the polycarbonate produced by the production method of the present invention include polycarbonate, polyester carbonate and the like.

In the present invention, when a polycarbonate is produced by a transesterification reaction, the raw material is not particularly limited as long as a dihydroxy compound is used as a main raw material, and various materials used for production by a normal transesterification reaction are used. Can be The dihydroxy compound as the main raw material may be used in the form of the dihydroxy compound itself, or may be used in the form of dicarbonate (self-condensation) or monocarbonate (self-esterification).

Examples of the raw materials that can be used include (1) a dihydroxy compound as the component (A) and a diester carbonate as the component (B) (carbonate ester-forming compound), and (2) a diester of the dihydroxy compound and the (B) component as the (A) component. (3) dicarbonate of dihydroxy compound as component (A) and dicarbonate of component (B), (2) dicarbonate of dihydroxy compound (self-condensation), (4) monocarbonate of dihydroxy compound (self-esterification) And the like. Among these, a raw material composed of a dihydroxy compound as the component (A) and a diester carbonate as the component (carbonate-forming compound) (1) is preferably used.

Here, examples of the dihydroxy compound as the raw material (A) component preferably used in the transesterification reaction include an aromatic dihydroxy compound and an aliphatic dihydroxy compound.

Examples of the aromatic dihydroxy compound as an example of the component (A) of the raw material I include those represented by the following general formula (I).

(I)

[Wherein, R ¹ is independently a halogen atom, an alkyl group having 1 to 8 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, an n-butyl group, an isobutyl group, an amyl group, an isoamyl group, A cycloalkyl group having 5 to 7 carbon atoms or an aryl group having 6 to 12 carbon atoms, m is an integer of 0 to 4, Z is a single bond, 101, one CO—, — S—, —SO—, —S0 ₂ —, CR ² R ³ — (where R ² and R ³ are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkyl group having 6 to 12 carbon atoms. A cycloalkylene group having 5 to 15 carbon atoms; a 1,1-cycloalkylidene group having 5 to 15 carbon atoms; a ω-alkylene group having 2 to 12 carbon atoms; (II) or (IΓ)

The bond represented by is shown. ]

Such aromatic dihydroxy compounds include, for example, 4,4 'dihydroxybiphenyl, 4,4'dihydroxy-1,2,2'-dimethylbiphenyl, 4,4 'dihydroxy3,3'-dimethylbiphenyl Dihydroxybiphenyls, such as 4,4'-dihydroxy-3,3'-dicyclohexylbiphenyl and 3,3'-difluoro-4,4'-dihydroxybiphenyl; bis (4-hydroxyphenyl) ether, Bis (hydroxyaryl) ethers such as bis (3-fluoro-4-hydroxyphenyl) ether and bis (4-hydroxy-13-methylphenyl) ether; bis such as 4,4'-dihydroxybenzophenone (Hydroxyaryl) ketones; bis (4-hydroxyphenyl) sulfide, bis (3-methyl-14-hydroxy) Phenyl) Surufi de like bis (arsenate mud Kishiariru) Surufi earth; bis (4-arsenate Dorokishifueniru) sulfoxy, bis (3-methyl-4-arsenide Dorokishifueniru) sulfoxide, bis (3-phenylene Bis (hydroxyaryl) sulfoxides such as ru-1-hydroxyphenylsulfoxide; bis (4-hydroxyphenyl) sulfone, bis (3-methyl-14hydroxyphenyl) sulfone, bis (3-phenyl4) Bis (hydroxyaryl) sulfones such as -hydroxyphenyl) sulfone; bis (4-hydroxyphenyl) methane, bis (3-methyl-4-hydroxyphenyl) methane, bis (3-chloro-4-hydroxyphenyl) methane, Bis (3,5-dibromo-1-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) 1-1-phenylmethane, 11-bis (4-hydroxyphenyl) 1-11,1-diphenylmethane, 1, 1 Bis (2-tert-butyl 4-hydroxy-5-methylphenyl) 1—Phenylmethane, 1, 1 Bis (4—hydroxyphenyl) ethane, 1, 1—Bis (2—tert—Butyl 4-hydroxy-13-methylphenyl) ethane, 1 Bis (4-fluoro-4-hydroxyphenyl) ethane, 1,1 Bis (4-hydroxyphenyl) 1-1-phenyl-2-ethane, 2- (3-methyl-4-hydroxyphenyl) 1-2- (4-phenyl) 1-phenylene, 1,1-bis (4-hydroxydroxyphenyl) 1,2,2—triphenylene, 2,2-bis (4-hydroxydroxyphenyl) propane, 2 2 — Bis (3-methyl-4-hydroxydroxyphenyl) propane, 22-bis (2-methyl-4-hydroxyphenyl) propane, 2,2-bis (3,5—dimethyl-4-hydroxyphenyl) propane, 1, 1-bis (2-tert-butyl-4-hydroxyl-5-methylphenyl) propane, 22-bis (3-chloro-4-hydroxyphenyl) propane, 2,2-bis (3-fluoro-4-h (Droxyphenyl) propane, 2,2-bis (3-bromo-4-hydroxyphenyl) pro. 2,2-bis (3,5-difluoro-4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane, 2,2-bis (35-dibromo one 4 - arsenide Dorokishifue two Le) flop ⁰ emissions, 2 2 - bis (3 - promoter 4-arsenide Dorokishi one 5 - black port phenylene Le) propane, 2, 2 - bis (3 - to inhibit Dorokishifuweniru) Kisafuruo Lopropane, 2 2 —bis (3 — phenyl 2 — hydroxy phenyl) propane, 2, 2 Bis (4-hydroxyphenyl) butane, 2,2-bis (3-methyl-14-hydroxyphenyl) butane, 1,1bis (2-butyl-4-hydroxy-5-methylphenyl) butane, 1,11 Bis (2-tert-butyl-4-hydroxy-5-methylphenyl) butane, 1,1-bis (2-tert-butyl-4-hydroxy-15-methylphenyl) isobutane, 1,1-bis (2-tert) — Amyle 4-hydroxy-5-methylphenyl) butane, 2,2-bis (3,5-dichlo-l-4-hydroxyphenyl) butane, 2, 2-bis (3,5-dihb-mo 4-hydroxyphenyl) Butane, 2,2-bis (4-hydroxyphenyl) 1-4-methylpentane, 4,4-bis (4-hydroxyphenyl) heptane, 1,1-bis (2-tert-butyl-4-hydroxy) One 5—me Bis (hydroxyaryl) alkanes such as thiophene) heptane, 2,2-bis (4-hydroxyphenyl) octane, 1,2-bis (4-hydroxyphenyl) ethane, and 1,1-bis (4- (Hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (3-methyl-4-1hydroxyphenyl) cyclohexane, 1,1-bis (3-cyclohexyl) 4-Hydroxyphenyl) cyclohexane, 1,1-bis (3-phenyl 4-hydroxyphenyl) Bis (hydroxyaryl) cycloalkanes such as cyclohexane; 1,1'-bis (4-hydroxyphenyl) Bis) (p-diisopropylbenzene, 1,1'-bis (4-hydroxyphenyl) 1 m-diisopropylbenzene, etc. Aryl) methyl} benzenes and the like. As the aromatic dihydroxy compound other than the above general formula (I), the following general formula (III)

