JP3386288B2 - Method for producing aromatic polycarbonate - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention
Construction method. More specifically, polymerization reaction rate, hue,
Regarding the method of manufacturing polycarbonate with excellent heat resistance
You. 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. [0005] One of the quaternary ammonium hydroxide compounds
Some tetramethylammonium hydroxides are strongly basic
And can be a transesterification catalyst for polycarbonate
You. However, it has decomposability, and the decomposition temperature is 135-1.
Since it is relatively low at 40 ° C, polycarbonate
Polymerization activity at high temperature when melt polymerization of nate
Is extremely low and only low-polymerized products can be obtained.
Was. Japanese Patent Application Laid-Open No. 60-51719 discloses a nitrogen-containing
A catalyst consisting of a combination of a basic compound and a boron compound
There has been proposed a method for producing polycarbonate using
You. If this catalyst system is used, relatively pale polycarbonate
Can be obtained, but has the problem of low polymerization activity.
Was. [0007] JP-A-2-124934 discloses a nitrogen-containing salt.
Basic compound, boron compound and alkali (earth) metal compound
Polycarbonate using a catalyst consisting of a combination of products
A method of manufacturing has been proposed. With this catalyst system,
Polymerization activity is relatively improved by the use of lukali (earth) metal compounds
However, when alkali metal compounds are used, the reaction conditions
Some salts are considered to be due to the branched structure in the polymer
Components that are insoluble in solvents such as methylene
You. Generation of insolubles due to the branched structure increases the degree of polymerization
It becomes more noticeable. [0008] Molding of the obtained polycarbonate
In some cases, the degree of polymerization decreases greatly. In addition, the resin
Oxidation reactions and other decomposition due to exposure to warm atmosphere
Coloring, insolubilization, formation of foreign substances, molecules due to reactions and side reactions
There is a problem such as a decrease in the amount. SUMMARY OF THE INVENTION The present inventor has set forth the above problems.
As a result of our hard work to solve the point, a certain structure
Use of a quaternary ammonium hydroxide compound having
Have been found to solve the above problems, and
Was. That is, an object of the present invention is to provide a method for melt polycondensation.
More fragrance with less coloration and less branching and insolubilization
To provide a method for producing aromatic polycarbonate.
You. Another object of the present invention is to provide a branching reaction during molding.
Side reactions such as burning,
Prevents color, insolubilization, formation of foreign matter or molecular weight reduction
To provide a method for producing an aromatic polycarbonate
And there. Still another object of the present invention is to provide a fragrance as described above.
Aromatic polycarbonate at high polymerization rate with high productivity
The purpose is to provide a method for doing this. Still another object of the present invention
Is for producing an aromatic polycarbonate as described above.
The object of the present invention is to provide a catalyst. Still another object of the present invention
And advantages will be apparent from the description below. [0011] That is, the present invention provides an aromatic compound
An aromatic dihydroxy compound and a carbonic acid diester,
Of a quaternary ammonium hydroxide compound represented by the formula (I)
Aromatic polycarbonate characterized by melt polycondensation in the presence
This is a method for producing carbonate. Embedded image Aromatic dihydroxylation usable in the present invention
The compound is not particularly limited, but is represented by the following formula (II).
Compounds. Embedded image 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
As a substituted or unsubstituted phenyl group, naphthyl group, etc.
Is mentioned. Halogen atoms include chlorine, bromine and iodine
Element and the like. R _Five Is a divalent hydrocarbon having 4 to 20 carbon atoms
And an aliphatic carbon such as an alkylene group or an alkenylene group.
Hydride group, butylene group, pentylene group, etc.
Is shown. 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.
No. Chlorine, bromine, iodine as halogen atoms
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. Bi
80-98 mol% of sphenol A and 2-2 of other components
What contains 0 mol% can be used. The carbonic diester is substituted with 6 to 20 carbon atoms.
Carbonates having an optionally substituted aryl group are preferred.
Good. Specifically, diphenyl carbonate, ditricarbonate
Carbonate, bis (chlorophenyl) carbonate
G, m-cresyl carbonate, dinaphthyl carbonate
And bis (diphenyl) carbonate
Can be. Diaryl carbonates as described above are aromatic
1.0 to 1 mol of the dihydroxy group compound
1.30 mol, preferably 1.01 to 1.20 mol
It is desirable to use it. The catalyst used in the present invention has the following general formula (I)
Is represented by Embedded image R represents an alkyl group having 10 to 20 carbon atoms.
Decyl, hexadecyl, octadecyl, aryl
Substituted or unsubstituted phenyl group, aralkyl
Examples of the group include a substituted or unsubstituted benzyl group.
