JP2009040842A - Catalyst for producing polycarbonate and method for producing polycarbonate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a catalyst for producing polycarbonate, for efficiently producing high quality polycarbonate while taking the environment into consideration, and to provide a method for producing polycarbonate using the above catalyst. <P>SOLUTION: The catalyst for producing polycarbonate contains a reaction product of (a) a carrier prepared by bonding diamine to silica gel with (b) a palladium compound and with (c) a metal compound having a redox catalytic performance. The method for producing polycarbonate includes a first step of reacting an aromatic dihydroxy compound and a monohydric phenol with carbon monoxide and oxygen to produce a polycarbonate prepolymer, and a second step of subjecting the polycarbonate prepolymer to solid polymerization or melt polymerization to produce polycarbonate, and uses the above catalyst. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a catalyst for producing polycarbonate and a method for producing polycarbonate. Specifically, high-quality polycarbonate useful as a resin material in the electric / electronic field, the automobile field, the optical part field, the structural material field, and the like is efficiently considered while considering the environment. The present invention relates to a catalyst for producing a polycarbonate that can be produced and a method for producing a polycarbonate using the catalyst.

  As a method for producing polycarbonate, a method (solution method) is generally known in which an aromatic dihydroxy compound such as bisphenol A and phosgene are reacted in the presence of an alkali. In this method, in addition to using highly toxic phosgene, there is a problem that a stoichiometric amount of alkali salt is by-produced. Also known is a method (melting method) in which a carbonic acid diester such as diphenyl carbonate is used as a carbonyl source and heated and reacted (melting method), but this melting method requires heating for the production and melting of the carbonic acid diester. There is a problem that the polycarbonate obtained by heating to a high temperature is colored.

As a new polycarbonate production method, a method based on an oxidative carbonylation reaction using a palladium / redox agent / onium halide catalyst has been proposed, but the reaction rate is insufficient and only a polycarbonate having a low polymerization degree can be obtained. . (For example, refer to Patent Document 1).
In order to solve this problem, a polycarbonate oligomer is produced by performing an oxidative carbonylation reaction in a catalyst system of palladium compound / inorganic redox catalyst / organic redox catalyst / onium halide compound / dehydrating agent, and then the ester exchange method is used to produce a polycarbonate. (For example, refer to Patent Document 2).
However, with the catalyst of Patent Document 2, a polycarbonate having a high degree of polymerization is obtained. However, since the palladium compound is dissolved in a solvent (homogeneous catalyst), there is a possibility that a palladium (0) cluster is formed and deactivated. The separation of the catalyst is difficult, and the metal component tends to remain in the polycarbonate.
Furthermore, a catalyst system comprising a polynuclear metal complex compound having a plurality of palladium atoms as metal centers and cross-linked by a heterobidentate ligand, a redox catalyst and an onium halide compound (see Patent Document 3), polyvinylpyrrolidone and the like A method for obtaining a polycarbonate using a catalyst system (see Patent Document 4) containing a complex obtained by reacting a catalyst carrier with a palladium compound and a metal compound having a redox catalytic ability has been proposed. Cannot be obtained.
Further, a polycarbonate oligomer is produced by performing an oxidative carbonylation reaction in a catalyst system comprising an onium halide compound / dehydrating agent on a catalyst system in which a palladium compound and a metal compound having a redox catalytic activity are reacted with a specific organic carrier. Then, there is a method of obtaining a polycarbonate by a solid phase polymerization method (see, for example, Patent Document 5).
However, in the method of Patent Document 5, a polycarbonate having a high degree of polymerization is obtained, but there is a problem that the particle diameter of the catalyst used is fine and handling is difficult.

JP-A-53-68744 JP 2000-297148 A JP 2002-69170 A JP 2004-352878 A JP 2006-89617 A

    An object of the present invention is to solve the above-mentioned problems in a polycarbonate production method, to provide a polycarbonate production catalyst that can be easily separated from polycarbonate and can be used repeatedly, and to use the catalyst to produce harmful chlorine. It is to efficiently produce high-quality polycarbonate without using halogenated organic solvents such as dichloromethane and chloroform, which are considered to adversely affect gas, phosgene, and the environment.

  As a result of intensive studies to achieve the above object, the present inventors have achieved the above object by a reaction product of a support in which diamine is bound to silica gel, a palladium compound, and a metal compound having a redox catalytic ability. Found that you can. The present invention has been completed based on such findings.

That is, the present invention provides the following (1) to (9).
(1) (a) a catalyst for producing a polycarbonate, comprising a reaction product of a carrier obtained by binding diamine to silica gel, (b) a palladium compound, and (c) a metal compound having a redox catalytic ability,
(2) Further, (d) a catalyst for producing a polycarbonate according to the above (1) containing an onium compound,
(3) Further, (e) a catalyst for producing a polycarbonate according to the above (1) or (2) containing an organic redox agent,
(4) Furthermore, the catalyst for polycarbonate production according to any one of the above (1) to (3), further comprising (f) a dehydrating agent,
(5) The catalyst for producing a polycarbonate according to any one of (1) to (4), wherein the diamine is ethylenediamine,
(6) The catalyst for producing a polycarbonate according to any one of the above (1) to (5), wherein the palladium compound of (b) is a divalent palladium compound,
(7) The catalyst for producing a polycarbonate according to the above (1) to (6), wherein the metal compound having redox catalytic ability of (c) is a cobalt compound,
(8) The catalyst for producing a polycarbonate according to the above (2) to (7), wherein the onium compound of (d) is a compound obtained by quaternizing part or all of nitrogen or phosphorus of an organic carrier or an inorganic carrier with an alkyl halide. ,
(9) A first step of producing a polycarbonate prepolymer by reacting an aromatic dihydroxy compound and a monohydric phenol with carbon monoxide and oxygen, and producing a polycarbonate by solid-phase polymerization or melt polymerization of the polycarbonate prepolymer. A method for producing a polycarbonate, comprising using the catalyst for producing a polycarbonate according to any one of (1) to (8) above in the first step.

The catalyst for producing a polycarbonate of the present invention can be easily separated by filtration or the like after completion of the reaction, the amount of metal remaining in the polycarbonate from which the catalyst is separated is extremely low, can be used repeatedly, and has high catalyst efficiency.
By using the polycarbonate production catalyst of the present invention, no harmful chlorine gas, phosgene, no halogenated organic solvent such as dichloromethane or chloroform, which is considered to have an adverse effect on the environment, the degree of polymerization is high and there is no coloration High quality polycarbonate can be produced efficiently.