H0- ¾-0H (III)

( ⁴ ) k

(In the formula, R ⁴ is each independently a halogen atom or an alkyl group having 1 to 8 carbon atoms, and k represents an integer of 0 to ^4. )

Dihydroxybenzenes represented by the formula: halogen- and alkyl-substituted dihydroxybenzenes There is a kind of zeng. For example, resorcin, 3-methyl resorcin, 3-ethyl resorcin, 3-propyl resorcin, 3-butyl resorcin, 3-tert-butyl resorcin, 3-phenyl resorcin, 3-cumyl resorcin, 2,3,4,4, 6-Tetrafluororesorcin, 2,3,4,6-Tetrabromoresorcin, Catechol, Hydroquinone, 3-Methylhydroquinone, 3-Ethylhydroquinone, 3-Propylhydroquinone, 3-Butylhydroquinone 3-tert-butylhydroquinone, 3-phenylhydroquinone, 3-cumylhydroquinone, 2,3,5,6-tetramethylhydroquinone, 2,3,4,6-tetra-tert-butylhydroquinone, 2,5-dichlorohydridoquinone, 2,3,5,6-tetrafluorohydroquinone, 2,3,5,6-tetrabromoha Dorokinon and the like.

Specific examples of the aliphatic dihydroxy compound as an example of the component (A) of the raw material I include, for example, butane-1,4-diol, 2,2-dimethylpropane-1,1,3-diol, hexane-1,1,6 —Diol, diethylene glycol, triethylene glycol, tetraethylene glycol, octaethylene glycol, dipropylene glycol, N, N-methyljetanolamine, cyclohexane-1,3 —diol, cyclohexane-1,4-diol , 1,4-dimethylolcyclohexane, p-xylylene glycol, 2,2-bis (4-hydroxycyclohexyl) propane and the like.

Further, in the present invention, as the dihydroxy compound, 2,2,2 ', 2'-tetrahydro 3,3,3', 3'-tetramethyl- 1,1'-spilove [1H-indene]- Spiro compounds such as 6,6′-diol can also be used. Instead of a part of the above dihydroxy compounds, hydroxyalkyl esters of biphenyldicarboxylic acid, hydroxyalkyl esters of bicyclohexyldicarboxylic acid and the like can be used. Dihydric alcohols may be used. In this case, polyester carbonate is obtained.

