JP3364368B2 - Method for producing aromatic polycarbonate - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention
And a method for producing the same. More specifically, excellent hydrolysis resistance
Polycarbonate with excellent polymerization reaction rate, hue, etc.
The present invention relates to a method for producing Bonate. 2. Description of the Related Art Polycarbonate is used for mechanical properties such as impact resistance.
Excellent heat resistance, transparency, etc.
Widely used. Such polycarbonate
The production method of aromatic dihydrogen such as bisphenol
A method for directly reacting a hydroxy compound with phosgene (see
Surface method) or aromatic dihydro such as bisphenol
Xylates and diaryls such as diphenyl carbonate
Transesterification reaction with carbonate in molten state (melt
Method) is known. [0003] Among such production methods, aromatic dihydro-
Transesterification of xy compounds with diaryl carbonates
Method for producing polycarbonate by reaction
To illustrate, this method uses a metal organic acid as a catalyst.
Salts, inorganic acid salts, oxides, hydroxides, hydrides or
Aromatic dihydroxy under reduced pressure using
The compound and the diaryl carbonate are, for example, finally
Transesterification while heating and melting at 250-330 ° C
It is a method of reacting. [0004] This method has a higher poly-polymethod than the aforementioned interface method.
It has the advantage of being able to produce carbonates at low cost.
However, because the polymer is exposed to high temperatures for a long time,
There was a problem that the phase was not favorable. Color like this
Various catalysts have been proposed to improve the phase.
Inferior to polycarbonate polymerized by surface method, still sufficient
is not. In the melt polymerization method, high temperature and reduced pressure are used in the presence of a catalyst.
Because the reaction is performed, the polymer is easily colored and side reactions occur.
Polycarbonate with Less Coloring Due to Branching Structure
Some catalyst systems for the production of
Kilammonium hydroxy and alkali metal, alkali
Catalyst systems combining earth metals have been proposed. I
However, when the above catalyst system is used, depending on the reaction conditions,
Methylene chloride possibly due to a branched structure in the polymer
In some cases, components that are insoluble in the solvent such as the above may be formed. Further, the obtained polycarbonate is resistant to hydrolysis.
Degradability is poor, and there is a case where the degree of polymerization decreases greatly in molding processing etc.
is there. In addition, because the resin is exposed to a high temperature atmosphere,
Coloring and insoluble due to chemical reaction, other decomposition reaction and side reaction
There are problems such as formation of foreign matter, generation of foreign matter, and decrease in molecular weight. Also,
Polymerization activity only with traalkyl ammonium hydroxide
Is insufficient, and it is difficult to obtain polycarbonate with a high degree of polymerization.
Problems. On the other hand, JP-A-6-14334 and JP-A-6-14334
JP-A-6-14335, JP-A-6-157778
, JP-A-6-136110, JP-A-7-974
No. 39, melt polycondensation in the presence of organosilicon compound
A method is disclosed, but in this case dibutyltin oxide
Although metal compound catalysts represented by Sid are used,
The polymerization activity at low temperatures is not sufficient, and coloring and the like are likely to occur. [0008] Accordingly, the present invention provides
The melt polymerization method has no coloration and has excellent hydrolysis resistance.
The purpose is to produce carbonate. SUMMARY OF THE INVENTION The present invention is directed to a specific catalyst system.
And polymerization in the presence of an organosilicon compound.
Polymer with little coloration and excellent hydrolysis resistance
Found that high volume polycarbonate can be produced
It is characterized by. That is, the present invention relates to an aromatic dihydroxy compound.