The polycarbonate production catalyst and polycarbonate production method of the present invention will be described in detail.
<(A) Carrier in which diamine is bonded to silica gel>
Silica gel is a hydrate of amorphous silicic acid and is represented by the SiO ₂ .nH ₂ O formula, but structurally, O is bonded to each vertex of the Si tetrahedron. Si is further bonded to O to have a three-dimensional network structure, and has a reactive hydroxyl group (silanol group) on the surface. The silica gel may be a natural product or a synthetic product (for example, a sol-gel method or a method in which silica hydrosol obtained by hydrolyzing silicon alkoxide is hydrothermally treated to obtain silica gel).
The catalyst for producing a polycarbonate of the present invention uses this silica gel bonded with a diamine as a carrier. Since the diamine is chemically bonded (hydrogen bond) with the silanol group on the surface of the silica gel, it is strongly supported on the surface, and the diamine once bonded is preferable in that it does not easily come off from the surface of the silica gel.
As the diamine for bonding, polymethylenediamine represented by the following general formula (1) is preferably used.
—NR ³ — (CR ¹ R ² ) _n —NR ⁴ R ⁵ (1)
In the general formula ^(1), R 1 ~R ⁵ represent a hydrogen atom or 1 to 10 carbon atoms, preferably 1 to 5 alkyl groups, may be the same or different. n represents an integer of 1 to 10, preferably 2 to 3.
Among these diamines, ethylenediamine is preferable, and a carrier represented by the following general formula (2) to which ethylenediamine is bonded is preferable because it can be easily obtained.
Silicagel- (X—NH—CH ₂ —CH ₂ —NH ₂ ) _n (2)
In general formula (2), X is a single bond, a methylene group, a polymethylene group having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms, an alkylene group, an alkylidene group, or a cycloalkylene group having 5 to 20 carbon atoms, preferably 5 to 10 carbon atoms. Group, a divalent organic group such as a cycloalkylidene group.
When X is not a single bond, silicagel-X-Cl formed by dehydration reaction using OH group of silanol group in silica gel in advance, for example, OH-X-Cl (X is a divalent organic group). The product of formula (2) is obtained by reacting with diamine. Specific examples of OH-X-Cl include 1-chloro-4-hydroxypropane, 1-chloro-6-hydroxyhexane, 1-chloro-4-hydroxycyclohexane, 1-chloro-4-hydroxybenzene, and the like. Is mentioned.
The carrier having diamine bonded to silica gel has an average particle size of about 50 to 1000 μm, preferably 50 to 200 μm.

<(B) Palladium compound>
The palladium compound is not particularly limited, but is preferably a divalent palladium compound, specifically, palladium (II) chloride, palladium (II) bromide, palladium (II) acetate, dichlorobis (acetonitrile) palladium. (II), dichlorobis (benzonitrile) palladium (II) and the like, and dichlorobis (acetonitrile) palladium (II) and dichlorobis (benzonitrile) palladium (II) having high solubility in a solvent are preferable. These palladium compounds may be used alone or in combination of two or more.

<(C) Metal compound having redox catalytic ability>
Examples of the metal in the metal compound having redox catalytic ability include lanthanoids, Group 5-7 transition metals, chromium, manganese, iron, cobalt, nickel, copper, and the like, and among these, cobalt is preferable. As the cobalt compound, cobalt (II) chloride, cobalt (II) acetate and the like are suitable. Of these, cobalt (II) chloride is preferred. The metal compound having redox catalytic activity is usually used in an amount of 0.5 to 100 mol, preferably about 2 to 10 mol, per 1 mol of the palladium compound. These metal compounds having redox catalytic ability may be used alone or in combination of two or more.
The reaction product is obtained by mixing the above components (a), (b) and (c) at room temperature in a solvent for dissolving the metal compound.
For example, after suspending a carrier in which a diamine is bound to silica gel in acetone, add an acetone solution of a palladium compound thereto, and stir at room temperature. After the palladium color disappears, a metal compound having redox catalytic ability The catalyst for producing polycarbonate of the present invention (hereinafter sometimes referred to as an immobilized catalyst) is obtained by adding an acetone solution of The solvent is not particularly limited as long as it can dissolve a palladium compound and a metal compound having redox catalytic ability, and acetone is particularly preferable.
These immobilized catalysts may be used alone or in combination of two or more.
For example, palladium (II) chloride as a palladium compound as component (b) and metal as a metal compound having redox catalytic ability as component (c) on a carrier represented by the above general formula (2) in which ethylenediamine is bonded to silica gel When the chloride (II) is reacted, the reaction product has a structure represented by the following general formula (3).
M in the general formula (3) represents a metal atom and is a lanthanoid, a Group 5-7 transition metal, chromium, manganese, cobalt, nickel, copper or the like.

Examples of commercially available carriers in which diamine is bonded to silica gel as component (a) include Diamine Silica manufactured by Fuji Silysia Chemical Co., Ltd. and Si-Diamine manufactured by Silicycle.
Diamine Silica and Si-Diamine are those in which X in the general formula (2) is a trimethylene group.

<(D) Onium compound>
The immobilization catalyst may contain an onium salt that is considered to activate a hydroxy compound, which is one of the starting materials for the production of polycarbonate described later. Examples of the onium salt include ammonium salts, oxonium salts, sulfonium salts, phosphonium salts, and selenonium salts. Of these, ammonium salts and phosphonium salts are preferred. For example, tetra (n-butyl) ammonium bromide, bis (triphenylphosphoranylidene) ammonium bromide, or the like is used as the ammonium salt. As the phosphonium salt, tetra (n-butyl) phosphonium bromide, tetraphenylphosphonium bromide, or the like is used.
In addition, as an onium compound, a compound in which nitrogen or phosphorus of an organic carrier or an inorganic carrier is partially or fully quaternized with an alkyl halide can be used. Organic carriers that can quaternize nitrogen or phosphorus with alkyl halides include diphenylphosphino-polystyrene, poly-4-vinylpyridine, poly-2-vinylpyridine, polyvinylpyrrolidone, bipyridino-polystyrene, N, N- (diisopropyl) Examples thereof include aminomethyl-polystyrene, N- (methylpolystyrene) -4- (methylamino) pyridine, N, N-diethanolaminomethyl-polystyrene, and inorganic carriers include diphenylphosphino-2-silica, pyridino-2 -Silica etc. are mentioned, and diphenylphosphino-polystyrene is particularly preferable. Examples of commercially available products include PS-Triphenylphosphine (PS-TPP) manufactured by Argonaut.
There is no restriction | limiting in particular as alkyl halide (RX), R is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, benzyl, etc. X includes bromine, chlorine, and iodine. Alkyl halides may be used alone or in combination of two or more.
The quaternization reaction of the organic carrier or inorganic carrier is not special and may be a general method. It can be obtained by heating the carrier and the alkyl halide in a solvent. The solvent is not particularly limited, and methanol, ethanol, dimethylformamide (DMF), tetrahydrofuran (THF) and the like are used, and methanol is preferable.
The onium compound is preferably a compound in which nitrogen or phosphorus of an organic carrier or an inorganic carrier is partially or fully quaternized with an alkyl halide. The onium salt may be about 0.1 mol% with respect to the hydroxy compound.

<(E) Organic redox agent>
Examples of the organic redox agent added as necessary include hydroquinone, benzoquinone, α-naphthoquinone, anthraquinone, catechol, 2,2′-biphenol, 4,4′-biphenol, and the like. These organic redox agents may be used alone or in combination of two or more. The organic redox agent is usually used in an amount of 0.5 to 100 mol, preferably about 5 to 50 mol, per 1 mol of the palladium compound.