Among them, in the present invention, the following general formula (IV)

(In the formula, R ⁵ , R ⁶ , R ⁷ and R ⁸ are a halogen atom, an alkyl group having 1 to 10 carbon atoms or a phenyl group.)

The aromatic dihydroxy compound represented by the following formula is preferably used.

Specifically, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) -1-methylpentane, 2 , 2-bis (4-hydroxyphenyl) octane, 4,4'-dihydroxy-2,2,2-triphenylene, 2,2-bis (3,5-jib-mouth 4-hydroxyphenyl) propane , 4,4'-dihydroxytetraphenylmethane, 2,2-bis (3-phenyl-4-hydroxyphenyl) propane and the like are preferably used.

In addition, these dihydroxy compounds may be used alone or in combination of two or more.

Examples of the carbonic acid diester used as the carbonic acid ester forming compound in the present invention include diaryl carbonate compounds, dialkyl carbonate compounds, and alkylaryl compounds.

Examples of the diaryl carbonate compound include, for example, the following general formulas (V) and (VI)

0

Ar ² OCOAr ² (V)

0 0

II II

Ar ² 0C0-Ar OCOAr ² (VI)

(In the formula, Ar ¹ represents a residue obtained by removing two hydroxyl groups from the aromatic dihydroxy compound, and Ar ² represents an aryl group.)

The compound represented by these is mentioned. Examples of the dialkyl carbonate compound include compounds represented by the following general formulas (VII) and (VIII)

0

R ⁹ OCOR ⁹ (VII)

0 0

-II II

R ⁹ 0C0-Ar ¹ — 0C0R ⁹ (VIII)

(In the formula, R ⁹ represents an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 4 to 7 carbon atoms, and Ar ¹ has the same meaning as described above.)

The compound represented by these is mentioned.

Examples of the alkylaryl carbonate compound include, for example, the following general formulas (I X) and (X)

0

Ar20C0R ⁹ (IX)

0 0

― II II

^{^{Ar 2 0C0 - Ar 1 - 0C0R}} 9 (X) '

(Where A, 8 1 " ² and 1 ^ have the same meaning as above.)

The compound represented by these is mentioned.

Specific examples of the carbonate Jiariru compounds, Jifue two Le carbonate, ditolyl Kabone, bis (black port phenyl) carbonate, di- _m - Kurejirukabo sulfonates, dinaphthyl carbonate, bis (Bifue two Lil) carbonate, Bisufu phenol A Bisufueniru Carbonate and the like.

Further, specific examples of the dialkyl carbonate compound include getyl carbonate, dimethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, bisphenol A bismethyl carbonate, and the like.

On the other hand, specific examples of the alkyl aryl carbonate compound include methyl phenyl carbonate, ethyl phenyl carbonate, butyl phenyl carbonate, cyclohexyl phenyl carbonate, and bisphenol A methyl phenyl carbonate. Examples of preferred carbonic diesters include diphenyl carbonate, bis (chlorophenyl) carbonate, dinaphthyl carbonate, getyl carbonate, dimethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate and the like. Is used.

Among these carbonic acid diesters, a carbonic acid diaryl compound, particularly difluorocarbonate, is preferably used.

These carbonic acid diesters may be used alone or in combination of two or more.

If necessary, a dicarboxylic acid or a dicarboxylic acid ester may be used instead of a part of the carbonic acid diester. In this case, polyester carbonate is obtained. Examples of the dicarboxylic acid and dicarboxylic acid ester include aromatic dicarboxylic acids such as isophthalic acid, terephthalic acid, diphenyl isophthalate, diphenyl terephthalate, dichloride isophthalate, dichloride terephthalate; succinic acid, glutaric acid, adipine Aliphatic dicarboxylic acids such as acid, pimelic acid, speric acid, azelaic acid, sebacic acid, decandioic acid, dodecandioic acid, diphenyl sebacate, diphenyl decandioate; cyclopropane dicarboxylic acid, 1,2- Cyclobutanedicarboxylic acid, 1,3-cyclobutanedicarboxylic acid, 1,2-cyclopentanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid Acid, 1,4-cyclohexanedicarboxylic acid, Diphenyl cyclopropanedicarboxylate, diphenyl 1,2-cyclobutanedicarboxylate, diphenyl 1,3-cyclobutanedicarboxylate, diphenyl 1,1,2-cyclopentanedicarboxylate, diphenyl 1,1,2-cyclohexanedicarboxylate, 1,3-cyclo Alicyclic dicarboxylic acids such as diphenyl hexanedicarboxylate and 1,4-six-open hexanedicarboxylate can be mentioned. The amount of the dicarboxylic acid and the dicarboxylic acid ester used is, for example, 50 mol% or less, preferably 30 mol% or less of the ester carbonate.

In addition, dihydric alcohols such as hydroxyalkyl esters of biphenyl carboxylic acid and hydroxyalkyl esters of bicyclohexyl carboxylic acid are used in combination with diester carbonate. And polyester as a raw material, polyester carbonate can be obtained.