Melt polycondensation of the compound with the diaryl carbonate
When producing carbonate, (A) basification with nitrogen
Compound (B) an alkali metal compound and / or an alkali
Lithium earth metal compound and (C) a compound represented by the following general formula
Silicon compound [Wherein, R ^a , R ^b , R ^c , R ^d Is German
In addition, a monovalent hydrocarbon group having 1 to 20 carbon atoms,
20 oxygen-containing hydrocarbon groups, hydroxyl groups, halogen atoms, water
Selected from elementary atoms. ] And / or represented by the following general formula:
Organosilicon compound to be used [Wherein R ^x , R ^y Each independently has 1 carbon atom
Monovalent hydrocarbon group of 20 to 20 carbon atoms containing 1 to 20
Selected from hydrocarbon groups, hydroxyl groups, halogen atoms, and hydrogen atoms
And n represents an integer of 1 or more. R ^x , R ^y Is repeated simply
The positions may be the same or different. ]
Characterized in that the reaction is carried out in the presence of a catalyst comprising
1 is a method for producing an aromatic polycarbonate. Aromatic dihydroxylation usable in the present invention
The compound is not particularly limited, but is represented by the following formula (1).
Compounds. Embedded image In the formula, X is: ## EQU1 ## Here, R _Three , R _Four Are the same or different,
Hydrogen atom, halogen atom or hydrocarbon having 1 to 12 carbon atoms
Elementary group. As the hydrocarbon group, a fatty acid having 1 to 12 carbon atoms
Aliphatic hydrocarbon group or aromatic hydrocarbon having 6 to 12 carbon atoms
Preferred are basic groups. Such aliphatic hydrocarbon groups include
A kill group, an alkenyl group, etc., a methyl group, an ethyl group.
And a propyl group. Also aromatic hydrocarbon groups
Is a substituted or unsubstituted phenyl group, naphthyl group
And the like. Halogen atoms include chlorine, bromine,
And urine. R _Five Is a divalent hydrocarbon group having 4 to 20 carbon atoms
And an aliphatic carbon such as an alkylene group or an alkenylene group.
A hydrogen group, such as a butylene group and a pentylene group;
Is done. Where R ₁ , R _Two Are the same or different,
A hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms
is there. As the hydrocarbon group, an aliphatic carbon having 1 to 12 carbon atoms
Examples include a hydride group or an aromatic group having 6 to 12 carbon atoms.
Can be. As the aliphatic hydrocarbon group, an alkyl group, a
Examples thereof include a alkenyl group, and more specifically, a methyl group,
Examples include an ethyl group and a propyl group. Also with aromatic groups
Substituted or unsubstituted phenyl group, naphthyl group, etc.
Is mentioned. Halogen atoms include chlorine, bromine and iodine
Element and the like. In the formula, m and n are the same or different, and 0 or
Represents an integer of 1 to 4. Specifically, the following compounds are listed.
Can be. Bis (4-hydroxyphenyl) methane,
1,1-bis (4-hydroxyphenyl) ethane, 2,
2-bis (4-hydroxyphenyl) propane, 2,2
-Bis (4-hydroxyphenyl) butane, 2,2-bi
Bis (4-hydroxyphenyl) octane, bis (4-hi
Droxyphenyl) phenylmethane, 2,2-bis (4
-Hydroxy-3-methylphenyl) propane, 1,1
-Bis (4-hydroxy-t-butylphenyl) propa
2,2-bis (4-hydroxy-3-bromophenyl)
B) bis (hydroxyaryl) alka such as propane
And 1,1-bis (4-hydroxyphenyl) cyclo
Pentane, 1,1-bis (4-hydroxyphenyl) si
Bis (hydroxyaryl) cyclo such as chlorohexane
Alkanes, 4,4'-dihydroxydiphenylate
4,4'-dihydroxy-3,3'-dimethylfe
Dihydroxyaryl ethers such as nyl ether,
4,4'-dihydroxydiphenyl sulfide, 4,
4'-dihydroxy-3,3'-dimethyldiphenyls
Dihydroxydiaryl sulfides such as sulfide,
4,4'-dihydroxydiphenylsulfoxide, 4,
4'-dihydroxy-3,3'-dimethyldiphenyls
Dihydroxydiaryl sulfoxides such as rufoxide
, 4,4'-dihydroxydiphenylsulfone, 4,
4'-dihydroxy-3,3'-dimethyldiphenyls
Dihydroxydiaryl sulfones such as rufone, 9,
Such as 9-bis (4-hydroxyphenyl) fluorene
And dihydroxydiaryls. Of these, in particular, 2,2-bis (4-
Hydroxyphenyl) propane (bisphenol A)
It is preferably used. These aromatic dihydroxy compounds
The objects can be used alone or in combination. Diaryl carbonate has 6 to 2 carbon atoms.