<(F) Dehydrating agent>
As the dehydrating agent added as necessary, molecular sieve, synthetic zeolite or the like is used, and there is no particular limitation. For example, synthetic zeolite A-3 and A-4 are preferable, and A-3 is more preferable. is there. There is no restriction | limiting also in a shape, A powder, a granular form, bead shape, spherical shape, and chip shape are used.

<Cocatalyst>
In the catalyst for producing a polycarbonate of the present invention, a promoter can be added for the purpose of improving the catalytic activity, the selectivity to the target polycarbonate, the yield, or the life. Any promoter can be used as long as it does not adversely affect the reaction, but heteropolyacids, onium salts of heteropolyacids, and the like are preferably used. Examples of the heteropolyacid include phosphotungstic acid, phosphomolybdic acid, silicotungstic acid, silicomolybdic acid, phosphotungstomolybdic acid, cytungstomolybdic acid, and phosphovanadomolybdic acid. These onium salts, alkali metal salts, alkaline earth metal salts, transition metal salts, and the like can also be used. These may be used alone or in combination of two or more. As a cocatalyst, heteropolyacids, onium salts of heteropolyacids, and the like may be used. Examples of the heteropolyacid include phosphotungstic acid, phosphomolybdic acid, silicotungstic acid, silicomolybdic acid, phosphotungstomolybdic acid, cytungstomolybdic acid, and phosphovanadomolybdic acid. These onium salts, alkali metal salts, alkaline earth metal salts, transition metal salts, and the like can also be used. These may be used alone or in combination of two or more.

This invention provides the manufacturing method of a polycarbonate with the said catalyst for polycarbonate manufacture.
In the polycarbonate production method of the present invention, an aromatic dihydroxy compound and monohydric phenol, carbon monoxide and oxygen are reacted in the first step to produce a polycarbonate prepolymer, and then in the second step, the polycarbonate prepolymer is produced. The target polycarbonate is produced by solid phase polymerization or melt polymerization of the polymer.

Hereinafter, the 1st process in the manufacturing method of the polycarbonate of this invention is demonstrated in detail. The polycarbonate production catalyst is used in this first step.
In the first step, a polycarbonate prepolymer is produced by an oxidative carbonylation reaction.
The reaction temperature in the oxidative carbonylation reaction is usually in the range of 30 to 180 ° C, preferably 50 to 150 ° C, more preferably 80 to 120 ° C. By setting the temperature to 180 ° C. or lower, side reactions such as a decomposition reaction are prevented, and the polycarbonate prepolymer is prevented from being colored. By making it 30 degreeC or more, it prevents that the reaction rate falls.
The reaction pressure is generally set to a pressurized state because a gaseous raw material such as carbon monoxide or oxygen is used, and the carbon monoxide partial pressure is 1 × 10 ^{−2 to} 20 MPa, preferably in the range of 1 × 10 ^-2 ~10MPa, oxygen partial pressure 1 × 10 ^-2 ~10MPa, preferably it may be in a range of 1 × 10 ^-2 ~5MPa. In particular, it is desirable to adjust the oxygen partial pressure so that the gas composition in the reaction system is out of the explosion range. When the reaction pressure is too low, the reaction rate decreases. Is expensive and economically disadvantageous. When an inert gas, hydrogen, or the like is used, the partial pressure is not particularly specified, but may be used within a practical pressure range as appropriate.
For example, in the case of a batch system, the reaction time is about 1 to 48 hours, preferably 2 to 36 hours, and more preferably 3 to 24 hours. By making it 1 hour or more, the yield is prevented from decreasing, and by making it 48 hours or less in which the improvement of the yield is not observed, a decrease in productivity is prevented.
The reaction method for producing the polycarbonate prepolymer is a batch system, a semi-continuous system in which raw materials and catalysts are continuously charged, a continuous system in which raw materials and catalysts are continuously charged, and reaction products are continuously extracted. Either is possible.
The catalyst for producing the polycarbonate is useful not only for aromatic dihydroxy compounds but also for carbonylation of monohydric phenols, and is applicable to the synthesis of diphenyl carbonate.

Next, the starting material in the polycarbonate production method of the present invention will be described.
<Aromatic dihydroxy compound>
There are various kinds of aromatic dihydroxy compounds, and 2,2-bis (4-hydroxyphenyl) propane [bisphenol A] is particularly preferable. Divalent phenols other than bisphenol A include 1,1-bis (4-hydroxyphenyl) methane; 1,1-bis (4-hydroxyphenyl) ethane; 9,9-bis (4-hydroxyphenyl) fluorene; 9 , 9-bis (3-methyl-4-hydroxyphenyl) fluorene; bis (4-hydroxyphenyl) cycloalkane; bis (4-hydroxyphenyl) sulfide; bis (4-hydroxyphenyl) sulfone; bis (4-hydroxyphenyl) ) Sulfoxide; bis (4-hydroxyphenyl) ether; bis (4-hydroxyphenyl) compounds other than bisphenol A such as bis (4-hydroxyphenyl) ketone or 2,2-bis (3,5-dibromo-4-hydroxy) Phenyl) propane; 2,2-bis (3,5-dichloro-4) Halogenated bisphenols such as hydroxyphenyl) propane. When these phenols have an alkyl group as a substituent, the alkyl group is preferably an alkyl group having 1 to 8 carbon atoms, particularly an alkyl group having 1 to 4 carbon atoms. These aromatic dihydroxy compounds may be used alone or in combination of two or more.

<Monohydric phenol>
There is no restriction | limiting in particular as monohydric phenol, Phenol, o-, m-, p-cresol, p-tert-butylphenol, p-tert-amylphenol, p-tert-octylphenol, p-cumylphenol, p-methoxy Examples include phenol and p-phenylphenol. Of these, p-tert-butylphenol and phenol are preferred.
The amount of monohydric phenol used is usually in the range of 5 to 70 mol% with respect to the aromatic dihydroxy compound.
These monohydric phenols can be used alone or in combination of two or more.

  The carbon monoxide with which the aromatic dihydroxy compound and the monohydric phenol are reacted in the first step may be a simple substance, or may be diluted with an inert gas or a mixed gas with nitrogen. Further, the oxygen reacted in the same manner in the first step may be pure oxygen or diluted with an inert gas, for example, an oxygen-containing gas such as air. Carbon monoxide and oxygen are involved in the reaction in appropriate amounts by maintaining the respective partial pressures.

There is no restriction | limiting in particular as a solvent which can be used in manufacture of the polycarbonate prepolymer of a 1st process.
For example, dichloromethane, chloroform, 1,2-dichloroethane, acetophenone, γ-butyrolactone, tetrahydrofuran and the like can be mentioned, but a non-halogen solvent is preferable in view of environmental problems. Solvents useful as non-halogen solvents include compounds having a carbonate bond. For example, dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate, propylene carbonate, diallyl carbonate, allyl methyl carbonate, bis (2-methoxyphenyl) carbonate, vinylene carbonate, dibenzyl carbonate, di (o-methoxyphenyl) carbonate, And methyl ethyl carbonate. Of these, propylene carbonate is preferred. These carbonate solvents may be used alone or in combination of two or more.