Hereinafter, these are collectively referred to as carbonic acid diester.

The amount of the carbonic acid diester to be used is generally 0.90 to 1.50 mol, preferably about 0.95 to 1.25 mol, per 1 mol of the dihydroxy compound as the main raw material.

In the present invention, phenols having higher acidity than the above-mentioned main raw material dihydroxy compound are used as a co-catalyst.

In the present invention, the acidity is high when the pKa value of a dihydroxy compound used as a main raw material is A and the pKa value of phenols as a cocatalyst is B. Preferably, B has a relationship of A−B≥2. Satisfaction.

If the dihydroxy compound and the co-catalyst phenols as the main raw materials do not satisfy the relationship of the above formula, sufficient catalytic activity, that is, the effect of promoting the transesterification reaction may not be obtained. The preferred pKa value of the co-catalyst phenols is 3-9. If the pKa value of the phenols is less than 3, the effect as a cocatalyst may be insufficient, while if it exceeds 9, the transesterification catalyst may be poisoned. For example, when the dihydroxy compound as the main raw material is 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), the preferred phenols used as the cocatalyst, that is, pK a rather than bisphenol A Phenols whose values are lower by 2 or more and whose pKa values are in the range of 3 to 9 include 4,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxybenzobenzophenone, and Examples thereof include ditrophenol, 3-nitrophenol, 2-nitrophenol, 4-honoremil phenol, and 4-cyanophenol.

These phenols may be used alone or in combination of two or more.

Fuwenoru such as the promoter, the main raw material is dihydric Dorokishi Compound 1 mole against 1 0 ⁶ -1 0 ¹ mole, preferably 1 0_ ⁵ to 1 0 ² mol added. Amount is not expected sufficient catalytic effect is less than 1 0 ⁶ mol, exceeds 1 0- ¹ mol, depends on the type of co-catalyst added, polycarbonate Bok things as a final product In some cases, the heat resistance, especially the heat resistance and the hydrolysis resistance may be reduced.

A basic compound is preferably used as the transesterification catalyst. In particular, an alkali metal compound, an alkaline earth metal compound, a nitrogen-containing basic compound and the like are preferably used.

Specific examples of the alkaline metal compound and alkaline earth metal compound include organic acid salts, inorganic acid salts, oxides, hydroxides, hydrides, and alcohol salts of alkaline metal and alkaline earth metals. And the like.

More specifically, the alkali metal compounds include sodium hydroxide, hydroxide hydroxide, lithium hydroxide, sodium hydrogen carbonate, lithium hydrogen carbonate, lithium hydrogen carbonate, sodium carbonate, carbonate carbonate, Lithium carbonate, sodium acetate, acetate acetic acid, lithium acetate, sodium stearate, potassium stearate, lithium stearate, sodium borohydride, lithium borohydride, sodium borohydride, sodium benzoate, benzoic acid Lithium, lithium benzoate, disodium hydrogen phosphate, dibasic hydrogen phosphate, dilithium hydrogen phosphate, disodium bisphenol A salt, dilithium salt, dilithium salt, sodium phenol potassium salt, potassium salt Lithium salts and the like can be mentioned.

Examples of the alkaline earth metal compounds include calcium hydroxide, potassium hydroxide, magnesium hydroxide, strontium hydroxide, calcium hydrogen carbonate, barium hydrogen carbonate, magnesium hydrogen carbonate, strontium hydrogen carbonate, and calcium carbonate. Examples include shim, barium carbonate, magnesium carbonate, strontium carbonate, calcium acetate, barium acetate, magnesium acetate, strontium acetate, calcium stearate, barium stearate, magnesium stearate, and sodium stearate. it can.

Examples of the nitrogen-containing basic compound include amine compounds such as trimethylamine represented by R ₃ N (where R is an alkyl group such as methyl and ethyl, and an aryl group such as phenyl and tolyl). Triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, dimethylamine Tertiary amide compounds such as benzylamine, triphenylamine, etc., dimethylamine, getylamine, dipropylamine, dibutylamine, dipentylamine, represented by R ₂ NH (wherein R is the same as above). Secondary amine compounds such as dihexylamine, methylbenzylamine, diphenylamine, etc., and methylamine, ethylamine, propylamine, butylamine represented by RNH ₂ (where R is the same as above) Primary amide compounds such as pentane, pentylamine, hexylamine, benzylamine, and phenylamine;

N, N-dimethyl 4-amino pyridine, 4-ethylpyramino pyridine, 4-pyrrolidino pyridine, 4-amino pyridine, 2-amino pyridine, 2-hydroxy pyridine, 4-hydroxy pyridine, 2-methoxy pyridine, 4-methoxy pyridine Methoxy pyridine, imidazole, 2-methylimidazole, 4-methylimidazole, 2-dimethylaminoimidazole, 2-methoxyimidazole, 2-phenylimidazole, 2-mercaptoimidazole, aminoquinoline, dia Nitrogen-containing heterocyclic compounds such as zabicyclooctane (DABC 0);