Carbonate having 0 optionally substituted aryl groups
Although there is no particular limitation as long as it is a
Nyl carbonate, ditolyl carbonate, bis (c
(Rolophenyl) carbonate, m-cresyl carbonate
G, dinaphthyl carbonate, bis (diphenyl) car
Bonate and the like can be mentioned. Zia as above
Reel carbonate is 1 mole of aromatic dihydroxy compound
1.0 to 1.30 mol, preferably 1.
Preferably, it is used in an amount of from 01 to 1.20 mol. The catalyst used in the present invention is (A) a nitrogen-containing salt.
Basic compound, (B) an alkali metal compound and / or
An alkaline earth metal compound and (C) represented by the following general formula:
Organosilicon compound to be used [Wherein, R ^a , R ^b , R ^c , R ^d Is German
In addition, a monovalent hydrocarbon group having 1 to 20 carbon atoms,
20 oxygen-containing hydrocarbon groups, hydroxyl groups, halogen atoms, water
Selected from elementary atoms. ] And / or represented by the following general formula:
Organosilicon compound to be used [Wherein R ^x , R ^y Each independently has 1 carbon atom
Monovalent hydrocarbon group of 20 to 20 carbon atoms containing 1 to 20
Selected from hydrocarbon groups, hydroxyl groups, halogen atoms, and hydrogen atoms
And n represents an integer of 1 or more. R ^x , R ^y Is repeated simply
The positions may be the same or different. ]
Become. (A) Specific examples of the nitrogen-containing basic compound and
As a result, tetramethylammonium hydroxide (Me
_Four NOH), tetraethylammonium hydroxide
(Et _Four NOH), tetrabutylammonium hydroxy
Sid (Bu _Four NOH), trimethylbenzylammonium
M-hydroxide (phenyl-CH _Two (Me) _Three NOH)
Having an alkyl, aryl, araryl group, etc.
Ammonium hydroxides, trimethylamine,
Liethylamine, dimethylbenzylamine, triphenyl
Tertiary amines such as _Two NH (where R is methyl
Alkyl such as ethyl, ethyl, phenyl, toluyl, etc.
An aryl group, etc.), RN
H _Two (Wherein R is as defined above)
, 2-methylimidazole, 2-phenylimidazo
And other imidazoles, tetramethylammonium
Acetate (Me _Four NOCOCH _Three Ammonium such as
Mucarboxylates or tetramethylammonium
Umboro hydride (Me _Four NBH _Four ), Tetrabuty
Luammonium tetraphenylborate (Bu _Four NBP
h _Four ), Tetramethylammonium tetraphenylbore
(Me _Four NBPh _Four ))
Can be. Of these, ammonium hydroxide
Are preferred, and tetramethylammonium hydro
Oxide (Me _Four NOH) is particularly preferred. These compounds
The substances may be used alone or in combination of two or more. (B) Alkali metal compounds, alkaline earths
As metal compounds, these hydroxides, bicarbonates,
Carbonates, acetates, borohydrides, stearates, ammonium salts
There are salts of benzoate and bisphenol. As a specific example of the alkali metal compound,
Is sodium hydroxide, potassium hydroxide, lithium hydroxide
, Sodium hydrogen carbonate, potassium hydrogen carbonate, hydrogen carbonate
Lithium, sodium carbonate, potassium carbonate, lithium carbonate
System, sodium acetate, potassium acetate, lithium acetate,
Sodium stearate, potassium stearate, steer
Lithium phosphate, sodium benzoate, potassium benzoate
System, lithium benzoate, disodium hydrogen phosphate, phosphorus
Dipotassium hydrogen oxyphosphate, dilithium hydrogen phosphate, bispheno
Disodium salt, dipotassium salt, dilithium
Salt, phenol sodium salt, potassium salt, lithium
Salts and the like can be mentioned. Specific examples of the alkaline earth metal compound
Examples include calcium hydroxide, barium hydroxide, hydroxyl
Magnesium iodide, strontium hydroxide, hydrogen bicarbonate
Cium, barium bicarbonate, magnesium bicarbonate, charcoal
Strontium hydrogen oxy, calcium carbonate, barium carbonate
, Magnesium carbonate, strontium carbonate, calcium acetate
Cium, barium acetate, magnesium acetate, acetate acetate
Nitium, calcium stearate, bali stearate
, Magnesium stearate, stearic acid
And nthium. These compounds may be used alone or in combination of two or more.