Next, the 2nd process in the manufacturing method of the polycarbonate of this invention is demonstrated in detail. In the second step, a polycarbonate having a target molecular weight can be obtained by solid-phase polymerization or melt polymerization of the polycarbonate prepolymer produced in the first step.
First, solid phase polymerization will be described in detail below.
In solid phase polymerization, a quaternary phosphonium salt is preferably used as a catalyst.
The quaternary phosphonium salt used in the solid phase polymerization is not particularly limited and may be any of various types. For example, the following general formula (4) or (5)
(PR ³ ₄ ) ⁺ (X ² ) ^- (4)
(PR ³ ₄ ) ⁺ ₂ (Y ¹ ) ² -... (5)
The compound represented by these can be used.

In the general formulas (4) and (5), R ³ represents an organic group. Examples of the organic group include a linear, branched, and cyclic alkyl group having 1 to 20 carbon atoms, which may or may not have a substituent, an aryl group having 6 to 20 carbon atoms and a substituent which may or may not have a substituent. An aralkyl group having 7 to 20 carbon atoms which may or may not be present. Examples of the alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n or isopentyl group, Examples include n or isohexyl group, n or isooctyl group, n or isodecyl group, n or isododecyl group, n or isotetradecyl group, cyclopentyl group, cyclohexyl group, methylcyclohexyl group and the like. Moreover, as a substituent of these alkyl groups, a halogen atom, an alkoxy group, an arylalkoxy group, an acyloxy group etc. are mentioned, for example.
Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, a naphthyl group, and a biphenyl group. Moreover, as a substituent of these aryl groups, a halogen atom, an alkoxy group, an arylalkoxy group, an acyloxy group etc. are mentioned, for example. Examples of the aralkyl group having 7 to 20 carbon atoms include benzyl group, phenethyl group, naphthylmethyl group, 1,1,1-triphenylmethyl group and the like. Examples of the substituent for these aralkyl groups include a halogen atom, an alkoxy group, an arylalkoxy group, and an acyloxy group.
The four R ^{3 s} may be the same or different from each other, and two R ³ may be bonded to form a ring structure.
X ² is a halogen atom, a hydroxyl group, an alkyloxy group, an aryloxy _{group, R'COO, HCO 3, (R'O} ) 2 P (= O) O or BR '&apos; ₄ can be a monovalent anion formation, such as Indicates a radical. Here, R ′ represents a hydrocarbon group such as an alkyl group or an aryl group, and the two R′Os may be the same as or different from each other. R ′ 'represents a hydrogen atom or a hydrocarbon group such as an alkyl group or an aryl group, and the four R ′'s may be the same as or different from each other. Y ¹ represents a group capable of forming a divalent anion such as CO ₃ .
Specific examples of X ² include hydroxide; borohydride; tetraphenylborate; alkyltriphenylborate; formate; acetate; propionate; butyrate; fluoride; chloride; Specific examples of Y ¹ include carbonate.

  Specific examples of the quaternary phosphonium salt represented by the general formula (4) or (5) include tetraphenylphosphonium hydroxide, tetranaphthylphosphonium hydroxide, tetra (chlorophenyl) phosphonium hydroxide, and tetra (biphenyl) phosphonium hydroxy. Tetra (aryl or alkyl) such as tetradosylphosphonium hydroxide, tetramethylphosphonium hydroxide, tetraethylphosphonium hydroxide, tetraisopropylphosphonium hydroxide, tetrabutylphosphonium hydroxide, tetrahexylphosphonium hydroxide, tetracyclohexylphosphonium hydroxide ) Phosphonium hydroxides, methyltriphenylphosphonium hydroxide, ethyltriphenylphosphonium Droxide, propyltriphenylphosphonium hydroxide, isopropyltriphenylphosphonium hydroxide, butyltriphenylphosphonium hydroxide, octyltriphenylphosphonium hydroxide, tetradecyltriphenylphosphonium hydroxide, cyclohexyltriphenylphosphonium hydroxide, benzyltriphenylphosphonium hydroxy , Ethoxybenzyltriphenylphosphonium hydroxide, methoxymethyltriphenylphosphonium hydroxide, acetoxymethyltriphenylphosphonium hydroxide, phenacyltriphenylphosphonium hydroxide, chloromethyltriphenylphosphonium hydroxide, bromomethyltriphenylphosphonium hydroxide, Biphenyl Phenylphosphonium hydroxide, naphthyltriphenylphosphonium hydroxide, chlorophenyltriphenylphosphonium hydroxide, phenoxyphenyltriphenylphosphonium hydroxide, methoxyphenyltriphenylphosphonium hydroxide, acetoxyphenyltriphenylphosphonium hydroxide, naphthylphenyltriphenylphosphonium hydroxide Mono (aryl) trialkylphosphonium hydroxides such as mono (aryl or alkyl) triphenylphosphonium hydroxides, phenyltrimethylphosphonium hydroxide, biphenyltrimethylphosphonium hydroxide, phenyltrihexylphosphonium hydroxide, biphenyltrihexylphosphonium hydroxide Do, Diaryl dialkylphosphonium hydroxides such as dimethyldiphenylphosphonium hydroxide, diethyldiphenylphosphonium hydroxide, di (biphenyl) diphenylphosphonium hydroxide; isopropyltriethylphosphonium hydroxide; isopropyltriethylphosphonium hydroxide; isopropyltributylphosphonium hydroxide; cyclohexyl Cyclohexyl triethylphosphonium hydroxide; cyclohexyl tributylphosphonium hydroxide; 1,1,1-triphenylmethyltrimethylphosphonium hydroxide; 1,1,1-triphenylmethyltriethylphosphonium hydroxide; 1,1,1 -Triphenylmethyltributylphos Mono (alkyl or aralkyl) totialkyl phosphonium hydroxides such as sulphonium hydroxides may be mentioned.