Tetramethylammonium Niu Muhi Dorokishido (Me ₄ NOH), tetra E chill ammonium two Umuhi Dorokishi de (E t ₄ NOH), tetra Petit Ruan monitor © Muhi Dorokishi de (B u ₄ NOH), trimethylbenzylammonium ammonium Niu Muhi Dorokishido [C ₆ Ammonium hydroxide having an alkyl group such as H ₅ CH ₂ (Me) ₃ NOH], an aryl group, an araryl group and the like;

Tetramethylammonium Niu arm borohydride high dry de (Me _₄ NBH _4), tetrabutyl ammonium Niu arm borohydride high dry de (Bu _₄ NBH _4), tetra-Petit Ruan monitor © Muhu Eniruporeto (Bu _₄ NBPh _4), tetramethylammonium Niu arm tetra And basic salts such as phenyl borate (Me ₄ NBPh ₄ ).

Among these nitrogen-containing basic compounds, trihexylamine, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, and dimethylaminopyridine are preferably used.

These basic compounds can be used alone or in combination. The amount of these basic compounds used is based on 1 mole of the main raw material dihydroxy compound. On the other hand, it is usually from 10 to ⁸ mol to 10 to ² mol, preferably from 10 to ⁷ mol to 10 to ³ mol. If the amount is less than 10 to ⁸ mol, the polymerization rate may be low. If the amount is more than 10 to ² mol, the quality of the final product, such as coloring and heat resistance, may be reduced.

The reaction temperature of the transesterification in the present invention is not particularly limited, but is usually from 100 to 300 ° C, preferably from 130 to 280 ° C, and more preferably according to the progress of the reaction. It is desirable to increase the temperature gradually. When the temperature of this transesterification reaction is lower than 100 ° C., the progress of the reaction is slow and the production time is long, which is not economical. If the temperature exceeds 300 ° C., side reactions may occur, or the resulting polycarbonate may be colored.

The pressure during the transesterification reaction is set according to the reaction temperature according to the vapor pressure of the monomer used. This is not limited, provided that it is set so that the reaction is performed efficiently. Usually, it is desirable to keep the pressure at atmospheric pressure or in the initial stage of the reaction, and to reduce the pressure in the latter stage of the reaction to distill off alcohols and phenols generated by the transesterification reaction.

Further, the reaction time of the transesterification reaction may be performed until a polymer having a target molecular weight is obtained, and is usually about 0.2 to about 10 hours.

The transesterification reaction is preferably performed in an atmosphere of an inert gas such as nitrogen or argon.If necessary, a branching agent, a terminal terminator, an antioxidant, etc. may be added, or an inert solvent may be used. May be.

As a branching agent that can be used in the present invention, a polyfunctional compound having three or more functional groups in one molecule is used. Examples of such a polyfunctional compound include phloroglucin, pyrogallol, and 1 1,1,1-tris (4-hydroxyphenyl) methane, 1,1,1-tris (4-hydroxyphenyl) ethane, 1,1,1-tris (4-hydroxyphenyl) propane, 1,1 , 1-Tris (3-methyl-4-hydroxyphenyl) ethane, 4,6-dimethyl-2,4,6-tris (4-hydroxyphenyl) -1,2-heptene, 4,6-dimethyl-2,4,6 —Tris (4-hydroxydroxyphenyl) heptane, 2,6-dimethyl 1,2,4,6-tris (4-hydroxyphenyl) 1,3-heptene, 1,3,5-tris (2-hydroxyphenyl) benzene, 1,3,5-tris (4-hydroxyxyphenyl) Benzene, tris (4-hydroxyphenyl) phenylmethane, 2,2-bis [4,4-bis (4-hydroxyphenyl) cyclohexyl] propane, 2,4-bis [1- (4-hydroxyphenyl) isopropyl ] Phenol, 2,6-bis (2'-hydroxy-1 5'-methylbenzyl) -1-methylphenol, 2- (4-hydroxyphenyl) 1-2- (2,4-dihydroxyphenyl) propane, a, a ', a "-Tris (4-hydroxyphenyl)-1,3,5-triisopropylbenzene, α-methyl-α,', '-Tris (4-hydroxyphenyl) 1-1, 4-Jethylben Hexakis [4- {a- (4-hydroxyphenyl) isopropyl] phenyl] mono-terephthalate, tetrakis (4-hydroxyphenyl) methane, tetrakis [4- {α- (4-hydroxyphenyl) isopropyl] } Phenoxy] methane, 1,4-bis [(4 ', 4 "—dihydroxytriphenyl) methyl] benzene, 2,4—dihydroxybenzoic acid, trimellitic acid, trimesic acid, pyromellitic acid, Cyanuric acid chloride, 3,3-bis (3-methyl-4-hydroxyphenyl) 1-2-oxo2,3-dihydroindole, 3,3-bis (4-hydroxydroxyaryl) oxyindole, 5 —Chloroisatin, 5,7-dichloroisatin, 5-bromoisatin florodalic acid, etc. are listed.