You. As a specific example, decyltrimethyla
Nmonium hydroxide, hexadecyltrimethylan
Monium hydroxide, octadecyltrimethylammonium
Ium hydroxide, dodecylbenzene trimethylan
Monium hydroxide, dodecylbenzyltrimethyla
And ammonium hydroxide. Of these, in the general formula (I), R represents an alkyl
Alkyl trimethyl ammonium hydroxy
And hexadecyltrimethyl ammonium
Hydroxide, octadecyltrimethylammonium
Muhydroxide is particularly preferred. These compounds are one kind
Alternatively, two or more kinds can be used in combination. The amount of the catalyst used is selected from the aromatics
10 moles per mole of dihydroxy compound ^-6 -10 ^-2 Mo
, Preferably 2 × 10 ^-6 -10 ^-3 Mole, especially preferred
Is 5 × 10 ^-6 -10 ^-Four Can be used. If the ratio exceeds the above range, coloring 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 method of charging the catalyst is a solid.
It does not matter whether it is liquid or liquid, but it is preferably a solution or a suspension.
It is liquid. The concentration of the solution or suspension is liquid
Any concentration that can be handled in a state is acceptable, and preferably 50 weight
%, More preferably 40% by weight or less. The solution
Or the concentration of oxygen dissolved in the suspension is 100ppm or less
And more preferably 50 ppm or less, more preferably
More preferably, it is 10 ppm or less. This range
If it exceeds, coloring or branching components may occur due to the effect of dissolved oxygen.
Easy to generate. Further, in the present invention, before the initiation of polymerization,
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. The sulfur-containing acidic compound and / or the acid
Derivatives formed from reactive compounds include sulfurous acid and sulfuric acid.
Acid, sulfinic acid compound, sulfonic acid compound and
These derivatives can be mentioned. Specifically, sulfuric acid
Derivatives include dimethyl sulfate, diethyl sulfate, sulfuric acid,
Dipropyl sulfate, dibutyl sulfate, diphenyl sulfate,
Cyl sulfite, diethyl sulfite, diphenyl sulfite, dode
Sodium silyl sulfate, sodium hexadecyl sulfate,
Dimethyl butyl tridecyl ammonium sulfate
Dimethyl ethyl hexadecyl ammonium sulfate
Trimethylhexadecyl ammonium sulfate, etc.
I can do it. As the sulfinic acid compound, benzene
Sulfinic acid, toluenesulfinic acid, naphthalenesul
Finic acid and the like can be mentioned. Sulfonic acid compound
And derivatives thereof include the following compounds:
I can do it. That is, benzenesulfonic acid, p
-Sulfonic acid such as toluenesulfonic acid, benzene sulfone
Methyl phonate, ethyl benzenesulfonate, benzenes
Butyl sulfonate, Octyl benzenesulfonate, Benze
Phenyl sulfonate, methyl p-toluenesulfonate
, Ethyl p-toluenesulfonate, p-toluenesulfur
Butyl phonate, octyl p-toluenesulfonate, p-
Sulfonate esters such as phenyl toluenesulfonate
, Ammonium p-toluenesulfonate, p-tolue
Tetrabutylphosphonium sulfonate, dodecylben
Sulfonates such as tetraphenylphosphonium zensulfonate
Ammonium phonate can be mentioned. These compounds may be used alone or in combination.
It can be used together. Of these, [B] pK
a sulfur-containing acidic compound having an a value of 3 or less and the acid
As a derivative formed from the compound, a sulfonic acid compound
And derivatives thereof are preferably used, especially benzene
Sulfonic acid, butyl benzenesulfonate, p-toluene
Sulfonic acid, ethyl p-toluenesulfonate, p-toluene
Butyl enesulfonate, sodium dodecyl sulfate, methyl
Trimethylhexadecyl ammonium sulfate, p-toluene
Tetrabutylphosphonium enesulfonate, dodecylbe
Tetraphenylphosphonium benzenesulfonate is preferred
Commonly used. Examples of the phenolic stabilizer include n
-Octadecyl-3- (4-hydroxy-3 ', 5'-
Di-t-butylphenyl) propionate, tetrakis
[Methylene-3- (3 ', 5'-di-t-butyl-4-
Hydroxyphenyl) propionate] methane, 1,
1,3-Tris (2-methyl-4-hydroxy-5-t
-Butylphenyl) butane, distearyl (4-hydro
Xy-3-methyl-5-tert-butyl) benzylmalone
4-Hydroxymethyl-2,6-di-tert-butyl
And the like, and when used alone, two or more
The above mixture may be used. As the thioether-based stabilizer, for example,
Dilauryl thiodipropionate, distearyl thi
Odipropionate, dimyristyl-3,3'-thiodi
Propionate, ditridecyl-3,3'-thiodipro
Pionate, pentaerythritol-tetrakis- (β
-Lauryl-thiopropionate).