  Furthermore, tetramethylphosphonium tetraphenylborate, tetraethylphosphonium tetraphenylborate, tetraphenylphosphonium tetraphenylborate, tetranaphthylphosphonium tetraphenylborate, tetra (chlorophenyl) phosphonium tetraphenylborate, tetra (biphenyl) phosphonium tetraphenylborate, tetratolylphosphonium Tetra (alkyl or aryl) phosphonium tetraphenylborates such as tetraphenylborate, methyltriphenylphosphonium tetraphenylborate, ethyltriphenylphosphonium tetraphenylborate, propyltriphenylphosphonium tetraphenylborate, butyltriphenylphosphonium tetraphenylborate, octyl Phenylphosphonium tetraphenylborate, tetradecyltriphenylphosphonium tetraphenylborate, cyclopentyltriphenylphosphonium tetraphenylborate, cyclohexyltriphenylphosphonium tetraphenylborate, benzyltriphenylphosphonium tetraphenylborate, ethoxybenzyltriphenylphosphonium tetraphenylborate, methoxymethyl Triphenylphosphonium tetraphenylborate, acetoxymethyltriphenylphosphonium tetraphenylborate, phenacyltriphenylphosphonium tetraphenylborate, chloromethyltriphenylphosphonium tetraphenylborate, bromomethyltriphenylphosphonium tetraphenylborate, biphenylto Such as phenylphosphonium tetraphenylborate, naphthyltriphenylphosphonium tetraphenylborate, chlorophenyltriphenylphosphonium tetraphenylborate, phenoxyphenyltriphenylphosphonium tetraphenylborate, acetoxyphenyltriphenylphosphonium tetraphenylborate, naphthylphenyltriphenylphosphonium tetraphenylborate Mono (aryl or alkyl) triphenylphosphonium tetraphenylborate, phenyltrimethylphosphonium tetraphenylborate, biphenyltrimethylphosphonium tetraphenylborate, phenyltrihexylphosphonium tetraphenylborate, biphenyltrihexylphosphonium tetraphenylborate, etc. And monoaryltrialkylphosphonium tetraphenylborate, dimethyldiphenylphosphonium tetraphenylborate, diethyldiphenylphosphonium tetraphenylborate, di (biphenyl) diphenylphosphonium tetraphenylborate and the like.

  Furthermore, as a counter anion, instead of the above hydroxides and tetraphenyl borates, aryloxy groups such as alkyltriphenylborate and phenoxide, alkyloxy groups such as methoxide and ethoxide, alkyls such as formate, acetate, propionate and butyrate Examples of the quaternary phosphonium salt include a carbonyloxy group, an arylcarbonyloxy group such as benzoate, and a halogen atom such as chloride and bromide.

  In addition to the compound represented by the general formula (4), those having a divalent counter anion represented by the general formula (5), such as bis (tetraphenylphosphonium) carbonate, bis (biphenyltriphenylphosphonium) Quaternary phosphonium salts such as carbonate, and further, for example, bis-tetraphenylphosphonium salt of 2,2-bis (4-hydroxyphenyl) propane, ethylenebis (triphenylphosphonium) dibromit, trimethylenebis (triphenylphosphonium)- Bis (tetraphenylborate) and the like can also be mentioned.

  Among these quaternary phosphonium salts, phosphonium salts having an alkyl group, specifically, tetramethylphosphonium methyltriphenyl are preferred because they have high catalytic activity, are easily thermally decomposed, and do not easily remain in the polymer. Borate, tetraethylphosphonium ethyltriphenylborate, tetrapropylphosphoniumpropyltriphenylborate, tetrabutylphosphoniumbutyltriphenylborate, tetrabutylphosphoniumtetraphenylborate, tetraethylphosphoniumtetraphenylborate, trimethylethylphosphoniumtrimethylphenylborate, trimethylbenzylphosphoniumbenzyltri Phenyl borate and the like are preferred.

Further, tetraalkylphosphonium salts such as tetramethylphosphonium hydroxide, tetraethylphosphonium hydroxide, and tetrabutylphosphonium hydroxide have a relatively low decomposition temperature, so that they are easily decomposed and are less likely to remain as impurities in the product polycarbonate. In addition, since the number of carbon atoms is small, the basic unit in the production of polycarbonate can be reduced, which is advantageous in terms of cost.
Further, tetraphenylphosphonium tetraphenylborate is preferably used from the balance between the catalytic effect and the quality of the obtained polycarbonate.
Furthermore, cyclohexyl triphenylphosphonium tetraphenylborate and cyclopentyltriphenylphosphonium tetraphenylborate can be preferably used in terms of excellent balance between the catalytic effect and the quality of the obtained polycarbonate.

As the reaction catalyst in this solid phase polymerization, preferably a quaternary phosphonium salt and other catalyst as required are used, but the catalyst remaining in the polycarbonate prepolymer production step may be used as it is. Alternatively, the catalyst may be added again in powder, liquid or gaseous state. The reaction temperature Tp (° C.) and reaction time at the time of carrying out this solid state polymerization reaction are the types and shapes of the crystallized polycarbonate prepolymer (chemical structure, molecular weight, etc.), the presence or absence of the catalyst in the crystallized polycarbonate prepolymer, and the type Or amount, type or amount of catalyst added as necessary, degree of crystallization of crystallized polycarbonate prepolymer, difference in melting temperature Tm '(° C), required degree of polymerization of desired aromatic polycarbonate, other Although it depends on the reaction conditions, etc., the temperature is preferably higher than the glass transition humidity of the target aromatic polycarbonate and in a range where the crystallized polycarbonate prepolymer during solid phase polymerization does not melt and remains in a solid state, more preferably Formula (6)
Tm′−50 ≦ Tp <Tm ′ (6)
Is carried out for 1 minute to 100 hours, preferably about 0.1 to 50 hours, to carry out a solid phase polymerization reaction.

  As such a temperature range, when manufacturing the polycarbonate of bisphenol A, for example, about 150-260 degreeC is preferable, and about 180-245 degreeC is especially preferable. In addition, in the polymerization step, in order to give heat to the polymer during polymerization as uniformly as possible and to advantageously extract by-products, stirring, rotating the reactor itself, or flowing with a heated gas, etc. Preferably used.

  Generally, the industrially useful aromatic polycarbonate has a weight average molecular weight of about 6000 to 200,000, and a polycarbonate having such a degree of polymerization can be easily obtained by carrying out the solid phase polymerization step. Since the crystallinity of the aromatic polycarbonate obtained by solid-phase polymerization of the crystallized polycarbonate prepolymer is higher than the crystallinity of the polycarbonate prepolymer before polymerization, in the method of the present invention, the crystalline aromatic A polycarbonate powder is obtained. The crystalline aromatic polycarbonate powder can be directly introduced into an extruder without cooling and pelletized, or can be directly introduced into a molding machine without cooling and molded. The ratio of prepolymerization and solid phase polymerization that contributes to the polymerization may be appropriately changed as necessary.

  The polymerization method in the swollen solid phase state is a method in which the polymerization is further performed by solid phase polymerization in a state where the polycarbonate prepolymer crystallized by the above method is swollen by a swelling gas described later. This method is a method for producing a polycarbonate by a melt polymerization reaction. When a low-molecular compound such as phenol produced as a by-product is degassed or extracted and removed, it is reduced from a polymer (oligocarbonate) that is swollen by a swelling gas. The method of degassing or extracting and removing the molecular compound utilizes the fact that the mass transfer rate is faster and the reaction can be performed with higher efficiency than the degassing or extracting and removing from the high viscosity molten polymer or the crystallized solid.

The swelling solvent used here is a single swelling solvent that can swell polycarbonate under the reaction conditions shown below, a mixture of these single swelling solvents, or a single swelling solvent or a mixture of them. Or the thing which mixed several types is shown.
The swollen state in this step refers to a state in which the polycarbonate prepolymer flakes which are reaction raw materials are increased in volume or mass above the thermal swelling value within the range of reaction conditions shown below. It is a single compound or a mixture thereof having a boiling point that completely evaporates in the range of reaction conditions, or usually having a vapor pressure of 6.7 kPa or more, and capable of forming the above swelling state at the same time.