Examples of the terminal terminating agent that can be used in the present invention include ο-η-butyl phenol, m-η-butyl phenol, ρ-η-butyl phenol, ο-isobutyl phenol, m-isobutyl phenol, p-isobutyl phenol, o-t-butylphenol, m-t-butylphenol, p-t-butylphenol, o-n-pentinophenol, m-n-pentinophenol, p-n-pentylphenol, o— n-hexylphenol, m-n-hexylphenol, p-n-hexylphenol, o-cyclohexylphenol, m-cyclohexylphenol, p-cyclohexylphenol, o-phenylphenol, m 1-phenylphenol, p-phenylphenol, o-n-nonylphenol, m—n—nonylphenol, p—n—nonylphenol, o—cumylphenol, m—cumylphenol, p—cumylphenol, 0-naphthylphenol, m—naphthylphenol, p—naphthylphenol, 2 , 6—Di-t-butylphenol, 2,5—Di-t-butylphenol, 2,4-Di-t-butylphenol, 3,5—Di-t-butylphenol, 2,5—Dimethylphenol, 3,5-Dicumylphenol, 1-Benzyl-4— (Hydroxybenzyl) benzene, Dibenzyl-41- (4-hydroxybenzyl) benzene, and 2,2,4-1 Trimethyl-4-1 (4-Hydroxyphenyl) ) Chromane and monovalent phenols such as chroman derivatives such as 2,4,4-trimethyl-41- (4-hydroxyphenyl) chroman.

Among such monovalent phenols, pt-butylphenol, p-cumylphenol, p-phenylphenol and the like are preferred, although not particularly limited in the present invention.

Other optional terminating agents include certain carbonic acid diester compounds. Specific examples of such a specific carbonic acid diester compound as a terminal terminator include carboxybutenylphenylphenyl carbonate, methylphenylbutylphenylcarbonylate, ethylphenylbutylphenylcarbonate, dibutyldiphenyldicarbonate. Nyl carbonate, biphenyl phenyl carbonate, cuminophenyl carbonate, dicumyl phenyl carbonate, naphthyl phenyl carbonate, dinaphthyl phenyl carbonate, carboxypropenyl phenyl carbonate, carboheptoxy phenyl phenyl Carbonate, carboxymethyl t-butyl phenyl carbonyl carbonate, carboxypropenyl phenyl carbonyl, chromanyl phenyl carbonate, dichromane carbonyl, etc. And the like. The C ₇ - _3. Primary alkyl carbonyl O carboxymethyl benzene, C ₇ - _3. - fatty alcohols, phenyl (C I _{1 2} - alkoxy) Benzoe one bets, Fuweniru di (C Bok _{1 2} - alkoxy) Benzoeto, Fuweniru tri (C _{i-1 2} - alkoxy) Benzoe Bok, phenyl (C I _{1 2} —Alkoxy) sulfonate. The amount of the terminal terminating agent used is preferably 0.05 to 10 mol% with respect to the dihydroxy compound as the main raw material. Of course, the amount of the terminal terminator used can be changed according to the molecular weight of the target polymer, etc., but usually, by using the amount in the above range, the hydroxyl terminal of the obtained polymer is sufficiently sealed. Therefore, a polymer sufficiently excellent in heat resistance and water resistance is obtained, which is preferable.

The above-mentioned monohydric phenol or carbonate diester compound as a terminal terminator may be partially added to the reaction system of the ester exchange reaction, and the remainder may be added as the ester exchange reaction proceeds. Further, in some cases, the whole amount may be added to the reaction system after the transesterification reaction has progressed to some extent.

Antioxidants that can be used in the present invention include tris (nonylphenyl) phosphite, trisphenyl phosphite, 2-ethylhexyl diphenyl phosphite, trimethyl phosphite, triethyl phosphite, and the like. Phosphorus antioxidants such as tricresyl phosphite and triaryl phosphite are preferably used.

The transesterification of the present invention is usually carried out without a solvent, but an inert solvent may be used if necessary.

Examples of the inert solvent that can be used in the present invention include aromatic compounds such as diphenyl ether, halogen diphenyl ether, diphenyl sulfone, benzophenone, polyphenyl ether, dichlorobenzene, and methylnaphthalene; carbon dioxide; Gases such as nitrous oxide and nitrogen, chlorofluorocarbons, alkanes such as ethane and propane, cyclohexane, tricyclo (5,2,10) —cycloalkanes such as decane, cyclooctane and cyclododecane , Ethylene, argen such as probe, or hexafluoride.