These may be used alone or in combination of two or more. As the phosphorus-based stabilizer, for example,
(2,4-di-t-butylphenyl) pentaerythri
Tildiphosphite, diphenyldecylphosphite,
Phenylisooctyl phosphite, 2-ethylhexyl
Arylalkyl phosphites such as rudiphenyl phosphite
Aite; trimethyl phosphite, triethyl phospha
Site, tributyl phosphite, trioctadecyl phosphite
Fight, distearyl pentaerythrityl diphospha
Site, tris (2-chloroethyl) phosphite, tri
Tris (2,3-dichloropropyl) phosphite
Alkyl phosphite; tricyclohexyl phosphite
Tricycloalkyl phosphite; triphenyl
Phosphite, tricresyl phosphite, tris (d
Tylphenyl) phosphite, tris (2,4-di-t)
-Butylphenyl) phosphite, tris (hydroxy
Triaryl phosphites such as phenyl) phosphite
G; trimethyl phosphate, triethyl phosphate
Tributyl phosphate, trioctadecyl phosphate
Distearyl pentaerythrityl phosphate
Tris (2-chloroethyl) phosphate
Alkyl phosphate; tricyclohexyl phosphate
Tricycloalkyl phosphate; triphenyl
Phosphate, tricresyl phosphate, tris (no
Nylphenyl) phosphate, 2-ethylphenyldiph
Triaryl phosphates such as phenyl phosphate
These may be used alone or in combination of two or more.
May be. The hindered amine stabilizers include
For example, bis (2,2,6,6-tetramethyl-4-pi
Peridyl) sebacate, 8-benzyl-7,7,9,9
-Tetramethyl-3-octyl-1,2,3-triaza
Spiro [4,5] undecane-2,4-dione, tetra
Kiss (2,2,6,6-tetramethyl-4-piperidi
Le) 1,2,3,4-butanetetracarboxylate
Even if these are used alone, two or more kinds are mixed.
May be used. In the present invention, an epoxy compound is used as a stabilizer.
Things can be used. Such epoxy compounds
Compounds with one or more epoxy groups in one molecule
You can. Specific examples of such an epoxy compound include:
Include epoxidized soybean oil, epoxidized linseed oil,
Luglycidyl ether, t-butylphenyl glycidyl
Ether, 3,4-epoxycyclohexylmethyl-
3 ', 4'-Epoxycyclohexylcarboxylate
G, 3,4-epoxycyclohexylethyleneoxy
Do, cyclohexylmethyl-3,4-epoxycyclo
Xyl carboxylate, 3,4-epoxy-6-methyl
Lecyclohexylmethyl-6'-methylsilohexylca
Ruboxylate, bisphenol-A diglycidyl ester
Ter, diglycidyl ester of phthalic acid, hexahydro
Diglycidyl ether of phthalic acid, bis-epoxydisi
Clopentadienyl ether, bis-epoxy ethylene
Glycol, bis-epoxycyclohexyl adipate
G, butadiene diepoxide, tetraphenylethylene
Epoxide, octyl epoxy tartrate, epoxidized
Libutadiene, 3,4-dimethyl-1,2-epoxy
Chlohexane, 3,5-dimethyl-1,2-epoxy
Chlohexane, 3-methyl-5-t-butyl-1,2-
Epoxycyclohexane, octadecyl-2,2-dimethyl
Cyl-3,4-epoxycyclohexylcarboxylate
G, N-butyl-2,2-dimethyl-3,4-epoxy
Cyclohexyl carboxylate, cyclohexyl-2
-Methyl-3,4-epoxycyclohexylcarboxy
Rate, N-butyl-2,2-dimethyl-3,4-epo
Xy-5-methylcyclohexylcarboxylate, e
Kutadecyl-3,4-epoxycyclohexylcarboxy
Silate, 2-ethylhexyl-3 ', 4'-epoxy
Cyclohexyl carboxylate, 4,6-dimethyl-
2,3-epoxycyclohexyl-3 ', 4'-epoxy
Cyclohexylcarboxylate, 4,5-epoxy
Tetrahydrophthalic anhydride, 3-tert-butyl-4,5-
Epoxy tetrahydrophthalic anhydride, diethyl-4,5
-Epoxy-cis-1,2-cyclohexyldicarboxy
Silate, di-n-butyl-3-t-butyl-4,5-
Epoxy-cis-1,2-cyclohexyldicarboxy
Rate and the like can be mentioned. Specific examples of the salicylic acid-based ultraviolet absorber include:
Typically, phenyl salicylate, pt-butylphenyl
Lusalicylate. Benzophenone UV
As the absorbent, 2,4-dihydroxybenzopheno
2-hydroxy-4-methoxybenzophenone,
2,2'-dihydroxy-4-methoxybenzopheno