May be. (C) Organosilicon compound used in the present invention
Is an organosilicon compound represented by the above general formula (I) and
And / or organosilicon compounds represented by the above general formula (II)
It is. Organic siliconization represented by the above general formula (I)
Compound R ^a , R ^b , R ^c , R ^d As charcoal
A monovalent hydrocarbon group having 1 to 20 carbon atoms, an acid having 1 to 20 carbon atoms
Hydrogen-containing hydrocarbon group, hydroxyl group, halogen atom, hydrogen atom
Selected from As a monovalent hydrocarbon group having 1 to 20 carbon atoms
Represents an alkyl group, specifically, a methyl group, an ethyl group,
Ropyl, n-propyl, n-butyl and the like.
Other hydrocarbon groups include aryl groups, alkyl groups
Specific examples include an aryl group and an arylalkyl group.
Include phenyl, tolyl, benzyl and the like.
You. Further, as an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms,
Specific examples include an alkoxy group and an aryloxy group.
Are methoxy, ethoxy, i-propoxy, n-
Propoxy, n-butoxy, phenoxy and the like
Can be Halogen atoms include fluorine and chlorine atoms
And a bromine atom. Organic siliconization represented by the above general formula (II)
Compound R ^x , R ^y Are each independently monovalent having 1 to 20 carbon atoms
Hydrocarbon groups, 1-20 oxygen-containing hydrocarbon groups, hydroxyl
Selected from groups, halogen atoms and hydrogen atoms. Carbon number 1
As the monovalent hydrocarbon group of 20, an alkyl group, specifically,
Is methyl, ethyl, i-propyl, n-propyl
Group, n-butyl group and the like, and other hydrocarbon groups.
Is an aryl group, an alkylaryl group, an aryl
And a phenyl group, a tolyl group.
Group, benzyl group and the like. In addition, C 1-20
Examples of the oxygen-containing hydrocarbon group include an alkoxy group and an arylo group.
Methoxy group, ethoxy group, etc.
Group, i-propoxy group, n-propoxy group, n-butoxy
And a phenoxy group and the like. As a halogen atom
Include fluorine, chlorine, bromine, etc.
You. Organic compounds represented by the above general formulas (I) and (II)
Representative examples of silicon compounds include methoxysila
, Ethoxysilane, n-propoxysilane, i-pro
Poxysilane, n-butoxysilane, s-butoxysila
, I-butoxysilane, n-octoxysilane,
Rohexoxysilane, phenoxysilane, dimethoxysi
Orchid, diethoxysilane, di-n-propoxysilane,
Di-i-propoxysilane, di-n-butoxysilane,
Di-s-butoxysilane, di-i-butoxysilane, di
-N-octoxysilane, dicyclohexoxysilane,
Diphenoxysilane, trimethoxysilane, triethoxy
Sisilane, Tri-n-propoxysilane, Tri-i-type
Ropoxysilane, tri-n-butoxysilane, tri-s
-Butoxysilane, tri-i-butoxysilane, tri-
n-octoxysilane, tricyclohexoxysilane,
Triphenoxysilane, tetramethoxysilane, tetra
Ethoxysilane, tetra-n-propoxysilane, tet
L-I-propoxysilane, tetra-n-butoxysila
, Tetra-s-butoxysilane, tetra-i-butoki
Sisilane, tetra-n-octoxysilane, tetracycl
Alhexoxysilane, tetraphenoxysilane, etc.