In addition, known additives such as plasticizers, pigments, lubricants, release agents, stabilizers, and inorganic fillers can be added to the polycarbonate obtained by the present invention. .

The polycarbonate obtained by the present invention can be blended with other polymers such as polyolefin and polystyrene. It is effective to use polyphenylene ether, polyether nitrile, terminal-modified polysiloxane compound, modified polypropylene, modified polystyrene and the like having a terminal group, NH ₂ group or the like at the terminal.

Hereinafter, the present invention will be described more specifically with reference to Examples of the present invention and Comparative Examples thereof, but the present invention is not limited to these Examples.

Example 1

2,2-bis (4-hydroxyphenyl) propane 22.8 g, diphenyl carbonate 21.4 g, sodium hydroxide 0.04 mg in a 50 Om 1 separable flask equipped with a stirrer and distillation apparatus Was introduced. To this was further added 13.9 mg of 412-to-mouth phenol. Thereafter, polymerization was carried out under an argon stream under the conditions of 180 ° C for 1 hour, 50mmHg, 240 ° C for 1 hour, and ImmHg, 270 ° C for 2 hours, and the resulting phenol was distilled off to obtain polyphenol. . Thermal analysis of this product showed a glass transition point (Tg) of 148 ° C. The reduced viscosity at 20 ° C. of a solution having a concentration of 0.2 g / d1 using methylene chloride as a solvent is 0.45 d1 / g, and the viscosity average molecular weight calculated from this value is 18 d / g. , 800.

Example 2

Polycarbonate was obtained in the same manner as in Example 1 except that 13.9 mg of 3-nitrophenol was added instead of 4-nitrophenol in Example 1. Thermal analysis of this product showed that the glass transition point (T g) was 146 ° C. The reduced viscosity at 20 ° C of a solution having a concentration of 0.2 g / d1 using methylene chloride as a solvent is 0.37 dL_g, and the viscosity average molecular weight calculated from this value is 14,800. Was.

Example 3

Polycarbonate was obtained in exactly the same manner as in Example 1, except that 11.9 mg of 4-cyanophenol was added instead of 4-nitrophenol in Example 1. Thermal analysis of this product showed a glass transition point (Tg) of 146 ° C. In addition, a solution of 0.2 g The reduced viscosity at ° C was 0.36 dl Zg, and the viscosity average molecular weight calculated from this value was 14,300.

Example 4

In Example 1, a polycarbonate was obtained in exactly the same manner as in Example 1, except that 22.Omg of 4-formylphenol was added instead of 412 trophenol. Thermal analysis of this product showed a glass transition point (T g) of 147. The reduced viscosity at 20 ° C of a 0.2 g / d 1 concentration solution using methylene chloride as a solvent was 0.41 dl / g, and the viscosity average molecular weight calculated from this value was 16,700. Was.

Example 5

A polycarbonate was obtained in exactly the same manner as in Example 1, except that 25.Omg of 4,4'-dihydroxydiphenylsulfone was added instead of 4-nitrophenol in Example 1. Thermal analysis of this product showed a glass transition point (Tg) of 148 ° C. The reduced viscosity at 30 of a solution having a concentration of 0.2 gZdI using methylene chloride as a solvent was 0.43 d1 Zg, and the viscosity average molecular weight calculated from this value was 17,700.

Example 6

A polycarbonate was obtained in exactly the same manner as in Example 1 except that 0.9 lmg of tetramethylammonium hydroxide was used instead of 0.04mg of sodium hydroxide. A thermal analysis measurement of the product showed that the glass transition point (T g) was 140.2 ° C. The reduced viscosity at 20 ° C of a 0.2 gZd 1 concentration solution using methylene chloride as a solvent was 0.29 dl Zg, and the viscosity average molecular weight calculated from this value was 11,100. .

Comparative Example 1

In Example 1, a polycarbonate was obtained in exactly the same manner as in Example 1, except that 22.Omg of 3-iodinol was added instead of 4-nitrophenol. Thermal analysis of this product showed that the glass transition point (T g) was 122 ° C. In addition, 0.2 g / d 1 solution with methylene chloride as a solvent at 20 ° C Was 0.15 dl Zg, and the viscosity average molecular weight calculated from this value was 4,900. This was brittle compared to the polycarbonate obtained in the example.

Comparative Example 2

Example 1 was repeated in exactly the same manner as in Example 1 except that the polymerization reaction was carried out using only 2,2-bis (4-hydroxyphenyl) propane, diphenyl carbonate, and sodium hydroxide. Polycarbonate was obtained. Thermal analysis of this product showed a glass transition point (Tg) of 127 ° C. Further, the reduced viscosity at 20 of a solution having a concentration of 0.2 gZd1 using methylene chloride as a solvent was 0.17 dlZg, and the viscosity average molecular weight calculated from this value was 5,700. This was brittle compared to the polycarbonate obtained in the example.