2,2'-dihydroxy-4,4'-dimethoxybenzene
Nzophenone, 2-hydroxy-4-methoxy-2'-
Carboxybenzophenone, 2-hydroxy-4-metho
Xy-5-sulfobenzophenone trihydrate, 2-
Hydroxy-4-n-octoxybenzophenone, 2,
2 ', 4,4'-tetrahydroxybenzophenone, 4
-Dodecyloxy-2-hydroxybenzophenone, bis
(5-benzoyl-4-hydroxy-2-methoxyfe
Nyl) methane, 2-hydroxy-4-methoxybenzof
And enone-5-sulfonic acid. Benzotriazole UV absorber
Is 2- (2'-hydroxy-5'-methylphenyl)
Benzotriazole, 2- (2'-hydroxy-3 ',
5'-di-t-butylphenyl) benzotriazole,
2- (2'-Hydroxy-3'-t-butyl-5'-me
Tylphenyl) -5-chlorobenzotriazole, 2-
(2'-Hydroxy-3 ', 5'-di-tert-butyl-f
Enyl) -5-chlorobenzotriazole, 2- (2 '
-Hydroxy-5'-octylphenyl) benzotria
Zol, 2- (2'-hydroxy-3 ', 5'-diamid
Ruphenyl) benzotriazole, 2- [2'-hydro
Xy-3 '-(3 ", 4", 5 ", 6" -tetrahydro
Phthalimidomethyl) -5'-methylphenyl] benzo
Triazole, 2,2'-methylenebis [4- (1,
1,3,3-tetramethylbutyl) -6- (2H-ben
Zotriazol-2-yl) phenol]
be able to. As a cyanoacrylate ultraviolet absorber
Is 2-ethylhexyl-2-cyano-3,3-dife
Nyl acrylate, ethyl-2-cyano-3,3-diph
And phenyl acrylate. These compounds are the above aromatic compounds
Melt polycondensation of droxy compound and diaryl carbonate
When producing polycarbonate by combining
The reaction system contains 10 to 40, preferably 15 carbon atoms in the reaction system.
To 40 phenols, aromatic aromatic dihydric compounds
0.05 to 10 mol%, preferably 0.5 to 7
Mole%, more preferably 1 to 5 mole%.
You. The pheno having 10 to 40 carbon atoms as described above
The following compounds are used as tools. o-
m-butylphenol, p-cyclohexylphenol
, O-phenylphenol, m-isobutylphenol
, Mn-nonylphenol, pt-butylpheno
, Om-pentylphenol, p-cumylpheno
, P-m-pentylphenol, o-naphthylfe
Knol, pn-pentylphenol, mn-hexyl
Phenol, 2,6-di-t-butylphenol,
2,4-di-tert-butylphenol, 3,5-di-tert-
Butylphenol, 2,6-dicumylphenol, 3,
5-Dicumylphenol, 2,2,2-trimethyl-4
-Monohydroxy such as (hydroxyphenyl) chroman
Monovalent phenols such as chroman derivatives are used. As described above, the combination of
The reacted catalyst allows the polycondensation reaction to proceed at a sufficient
Of low molecular weight polycarbonate with high polymerization activity
Is preferred. In the presence of such a catalyst, the aromatic dihydro
The polycondensation reaction between a xy compound and a carbonic acid diester has been
Under the same conditions as the polycondensation reaction conditions
it can. 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 to 190 ° C., about 0.5 to 5 hours, preferably
0.5 to 4 hours, more preferably 0.5 to 3 hours
The aromatic dihydroxy compound and the diarylca
And carbonate. Then increase the vacuum of the reaction system.
While increasing the reaction temperature to obtain aromatic dihydroxy compounds
And carbonic acid diester, and finally 5 mmH
g, preferably 1 mmHg or less,
Aromatic dihydroxy compound and carbonate carbonate at -320 ° C
To 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 (measured in methylene chloride at 20 ° C with an Ubbeloth viscometer)
Is 0.1 to 1.0, preferably 0.2 to 0.8.
You. 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 and the
The reaction is suppressed, and even if the polymerization is high,
Polycarbonate with low generation of insoluble matter and foreign matter
it can. Branching reaction and other side reactions also occur during molding.