Coxysilane, aryloxysilanes; methylsila
, Ethylsilane, n-propylsilane, i-propyl
Silane, n-butyl silane, s-butyl silane, i-butyl
Tylsilane, n-octylsilane, cyclohexylsila
Phenylsilane, dimethylsilane, diethylsila
, Di-n-propylsilane, di-i-propylsila
Di-n-butylsilane, di-s-butylsilane, di
-I-butylsilane, di-n-octylsilane, dicycl
Rohexylsilane, diphenylsilane, trimethylsila
, Triethylsilane, tri-n-propylsilane,
L-i-propylsilane, tri-n-butylsilane, g
Lys-butyl silane, tri-i-butyl silane, tri
-N-octylsilane, tricyclohexylsilane,
Riphenylsilane, tetramethylsilane, tetraethyl
Silane, tetra-n-propylsilane, tetra-i-oop
Propyl silane, tetra-n-butylsilane, tetra-s
-Butylsilane, tetra-i-butylsilane, tetra-
n-octylsilane, tetracyclohexylsilane, te
Traphenylsilane, tetramethylsilane, tetraethyl
Silane, tetraphenylsilane, tetratolylsila
Alkyl silanes such as
Silanes: methyl silane triol, ethyl silane
Riol, n-propylsilanetriol, i-propyl
Lusilanetriol, n-butylsilanetriol,
Phenylsilanetriol, dimethylsilanediol, di
Ethylsilanediol, di-n-propylsilanediol
, Di-i-propylsilanediol, di-n-butyl
Silanediol, diphenylsilanediol, trimethyl
Lucilanol, triethylsilanol, tri-n-pro
Pyrsilanol, tri-i-propylsilanol, tri
-N-butylsilanol, triphenylsilanol,
Ethoxysilanetriol, ethoxysilanetriol,
n-propoxysilanetriol, i-propoxysila
Triol, n-butoxysilanetriol, pheno
Xysilanetriol, dimethoxysilanediol, di
Ethoxysilanediol, di-n-propoxysilanedi
All, di-i-propoxysilanediol, di-n-
Butoxysilanediol, diphenoxysilanediol
, Trimethoxysilanol, triethoxysilanol
, Tri-n-propoxysilanol, tri-i-pro
Poxysilanol, tri-n-butoxysilanol,
Silanols such as rifenoxysilanol; tetraclo
Rosilane, tetrabromosilane, trichlorosilane,
Libromosilane, dichlorosilane, dibromosilane,
Halogenated silanes such as lorosilane and bromosilane;
1,1,3,3-tetramethyldisiloxane, 1,1,
3,3-pentamethyldisiloxane, 1,1,3,3-
Hexamethyldisiloxane, 1,1,3,3-tetrae
Tildisiloxane, 1,1,3,3-pentaethyldisi
Loxane, 1,1,3,3-hexaethyldisiloxa
1,1,3,3-tetra-n-butyl disiloxa
, 1,1,3,3-penta-n-butyldisiloxa
1,1,3,3-hexa-n-butyl disiloxa
1,1,3,3-tetraphenyldisiloxane,
1,1,3,3-pentaphenyldisiloxane, 1,
1,3,3-hexaphenyldisiloxane, 1,1,
3,3,5,5-hexamethyltrisiloxane, hexa
Methylcyclotrisiloxane, hexaphenylcycloto
Risiloxane, dimethylpolysiloxane, diethylpoly
Siloxane such as siloxane and diphenylpolysiloxane
And the like, and when used alone, two or more kinds are mixed.
You may use it. Of these, alkoxysilanes are preferred.