The results of Examples 1 to 6 and Comparative Examples 1 and 2 are summarized in the following table.

table 1

The obtained polycarbonate The co-catalyst phenols added The pKa value The viscosity average molecular weight of

(Mv)

Example 14 4-tutrophenol 7.16 "18,800 Example 2 3-dinitrophenol 8.36" 14,800 Example 3 4-cyanophenol 7.95 ° 14,300 Example 4 4-formylphenol 7.62 "16,700

4,4 'Jihi Drojijifu

Example 5 8.00 °

Ninores Norephone 17,700 Example 6 4-Nitrophenol 7.16 "11,100 Comparative Example 13 3-Iodide phenol 9.03 ° 4,900 Comparative Example 2, 5,700 Reference: pKa value of 2,2-bis (4-hydroxyphenyl) propane: 10.92 ⁾

(1) This pKa value is taken from C. H. Rochester et al., "The Chemistry of The Hydroxyl Group" (Ed. S, Patai) Interscience, New York, 1971 p374.

(2) This pKa value is calculated by the calculation method according to Ha Kett's rule described in the above text.

As can be seen from Table 1, the difference between the pKa value of the main raw material 2,2-bis (4-hydroxyphenyl) propane and the pKa value of the phenols added as cocatalysts is 2 or more. Thus, a polycarbonate having a sufficiently large molecular weight can be obtained.

The viscosity average molecular weight (Mv) in the table is

[η = 1.23 x 10-4 (Μν) ⁰ · ⁸³ was calculated. Industrial applications

According to the method for producing a polycarbonate of the present invention, when producing a polycarbonate by a transesterification method, the amount of a conventionally used transesterification catalyst is reduced, and a high-quality polycarbonate can be produced with high productivity. It becomes possible to manufacture well.

Claims

The scope of the claims

1. When producing a polycarbonate by transesterification, phenols selected from the group consisting of monohydric phenols, dihydric phenols and mixtures thereof and having a higher acidity than the dihydroxy compound of the main raw material are added to the reaction system. for dihydric mud alkoxy compounds 1 mol of the main raw material, 1 0- ^6-1 0-, and molar addition, the preparation of polycarbonate Bok, characterized in that to exist under the reaction of an ester exchange catalyst.

2. The production of polycarbonate according to claim 1, wherein in the transesterification reaction, 0.9 to 1.5 mol of the carbonic acid diester is used as the carbonic acid ester-forming compound per mol of the dihydroxy compound as the main raw material. Law.

3. The polycarbonate according to claim 2, wherein A and B have a relationship of A—B≥2, where A is the pKa value of the dihydroxy compound as the main raw material and B is the pKa value of the phenols. Manufacturing method.

4. The method for producing a polycarbonate according to claim 3, wherein the pKa value of the phenols is 3 to 9.

5. The phenols are 4,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxybenzophenone, 4-nitrophenol, 3-nitrophenol, 2-nitrophenol, and 2-formylphenol. 5. The method for producing a polycarbonate according to claim 4, which is selected from the group consisting of ethanol, 4-cyanophenol, and a mixture thereof.

6. Claims wherein the phenols are selected from the group consisting of 4,4'-dihydroxydiphenylsulfone, 4-nitofenphenol, 3-ditrophenol, 4-formylphenol and 4-cyanophenol. Polycarbonate described in 5 The method of manufacturing nets.

7. The dihydroxy compound as the main raw material has the following general formula

(In the formula, R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a halogen atom, an alkyl group having 1 to 10 carbon atoms or a phenyl group.)

3. The method for producing a polycarbonate according to claim 2, which is represented by:

8. The process for producing a polycarbonate according to claim 7, wherein the dihydroxy compound as a main raw material is 4,4'-bis (4-hydroxyphenyl) propane.

9. The method according to claim 8, wherein the carbonic acid diester is selected from the group consisting of diphenyl carbonate, bis (chlorophenyl) carbonate, dinaphthyl carbonate, dimethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, and a mixture thereof. Production method of polycarbonate.

10. The method for producing a polycarbonate according to claim 9, wherein the carbonic acid diester is diphenyl carbonate.

1 1. The process for producing a polycarbonate according to claim 2, wherein the transesterification catalyst is a basic catalyst.

12. The transesterification catalyst is selected from the group consisting of alkali metal compounds, alkaline earth metal compounds, nitrogen-containing basic compounds, and mixtures thereof. The method for producing a polycarbonate according to range 11.

13. The process for producing a polycarbonate according to claim 12, wherein the transesterification catalyst is sodium hydroxide or tetramethylammonium hydroxide.

14. The dihydroxy compound used as the main raw material is 4,4'-bis (4-hydroxyphenyl) propane, the carbonic acid diester is diphenyl carbonate, and the ester exchange catalyst is sodium hydroxide or tetramethylammonium. 7. The method for producing a polycarbonate according to claim 6, which is muhydroxide.