Is suppressed, and burns, coloring, insolubilization, and foreign matter generation
Production of polycarbonate with low molecular weight reduction
Can be. Further, according to the method of the present invention,
High quality polycarbonate efficiently and therefore high productivity
Can be manufactured. According to the method of the present invention,
Use the polymerization equipment repeatedly without washing it for a long time.
Continue to produce high quality polycarbonate as above
Therefore, the method of the present invention
This is very advantageous as a method for industrial production. The present invention will be described below with reference to examples. Book
In the present invention, physical properties were measured according to the following methods. (I) Intrinsic viscosity [η]: Ube in methylene chloride at 20 ° C
It was measured with a rote viscometer. (Ii) Filterability: Nitrogen was removed from the polymer in a SUS316 test tube.
Polymer obtained by treating at 290 ° C for 20 hours in a stream of air
Was crushed. 5 g of polymer in 100 ml of methylene chloride
It was added to the solution and irradiated with ultrasonic waves to dissolve it. Obtained polymer solution
0.5 kg / cm with 1 micron Millipore filter
^Two , And evaluated under the following three stages. "Good" ... Filtered in less than 15 minutes. "Somewhat bad" ... Filtered in 15 to 30 minutes. "Poor": The filtration time exceeds 30 minutes. (Iii) Polymer color tone (L value / b value): 3 mm thick
Cylinder temperature 300 ° C Injection pressure 100kg
/ Cm ^Two Molded at a mold temperature of 90 ° C, and the X, Y, Z values are
Colorland Color Defef manufactured by Denshoku Kogyo
ence meter ND-1001DP
The L value and the b value were measured by an excess method. (Iv) Gel evaluation: 10 g of polymer in a stainless steel container
290 ° C./0.3-0.5 mmHg / 20 hours
After heat treatment under the conditions, to methylene chloride 500-1000ml
After dissolution, the insoluble matter was collected. Dry weight dissolution of the insolubles
Expressed as a percentage by weight relative to the weight of the previous sample. (V) polymerization activity: polymerization in which the intrinsic viscosity [η] becomes 0.45
The time (hour) was measured. Examples 1 to 6 Bisphenol A (BP
A) 228 parts, diphenyl carbonate 225 parts and
The catalysts of the types and amounts shown in Tables 1-2 were stirred with a stirrer,
And a reaction tank (100 liter capacity) equipped with a decompression device.
After replacing with nitrogen, the mixture was dissolved at 140 ° C. 30 minutes
After stirring, the internal temperature was raised to 180 ° C, and the pressure was gradually reduced to 100 ° C.
Distill off the phenol produced by reacting at 30 mmHg for 30 minutes
did. Furthermore, the pressure was gradually reduced while the temperature was raised to 200 ° C., and 50 m
The reaction was carried out while distilling phenol at mHg for 30 minutes.
A tell exchange reaction was performed. Next, the reaction solution was transferred to a second reaction tank,
Gradually raise and lower the temperature to 20 ° C and 30mmHg,
30 minutes at pressure, further 10 mmHg at 240 ° C, 260 ° C
Up to 1 mmHg at 270 ° C and below 1 mmHg
The temperature was repeatedly increased and reduced by the same procedure to continue the reaction. Next, the stirring power was measured at 270 ° C. and 1 mmHg.
[Η] =
The polymerization time to obtain 0.45 was determined, and finally [η] = 0.
Polycarbonate is produced by performing polycondensation with the goal of 5.
did. Table 1 shows the results of measuring the physical properties of the obtained polymer.
It is shown in FIG. [Table 1] [Table 2] The polycarbonate produced according to the invention
Has a fast polymerization rate and produces little insoluble
I can pass. Low gel formation and extremely high continuous productivity
No. [Comparative Examples 1-3] The catalysts shown in Table 3 were used.
The reaction was carried out in the same manner as in Example 1 except that
Table 3 shows the physical properties of the polymer. [Table 3] According to Comparative Example 1, the reaction rate at a high temperature was extremely low.
However, a polymer having a very low degree of polymerization was not obtained. Comparative example
According to 2, the reaction rate is low and the productivity is extremely low.
Was. According to Comparative Example 3, the reaction rate was relatively improved
However, the gel production rate was high and the continuous productivity was low.

(56) References US Patent 5,340,905 (US, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 64/00-64/42

Claims (1)

(57) [Claim 1] Melt polycondensation of an aromatic dihydroxy compound and a carbonic acid diester in the presence of a quaternary ammonium hydroxide compound represented by the following general formula (I): A method for producing an aromatic polycarbonate. Embedded image