, Especially tetramethoxysilane, tetraethoxysila
, Tetra-n-propoxysilane, tetra-i-pro
Poxysilane, tetra-n-butoxysilane, tetra-
s-butoxysilane, tetra-i-butoxysilane, te
Tora-n-octoxysilane, tetracyclohexoxy
Tetraalkoxy such as silane and tetraphenoxysilane
Silanes are particularly preferred. The amount of these compounds used is
(A) 10 parts of nitrogen-containing basic compound per 1 mole of hydroxy compound ^-6 -10 ^-1 Mol (B) alkali metal compound and / or alkaline earth
10 metal compounds ^-8 -10 ^-Four 10 mol (C) organosilicon compound ^-6 -10 ^-1 Molar is preferred. More preferably, aromatic dihydroxylation
(A) 10 parts of nitrogen-containing basic compound per mole of compound ^-Five -10 ^-3 Mol (B) alkali metal compound and / or alkaline earth
10 metal compounds ^-7 -10 ^-Five 10 mol (C) organosilicon compound ^-Five -10 ^-3 Molar is preferred. Above this range, colored or branched components
Is easy to produce, and below this range, the effect of the catalyst is low.
In addition, a sufficient reaction rate cannot be obtained, and the physical properties are likely to deteriorate. In the present invention, the catalyst and the organosilicon compound
The method of charging the material may be either solid or liquid, but is preferred.
Or a solution or suspension. With solution or suspension
The concentration at the time of processing should be a concentration that can be handled in the liquid state.
And preferably 30% by weight or less, more preferably 20% by weight.
% Or less. Oxygen dissolved in the solution or suspension
The concentration is preferably 100 ppm or less, more preferably
50 ppm or less, more preferably 10 ppm or less
Is preferred. Beyond this range, due to the effect of dissolved oxygen
Coloring or branched components are easily formed. Further, in the present invention, before polymerization is started,
During fusion, at least once in the molten state after polymerization
It is also preferable to add various stabilizers. As the stabilizer
The sulfur-containing acidic compound and / or the acid compound
Derivatives, phenolic stabilizers, thioe
-Tel stabilizer, phosphorus stabilizer, hindered amine based stabilizer
Stabilizer, epoxy compound, salicylic acid UV absorber,
Nzotriazole UV absorbers
You. As described above, the combination in the above-mentioned amount is used.
Reacting in the presence of a catalyst and an organosilicon compound
Allows the polycondensation reaction to proceed at a sufficient
To produce high polycarbonate with high polymerization activity
And the resulting polycarbonate is resistant to hydrolysis
Excellent in properties and preferred. The presence of such a catalyst and an organosilicon compound
Currently, aromatic dihydroxy compounds and diaryl carbonates
The polycondensation reaction with a salt is a polycondensation reaction known in the art.
It can be performed under the same conditions as the above. Specifically, the first-stage reaction is carried out at 80 to 25
0 ° C, preferably 100 to 230 ° C, more preferably
At a temperature of 120-190 ° C, 0-5 hours, preferably 0
~ 4 hours, more preferably 0 ~ 3 hours, under reduced pressure, fragrance
Reaction between an aromatic dihydroxy compound and a diaryl carbonate
Respond. Then, while increasing the degree of vacuum in the reaction system,
To increase the aromatic dihydroxy compound and the diaryl car
Reaction with Bonate, finally 5mmHg or less,
Preferably under a reduced pressure of 1 mmHg or less, 240 to 320
Aromatic dihydroxy compound and diaryl carbonate at ℃
And a polycondensation reaction with The above-mentioned polycondensation reaction is carried out continuously.
Or a batch process. In addition, the above reaction
The reactor used for the reaction is a tank type
It may be of a type or a tower type. The reaction product obtained as described above
Polycarbonate, which is usually measured at 20 ° C.
Viscosity (methylene chloride solvent (weight ratio 40/6)
0)) is 0.1 to 1.0, preferably 0.2 to 0.8
is there. In the present invention, the poly
Normal carbonates do not impair the purpose of the present invention.