Such a swelling solvent is not particularly limited as long as it satisfies the above swelling conditions. For example, an aromatic compound or an oxygen-containing compound having a solubility parameter in the range of 4 to 20 (cal / cm ³ ) ^1/2 , preferably in the range of 7 to 14 (cal / cm ³ ) ^1/2 is applicable. Examples of the swelling solvent include aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, diethylbenzene, propylbenzene, and dipropylbenzene; ethers such as tetrahydrofuran and dioxane; ketones such as methyl ethyl ketone and methyl isobutyl ketone. Can be mentioned. Among these, a single compound or a mixture of aromatic hydrocarbons having 6 to 20 carbon atoms is preferable.
In addition, as a condition of the poor solvent mixed with the swelling solvent, the solubility of polycarbonate in the solvent is 0.1% by mass or less under the following reaction conditions, and it has a linear or branched chain that is less likely to participate in the reaction. A saturated hydrocarbon compound having 4 to 18 carbon atoms or an unsaturated hydrocarbon compound having 4 to 18 carbon atoms and a low degree is preferable. If the boiling point of both the swelling solvent and the poor solvent exceeds 250 ° C., it is difficult to remove the residual solvent, and the quality may be deteriorated.

  When such a poor solvent and a swelling solvent are mixed and used, it is sufficient that the swelling solvent is incorporated in the mixed solvent in an amount of 1% by mass or more, and preferably 5% by mass or more of the swelling solvent is mixed in the mixed solvent. To be present inside. In this swelling solid phase polymerization step, the reaction temperature is preferably 100 to 240 ° C., and the pressure during the reaction is preferably 1330 Pa to 0.5 MPa · G, particularly preferably atmospheric pressure. If the reaction temperature is lower than the above range, the melt polymerization reaction does not proceed, and the reaction temperature exceeds the melting point of the polycarbonate prepolymer, so that the solid phase cannot be maintained and the phenomenon such as fusion occurs between the particles. The operability is significantly reduced. Therefore, the reaction temperature needs to be lower than the melting point.

  The swelling solvent gas may be supplied to the reactor in a liquid state and vaporized in the reactor, or may be vaporized in advance by a heat exchanger or the like and then supplied to the reactor. As the gas supply amount, it is preferable to supply 0.5 liters (standard state) / hour or more of gas per 1 g of the polycarbonate prepolymer to the reactor. The flow rate of the swelling solvent gas is closely related to the reaction rate and acts as a heat medium at the same time as the phenol removal effect, so that the reaction rate improves as the gas flow rate increases. There is no particular limitation on the reactor used for such swelling solid phase polymerization.

Next, the melt polymerization will be described in detail.
In the production method of the present invention, it is necessary to use a combination of a nitrogen-containing organic basic compound and a quaternary phosphonium salt containing an aryl group as a polymerization catalyst in the melt polymerization reaction. There is no restriction | limiting in particular as said nitrogen-containing organic basic compound, There exist various things. For example, aliphatic tertiary amine compounds such as trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, dimethylbenzylamine, aromatic tertiary amine compounds such as triphenylamine, N, N -Dimethyl-4-aminopyridine, 4-diethylaminopyridine, 4-pyrrolidinopyridine, 4-aminopyridine, 2-aminopyridine, 2-hydroxypyridine, 4-hydroxypyridine, 2-methoxypyridine, 4-methoxypyridine, imidazole , 2-methylimidazole, 4-methylimidazole, 2-dimethylaminoimidazole, 2-methoxyimidazole, 2-mercaptoimidazole, aminoquinoline, diazabicyclooctane (DABCO) and other nitrogen-containing heterocycles Compounds, and the like.

Furthermore, the general formula (7)
(NR ³ ₄ ) ⁺ (X ² ) ⁻ (7) or
General formula (8)
(NR ³ ₄ ) ⁺ ₂ (Y ¹ ) ^2- (8) or
Formula (9) [(NR ³ ₄ ) ⁺ O ⁻ ] _n —P (═O) R ′ _3-n (9)
The quaternary ammonium salt represented by these can be mentioned. In the above general formula (7), (8) or (9), R ³ represents an organic group, for example, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group or a cyclohexyl group. And an aryl group such as a cycloalkyl group, a phenyl group, a tolyl group, a xylyl group, a naphthyl group, and a biphenyl group, and an arylalkyl group such as a benzyl group. The four R ³ may be the same with or different from each other, or may form a ring structure are two R ^3. In the general formula (7), X ² represents a halogen atom, a hydroxyl group, an alkyloxy group, an aryloxy group, an alkylcarbonyloxy group, an arylcarbonyloxy group, HCO ₃ or BR _{4. In} the general formula (8), Y 2 ¹ represents CO ₃ . Here, R represents a hydrogen atom or a hydrocarbon group such as an alkyl group or an aryl group, and the four Rs may be the same or different. In the general formula (9), R ′ represents a hydrocarbon group, an alkyloxy group, an aryloxy group or a hydroxyl group, R ′ may be the same or different, and n represents an integer of 1 to 3.

  Examples of such quaternary ammonium salts include ammonium hydroxides having an alkyl group, aryl group, araryl group, and the like such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, and trimethylbenzylammonium hydroxide. And basic salts such as tetramethylammonium borohydride, tetrabutylammonium borohydride, tetrabutylammonium tetraphenylborate, and tetramethylammonium tetraphenylborate. Moreover, a bivalent anion like General formula (8) may be sufficient, for example, bis (tetramethylammonium) carbonate etc. are mentioned. Alternatively, it may be a phosphate as represented by the general formula (9), and examples thereof include tetramethylammonium phosphate, tetramethylammonium phenylphosphate, and tetramethylammonium diphenylphosphate. Among these nitrogen-containing organic basic compounds, a quaternary ammonium salt represented by the above general formula (7) from the viewpoints of high catalytic activity, easy thermal decomposition and hardly remaining in the polymer, Specifically, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, tetramethylammonium borohydride, and tetrabutylammonium borohydride are preferable, and tetramethylammonium hydroxide is particularly preferable. This nitrogen-containing organic basic compound may be used alone or in combination of two or more.

On the other hand, as the quaternary phosphonium salt, the compounds used in the solid phase polymerization can be similarly used.
More preferably, in the production method of the present invention, a nitrogen-containing organic basic catalyst and a quaternary phosphonium represented by the following general formula (10), (11) or (12) are used as a polymerization catalyst in the melt polymerization reaction. It is desirable to use a combination of compounds. Here, the general formula (10) is

[Wherein R ⁴ represents an organic group and may be the same or different from each other, and X ³ represents a halogen atom, a hydroxyl group, an alkyloxy group, an aryloxy group, an alkylcarbonyloxy group, an arylcarbonyloxy group, HCO ₃ or BR ₄ (wherein R represents a hydrogen atom or a hydrocarbon group, four Rs may be the same or different from each other, and n represents an integer of 0 to 4). ,

[Wherein R ⁴ is the same as in general formula (10) and Y ¹ represents CO ₃ ], and general formula (12) is

[Wherein, R ⁴ is the same as in formula (10), R ′ represents a hydrocarbon group, an alkyloxy group, an aryloxy group or a hydroxyl group, n is an integer of 1 to 4, and m is 1 to 3. Represents an integer].

This quaternary phosphonium salt may be used alone or in combination of two or more. In addition, the nitrogen-containing organic basic compound and the quaternary phosphonium salt containing an aryl group each preferably have a metal impurity content of 50 ppm or less, and an alkali metal and alkaline earth metal compound content of 30 ppm or less. Are more preferable, and those of 10 ppm or less are particularly preferable. Furthermore, the total amount of each metal impurity in the nitrogen-containing organic basic compound and the quaternary phosphonium salt containing an aryl group is preferably 50 ppm or less with respect to the total amount of both, and the nitrogen-containing organic basic The total content of alkali metal and alkaline earth metal compound in the quaternary phosphonium salt containing the compound and aryl group is more preferably 30 ppm or less, particularly preferably 10 ppm or less, based on the total amount of both. It is. In the present invention, as the polymerization catalyst, the nitrogen-containing organic basic compound is 10 ⁻¹ to 10 ⁻⁸ mol, preferably 10 ⁻² to 10 ⁻⁷ mol, for example, an aromatic dihydroxy compound as a raw material, more preferably using 10 ^-3 to 10 ^-6 mol, 10 ^-1 to 10 ^-8 mole of quaternary phosphonium salts containing an aryl group, preferably 10 ^-2 to 10 ^-7 mol, more preferably 10 ^-3 to 10 ^It is desirable to use ^-6 mol. By using the nitrogen-containing organic basic compound in an amount of 10 ⁻⁸ mol or more, the catalyst activity at the initial ^stage of the reaction is secured, and by making it 10 ⁻¹ mol or less, an increase in cost is prevented. On the other hand, when the amount of the quaternary phosphonium salt containing an aryl group is 10 ⁻⁸ mol or more, catalytic activity in the late stage of the reaction is ensured, and when it is 10 ⁻¹ mol or more, an increase in cost is prevented.

Moreover, the total amount of the quaternary phosphonium salt containing a nitrogen-containing organic basic compound and an aryl group is usually 2 × 10 ⁻¹ to 2 × 10 ⁻⁸ mol with respect to 1 mol of the aromatic dihydroxy compound as a raw material, The amount is preferably 2 × 10 ^{−2 to} 2 × 10 ⁻⁷ mol, more preferably 2 × 10 ⁻³ to 2 × 10 ⁻⁶ mol. Amount by the 2 × 10 ^-8 mole or more additives, catalytic effect is exhibited also by the 2 × 10 ^-1 mol, the physical properties of the polycarbonate which is the final product, in particular, heat resistance, resistance to water Prevents degradation of degradability and prevents cost increase. No unnecessary amount is added. Further, in the present invention, the polymerization activity is increased by a combination of a nitrogen-containing organic basic compound and a quaternary phosphonium salt containing an aryl group as a polymerization catalyst. In the obtained polycarbonate, it is preferable to reduce the number of metals that adversely affect hydrolysis resistance and colorability as much as possible. That is, the quaternary phosphonium salt containing an aryl group substantially eliminates the use of a metal catalyst that has been used in the late stage of the conventional reaction.

  In carrying out the melt polymerization reaction in the production method of the present invention, the reaction temperature is not particularly limited and is usually selected in the range of 100 to 330 ° C, preferably in the range of 180 to 300 ° C, more preferably the reaction temperature. A method of gradually raising the temperature to 180 to 300 ° C. in accordance with the progress is preferable. If the temperature of the melt polymerization reaction is less than 100 ° C., the reaction rate is slow. On the other hand, if it exceeds 330 ° C., side reactions occur or the resulting polycarbonate is colored, which is not preferable. The reaction pressure is set according to the vapor pressure of the monomer used and the reaction temperature. This should just be set so that reaction may be performed efficiently, and is not limited. Usually, in the initial stage of the reaction, the atmospheric pressure (normal pressure) or pressurized state from about atmospheric pressure to about 5 MPa is maintained, and in the latter stage of the reaction, the reduced pressure state, preferably finally about 1.3 to 13 kPa. There are many cases. Furthermore, reaction time should just be performed until it becomes the target molecular weight, and is about 0.2 to 10 hours normally.

  And although said melt polymerization reaction is normally performed in absence of an inert solvent, you may perform it in presence of the inert solvent about 1-150 mass% of the polycarbonate obtained as needed. . Here, examples of the inert solvent include aromatic compounds such as diphenyl ether, halogenated diphenyl ether, benzophenone, polyphenyl ether, dichlorobenzene, and methylnaphthalene, tricyclo (5,2,10) decane, cyclooctane, and cyclodecane. And cycloalkane. Moreover, you may carry out in inert gas atmosphere as needed, Here, as inert gas, gas, such as argon, a carbon dioxide, dinitrogen monoxide, nitrogen, chlorofluoro hydrocarbon, ethane, and propane, for example There are various types such as alkanes such as alkene such as ethylene and propylene.

  In the melt polymerization reaction, an antioxidant may be added to the reaction system as necessary. The antioxidant is preferably a phosphorus-based antioxidant, such as trimethyl phosphite, triethyl phosphite, tributyl phosphite, trioctyl phosphite, trinonyl phosphite, tridecyl phosphite, trioctadecyl phosphite, distearyl. Trialkyl phosphites such as pentaerythryl diphosphite, tris (2-chloroethyl) phosphite, tris (2,3-dichloropropyl) phosphite, tricycloalkyl phosphites such as tricyclohexyl phosphite, triphenyl phosphite , Tricresyl phosphite, tris (ethylphenyl) phosphite, tris (butylphenyl) phosphite, tris (nonylphenyl) phosphite, tris (hydroxyphenyl) phosphat Triaryl phosphites such as 2-ethylhexyl diphenyl phosphite, trialkyl phosphates, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tridecyl phosphate, trioctadecyl phosphate, distearyl pentaerythrityl diphosphate , Trialkyl phosphates such as tris (2-chloroethyl) phosphate, tris (2,3-dichloropropyl) phosphate, tricycloalkyl phosphates such as tricyclohexyl phosphate, triphenyl phosphate, tricresyl phosphate, tris (nonylphenyl) phosphate , Triaryl phosphates such as 2-ethylphenyldiphenyl phosphate And the like.

  EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.

<Production Example 1 (Preparation of immobilized catalyst A)>
Diamine-Silica (manufactured by Fuji Silysia Chemical Ltd., functional group concentration 0.88 mmol / g, average particle size 90 μm) 2.34 g was suspended in 30 ml of acetone. To this was slowly added an acetone solution of dichlorobis (benzonitrile) palladium (II) [dichlorobis (benzonitrile) palladium (II): 0.5 mmol, dichloromethane: 10 ml], followed by an acetone solution of cobalt (II) chloride [chloride. Cobalt (II): 1.5 mmol, acetone: 20 ml] was added, and the mixture was stirred at room temperature for 1 hour. Thereafter, the precipitate was filtered, washed with acetone, and vacuum-dried at 70 ° C. for 24 hours to obtain the target immobilized catalyst A. The obtained catalyst remained a Diamine-Silica average particle size of 90 μm.

<Production Example 2 (Preparation of immobilized catalyst B)>
PS-TPP (manufactured by Argonaut, TPP: 2.22 mmol / g, Lot No. 0289) 5.00 g, 1-bromobutane 1.52 g and methanol 70 ml were placed in an autoclave having a content of 200 ml, purged with nitrogen, and 100 ° C. The mixture was heated and stirred and cooled after 48 hours. The precipitate was filtered, washed with methanol, and vacuum dried at 80 ° C. for 24 hours. The yield is 6.19 g, and it can be seen that 78% of the phosphorus is quaternized from the increase.

Example 1
In an autoclave having an internal volume of 30 ml, bisphenol A: 4.16 mmol, immobilized catalyst A obtained in Production Example 1: 96.2 mg, tetrabutylammonium bromide 201 mg, benzoquinone 67.6 mg, and dried at 210 ° C. overnight. Synthetic zeolite A-3 powder (made by Wako Pure Chemical Co., Ltd., particle size of less than 75 μm) 1.0 g, 10 ml of propylene carbonate dehydrated overnight with molecular sieve 3A, carbon monoxide 6.0 MPa, oxygen 0.3 MPa Filled at 25 ° C. After sealing, the container was closed and heated at 95 ° C. for 24 hours. After completion of the reaction, the synthetic zeolite and the immobilized catalyst were separated, and the target polycarbonate prepolymer was obtained by methanol reprecipitation, followed by vacuum drying at 70 ° C. for 24 hours. The color of the polycarbonate prepolymer powder visually was light brown.

[Example 2]
In a 30 ml autoclave, bisphenol A: 4.16 mmol, immobilized catalyst A obtained in Production Example 1: 40.0 mg, immobilized catalyst B obtained in Production Example 2: 245 mg, dried at 210 ° C. overnight 1.0 g of treated synthetic zeolite A-3 powder (particle size less than 75 μm, manufactured by Wako Pure Chemical Industries, Ltd.) and 10 ml of propylene carbonate dehydrated overnight with molecular sieve 3A were added, carbon monoxide 6.0 MPa, oxygen 0.00%. 3 MPa was charged at 25 ° C. After sealing, the container was closed and heated at 95 ° C. for 24 hours. After completion of the reaction, the synthetic zeolite and the immobilized catalyst were separated, and the target polycarbonate prepolymer was obtained by methanol reprecipitation, followed by vacuum drying at 70 ° C. for 24 hours. The color of the polycarbonate prepolymer powder visually was white.

Example 3
The same operation as in Example 2 was carried out except that 22.3 mg of the immobilized catalyst A of Example 2 was used.

Example 4
Instead of the synthetic zeolite A-3 powder (made by Wako Pure Chemical Co., Ltd., particle size less than 75 μm) dried at 210 ° C. overnight in Example 2, 3.0 g of molecular sieve 3A beads (manufactured by Aldrich: 8-12 mesh) are used. Otherwise, the same procedure as in Example 2 was performed.

Example 5
In Example 2, it carried out like Example 2 except not having used immobilization catalyst B and synthetic zeolite A-3.

  Table 1 shows the yield (%), number average molecular weight (Mn), and weight average molecular weight (Mw) of the polycarbonate prepolymer obtained in Examples 1 to 5.

Example 6 (Production of polycarbonate)
<First step>
Synthesis in which autoclave having an internal volume of 100 ml was dried at 210 ° C. overnight at bisphenol A: 12.48 mmol, p-tert-butylphenol 6.72 mmol, immobilized catalyst A obtained in Production Example 1: 100.5 mg Zeolite A-3 powder (made by Wako Pure Chemical Co., Ltd., particle size of less than 75 μm) 3.0 g, 30 ml of propylene carbonate dehydrated overnight in molecular sieve 3A, carbon monoxide 6.0 MPa, oxygen 0.3 MPa at 25 ° C. Filled with. After sealing, the container was closed and heated at 100 ° C. for 24 hours. After completion of the reaction, the synthetic zeolite and the immobilized catalyst were separated, and the target polycarbonate prepolymer was obtained by methanol reprecipitation, followed by vacuum drying at 70 ° C. for 24 hours.

<Second step>
300 ppm of cyclohexyl triphenylphosphonium tetraphenylborate is added to 500 mg of the polycarbonate prepolymer obtained in the first step, put into a SUS tube having an inner diameter of 1.3 cm, introduced at a rate of 100 ml / min of nitrogen gas, and at 190 ° C. for 2 hours. Solid phase polymerization was carried out at 210 ° C. for 2 hours and at 230 ° C. for 4 hours for a total of 8 hours to obtain the target polycarbonate. The amount of residual palladium in the polycarbonate was 25 ppm or less. Table 2 shows the molecular weight (Mn, Mw) of the polycarbonate prepolymer obtained in the first step and the polycarbonate obtained in the second step.

[Comparative Example 1]
In Example 6, except that no use of a p-tert-butylphenol was carried out in the same manner as in Example 6. The molecular weights (Mn, Mw) of the polycarbonate prepolymer obtained in the first step and the polycarbonate obtained in the second step are shown in Table 2 above.

  The present invention provides a polycarbonate useful as a resin material or the like in the electric / electronic field, the automobile field, the optical component field, the structural material field, or the like.

Claims (9)

  A catalyst for producing a polycarbonate, comprising a reaction product of (a) a carrier obtained by binding diamine to silica gel, (b) a palladium compound, and (c) a metal compound having redox catalytic ability.   The catalyst for producing a polycarbonate according to claim 1, further comprising (d) an onium compound.   The catalyst for producing a polycarbonate according to claim 1 or 2, further comprising (e) an organic redox agent.   The polycarbonate production catalyst according to any one of claims 1 to 3, further comprising (f) a dehydrating agent.   The catalyst for producing a polycarbonate according to any one of claims 1 to 4, wherein the diamine is ethylenediamine.   The catalyst for producing a polycarbonate according to any one of claims 1 to 5, wherein the palladium compound (b) is a divalent palladium compound.   The catalyst for producing a polycarbonate according to claim 1, wherein the metal compound having redox catalytic ability of (c) is a cobalt compound.   The catalyst for producing a polycarbonate according to claim 2, wherein the onium compound (d) is a compound obtained by quaternizing part or all of nitrogen or phosphorus of an organic carrier or an inorganic carrier with an alkyl halide.   A first step of producing a polycarbonate prepolymer by reacting an aromatic dihydroxy compound and a monohydric phenol with carbon monoxide and oxygen, and a second step of producing a polycarbonate by solid-phase polymerization or melt polymerization of the polycarbonate prepolymer. A process for producing a polycarbonate comprising the steps of: using the catalyst for producing a polycarbonate according to claim 1 in the first step.