Heat stability, UV absorber, release agent, colorant, antistatic
Agent, lubricant, antifogging agent, natural oil, synthetic oil, wax, organic
A filler, an inorganic filler, and the like may be added. According to the present invention, the polymer color tone is good,
Production of high molecular weight polycarbonate with excellent hydrolysis resistance
it can. Hereinafter, the present invention will be described with reference to examples. Book
In the present invention, physical properties were measured according to the following methods. (I) Intrinsic viscosity [η]: 2 in methylene chloride
It was measured at 0 ° C. with an Ubbeloth viscometer. (Ii) Hue: (a) L / b: Injection molded plate having a thickness of 3 mm was subjected to cylinder temperature
300 ° C injection pressure 100kg / cm ^Two At a mold temperature of 90 ° C
After molding, the X, Y and Z values were measured using Colora manufactured by Nippon Denshoku Industries Co., Ltd.
nd Color Difference Meter
L / b was measured by a transmission method using ND-1001DP. (B) Haze: NDH manufactured by Nippon Denshoku Industries Co., Ltd.
Measured at -200. (Iii) Hydrolysis resistance: the polymer was sealed in water at 125 ° C.
Reduction rate of intrinsic viscosity after 14 hours in a toclave
I asked. Examples 1 to 5 and Comparative Examples 1 to 3
228 parts of Nord A (BPA), diphenyl carbonate
220 parts and the type and amount of catalyst shown in Tables 1 and 2
Equipped with a stirrer, still and depressurizer for silicon compounds
Discharge at 140 ° C after charging the reaction tank with nitrogen
did. After stirring for 30 minutes, the internal temperature was raised to 180 ° C,
Pheno which reacts for 30 minutes at 100mmHg by gradually reducing pressure
Was removed. Further, the pressure was gradually reduced while increasing the temperature to 200 ° C.
Reacted while distilling phenol at 50 mmHg for 30 minutes
I let you. Further gradually to 220 ° C. and 30 mmHg
Raise the temperature and reduce the pressure, and at the same temperature and pressure for 30 minutes, and further 240 ° C 1
0mmHg, 260 ° C 1mmHg, 270 ° C 1mm
Repeat the heating and depressurization in the same procedure as above until the pressure drops below Hg
The reaction was continued. Finally, polymerization was carried out at the same temperature and pressure for 2 hours,
A carbonate resin was produced. Measure the physical properties of these polycarbonate resins
The results are shown in Tables 1 and 2. The polycarbonate produced according to the present invention
Has good hydrolysis resistance, high polymerization rate,
Was also good. On the other hand, according to Comparative Examples 1 and 2,
If the polymer produced has poor hydrolysis resistance,
According to the report, the reaction speed at low temperature is slow and the hue is deteriorated.
Was. [Table 1] [Table 2]

Continuation of front page (72) Inventor Katsushi Sasaki 2-1 Hinode-cho, Iwakuni-shi, Yamaguchi Prefecture Teijin Limited Iwakuni Research Center (56) References JP-A-6-234843 (JP, A) (58) Field (Int.Cl. ⁷ , DB name) C08G 64/00-64/42

Claims (1)

(57) [Claim 1] When a polycarbonate is produced by melt-polycondensation of an aromatic dihydroxy compound and a diaryl carbonate, (A) a nitrogen-containing basic compound, and (B) an alkali metal compound And / or an alkaline earth metal compound and (C) an organosilicon compound represented by the following general formula: [Wherein, R ^a , R ^b , R ^c , and R ^d each independently represent a monovalent hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, a hydroxyl group, a halogen atom, Selected from hydrogen atoms. And / or an organosilicon compound represented by the following general formula: [Wherein, R ^x and R ^y each independently represent a monovalent hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms,
It is selected from a hydroxyl group, a halogen atom and a hydrogen atom, and n represents an integer of 1 or more. R ^x and R ^y may be the same or different between repeating units. Wherein the reaction is carried out in the presence of a catalyst comprising: