JPH1036497A - Production of polycarbonate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a stabilized polycarbonate excellent in color tone and contg. only a small amt. of remaining phenol. SOLUTION: An aromatic polycarbonate is produced by the melt polycondensation of an aromatic dihydroxy compd. and a diphenyl carbonate. After the intrinsic viscosity of the polycarbonate has reached at least 0.3dl/g, a compd. of the formula (wherein R<1> represents a chlorine atom, methoxycarbonyl group or ethyoxycarbonyl group; and R<2> represents a 1-30C alkyl group, 1-30C alkoxyl group, 6-30C aryl group or 6-30C aryloxy group) is added to form a polycarbonate having blocked terminals and an intrinsic viscosity change of within 0.1dl/g based on the intrinsic viscosity at the time of the addition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for producing polycarbonate. More specifically, the present invention relates to a method for producing a polycarbonate having a terminal terminated or an increased degree of polymerization utilizing the reactivity of a terminal phenolic hydroxyl group of the polycarbonate.

[0002]

2. Description of the Related Art Polycarbonate is widely used because of its excellent mechanical properties such as impact resistance, heat resistance and transparency. As a method for producing such a polycarbonate, a method of directly reacting phosgene with an aromatic diol such as bisphenol A (interfacial polymerization method) or a method in which an aromatic dihydroxy compound such as bisphenol and a diallyl carbonate such as diphenyl carbonate are melted are used. A method of transesterification (melting method) and the like are known. Among such production methods, the method of transesterification (melting method) between an aromatic dihydroxy compound and diallyl carbonate uses a toxic halogen compound such as phosgene or methylene chloride as a solvent, as compared with an interfacial polymerization method. There is no problem in using it as it is, and there is an advantage that it can be manufactured at low cost, and it is considered that it is promising in the future.

In the melting method, the following method is known as a method characteristic of the diallyl carbonate used.

US Pat. No. 4,310,656 discloses a method for transesterifying a mixture of bis (ortho-haloaryl) carbonate / ortho-haloaryl-aryl-carbonate and dihydroxyphenol. As bis (ortho-haloaryl) carbonate, bis (o-chlorophenol) carbonate, bis (o-fluorophenol) carbonate and the like are described, and as ortho-haloaryl-arylcarbonate, o-chlorophenyl-phenyl carbonate, o -Fluorophenyl-phenyl carbonate and the like are described.

US Pat. No. 4,329,443 discloses a method for transesterifying a bis (ortho-haloaryl) ester or bis (ortho-haloaryl) carbonate with dihydroxyphenol. As the bis (ortho-haloaryl) ester, bis (o-chlorophenol) ester, bis (o-trifluoromethylphenol) ester and the like are described. As the bis (ortho-haloaryl) carbonate, US Pat. Compounds similar to those described in 310,656 are described.

US Pat. No. 4,323,668 discloses a method for transesterifying (ortho-alkoxycarbonylaryl) carbonate with dihydroxyphenol. As the (ortho-alkoxycarbonylaryl) carbonate, bis (o-methoxycarbonylphenyl) carbonate, bis (o-ethoxycarbonylphenyl) carbonate and the like are described.

[0007] Further, in the polymerization of polycarbonate by a melting method, use of a terminal blocking agent has been studied in order to improve the quality of the polymer such as the hue, heat resistance and hydrolysis resistance of the produced polycarbonate.

Japanese Patent Application Laid-Open No. 63-179301 discloses a bisphenol A polycarbonate terminated with methyl salicylate as a basic material of an optical information recording medium.

Japanese Patent Application Laid-Open No. 2-175723 discloses that an aromatic dihydroxy compound and a carbonic acid diester are converted to a compound having 1 carbon atom.
Polycondensation is carried out in the presence of 0 to 40 phenols so that the ratio of terminal hydroxyl groups is 30% or less and the intrinsic viscosity is 0.3 to 1.
A method for producing a polycarbonate that is 0 dl / g (20 ° C. in methylene chloride) is disclosed. Carbon number 10
As the phenols Nos. To 40, butylphenol, cumylphenol, phenylphenol and the like are disclosed.

Japanese Unexamined Patent Publication (Kokai) No. 6-157739 discloses a method for producing an aromatic polycarbonate by melt-polycondensing an aromatic dihydroxy compound and a carbonic acid diester in at least two reactors connected in series. Discloses a method for adding an endcapping agent to at least one reactor in which the intrinsic viscosity of the polymer has reached 0.20 dl / g at the reactor inlet.

Examples of the terminal blocking agent include carbonic acid diesters having 17 to 50 carbon atoms, carbonic acid diesters having 13 to 16 carbon atoms,
Epoxy compounds having 2 to 50 carbon atoms and monoesters having 5 to 40 carbon atoms are mentioned. However, these exemplified compounds do not disclose the terminal blocking agent used in the present invention.

Japanese Patent Application Laid-Open No. 7-238156 discloses a polycarbonate obtained by a melting method having a hydroxyl terminal of 30 mol% or less, a sodium content of 1 ppm or less, and a chlorine content of 20 ppm or less. It is disclosed in the same publication that such a polycarbonate is obtained by allowing a phenol having 10 to 40 carbon atoms or a carbonic acid diester having 17 to 50 carbon atoms to be present when the aromatic dihydroxy compound and the carbonic acid diester are melt-polycondensed. Have been. However, none of these exemplified compounds discloses the terminal blocking agent used in the present invention.

[0013] Further, there is also known a method for producing a polycarbonate having an increased degree of polymerization by adding a certain compound to a reaction system when producing a polycarbonate by a transesterification method.

Japanese Patent Application Laid-Open No. 7-90074 discloses that when a polycarbonate is produced from a dihydroxy compound and a carbonic acid diester by a transesterification method, the activity of a divalent or higher valent compound becomes higher after the transesterification reaction rate exceeds 70%. Disclosed is a method for producing a polycarbonate having an increased degree of polymerization by adding a diester, an acid halide or an acid anhydride.

As the active diester, bis (4-
Carbonate compounds such as nitrophenyl) carbonate and carboxylic esters such as bis (4-cyanophenyl) terephthalate are disclosed. However, these exemplified compounds do not disclose the dicarbonate compound in the setting used in the present invention.

[0016]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a method for producing a polycarbonate having a terminal terminated or an increased degree of polymerization by utilizing the reactivity of a terminal phenolic hydroxyl group of the polycarbonate by melt polycondensation. Is to provide.

It is another object of the present invention to rapidly block at least a portion of the terminal phenolic hydroxyl groups of the polycarbonate and thereby sufficiently modify the polycarbonate, for example to provide a polycarbonate having excellent mold release properties. To provide a method for producing polycarbonate.

Still another object of the present invention is to provide excellent color tone,
Another object of the present invention is to provide a method for producing a stabilized polycarbonate having a small residual amount of phenols derived from a terminal blocking agent.

Yet another object of the present invention is to provide a method for rapidly producing a polycarbonate having an increased degree of polymerization by melt polycondensation.

It is still another object of the present invention to provide a method for producing a polycarbonate having an excellent color tone and an increased degree of polymerization at a high productivity and at a low cost.

Other objects and advantages, such as the present invention, will become apparent from the following description.

[0022]

According to the present invention, the above objects and advantages of the present invention are firstly achieved in a method for producing an aromatic polycarbonate by melt-polycondensing an aromatic dihydroxy compound and diphenyl carbonate. ,
The intrinsic viscosity of the polycarbonate is at least 0.3 dl /
g, the following equation (1)

[0023]

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Wherein R ¹ is a chlorine atom, a methoxycarbonyl group or an ethoxycarbonyl group;
² is an alkyl group having 1 to 30 carbon atoms, an alkoxyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aryloxy group having 6 to 30 carbon atoms, wherein Alkyl groups and alkoxyl groups having 1 to 30 carbon atoms are methoxycarbonyl, ethoxycarbonyl,
It may be substituted by (o-methoxycarbonylphenyl) oxycarbonyl or (o-ethoxycarbonylphenyl) oxycarbonyl, and an aryl group having 6 to 30 carbon atoms and an aryloxy group having 6 to 30 carbon atoms are methoxycarbonyl, Ethoxycarbonyl, (o-methoxycarbonylphenyl) oxycarbonyl, (o-ethoxycarbonylphenyl) oxycarbonyl, which may be substituted by alkyl having 1 to 30 carbons or alkoxyl having 1 to 30 carbons] To produce an end-capped polycarbonate having a change in intrinsic viscosity within 0.1 dl / g based on the intrinsic viscosity at the time of addition.

The compounds represented by the above formula (1) used in the present invention include carbonates and carboxylic esters according to the definition of R ² .

In the formula (1), R ¹ is a chlorine atom, a methoxycarbonyl group (CH ₃ OCO—) or an ethoxycarbonyl group (C ₂ H ₅ OCO—). Of these, a chlorine atom and a methoxycarbonyl group are preferred,
A methoxycarbonyl group is particularly preferred.

R ² is an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms or an aryloxy group having 6 to 30 carbon atoms.

The alkyl group having 1 to 30 carbon atoms may be linear, branched, or cyclic, and may have an unsaturated group. Such alkyl groups include, for example, methyl, ethyl, n-propyl, n
Linear alkyl groups such as -butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-nonyl group, n-dodecanyl group, n-lauryl group, n-palmityl group, stearyl group; isopropyl Alkyl groups having an unsaturated group such as an allyl group, a butenyl group, a pentenyl group, a hexenyl group, a dodecenyl group, an oleyl group, that is, an alkenyl group; And cycloalkyl groups such as cyclopentyl group and cyclohexyl group. Among them, from the viewpoint of improving the releasability of the polymer, a long-chain alkyl group,
Specifically, a lauryl group, a stearyl group, and a dodecenyl group are particularly preferred.

The alkoxyl group having 1 to 30 carbon atoms may be linear, branched or cyclic, and may have an unsaturated group. Examples of such alkoxyl groups include methoxy, ethoxy, n-propoxy, n-butoxy, n-pentoxy, n-hexoxy, n-octoxy, n-nonyloxy, n-decanyloxy, and n Linear alkoxyl groups such as -lauryloxy group, n-palmityloxy group, stearyloxy group; iso-propyl group, t
A branched chain alkoxyl group such as -butyloxy group or 4-butylnonyloxy group; an alkoxy group having an unsaturated group such as allyloxy group, butenyloxy group, pentenyloxy group, hexenyloxy group, dodecenyloxy group or oleyloxy group; cyclopentyloxy And cycloalkyloxy groups such as a hexohexyloxy group. Among these, a long-chain alkyl group such as a lauryloxy group, a stearyloxy group, or a dodecenyloxy group is particularly preferable from the viewpoint of improving the releasability of the polymer.

As mentioned above, the alkyl group having 1 to 30 carbon atoms and the alkoxyl group having 1 to 30 carbon atoms are methoxycarbonyl, ethoxycarbonyl, (o-methoxycarbonylphenyl) oxycarbonyl

[0031]

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Or (o-ethoxycarbonylphenyl) oxycarbonyl

[0033]

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May be substituted with

The aryl group having 6 to 30 carbon atoms includes, for example, phenyl, naphthyl, biphenyl, anthranyl and the like.

The aryloxy group having 6 to 30 carbon atoms includes, for example, phenoxy, naphthoxy, biphenyloxy, anthranyloxy and the like.

The aryl group having 6 to 30 carbon atoms and the aryloxy group having 6 to 30 carbon atoms are methoxycarbonyl, ethoxycarbonyl, (o-methoxycarbonylphenyl) oxycarbonyl, (o-ethoxycarbonylphenyl) oxycarbonyl, It may be substituted by alkyl having 1 to 30 carbons or alkoxyl having 1 to 30 carbons. Alkyl having 1 to 30 carbons and 1 carbon
As the alkoxyl to -30, the same as the above-mentioned exemplified groups can be mentioned here.

The compounds represented by the above formula (1) may, R ²
For convenience, based on the definition of

[0039]

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Here, the definition of R ¹ is the same as in formula (1) and R ²¹ is an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, and these groups are represented by the formula (1) )
May be substituted with the substituent defined in the above.

A carbonate compound represented by the following formula (1) -2:

[0042]

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Here, the definition of R ¹ is the same as in the formula (1), and R ²² is an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, and these groups are represented by the formula (1) )
May be substituted with the substituent defined in the above.

The carboxylic acid aryl esters represented by the following formulas can be classified.

Examples of the carbonate compound represented by the above formula (1) -1 include 2-chlorophenyl-phenyl carbonate, 2-chlorophenyl-4'-methylphenyl carbonate, 2-chlorophenyl-4'-ethylphenyl carbonate and 2-chlorophenyl-4'-methylphenyl carbonate. Chlorophenyl-4'-
n-butylphenyl carbonate, 2-chlorophenyl-4'-t-butylphenyl carbonate, 2-chlorophenyl-4'-nonylphenyl carbonate, 2-chlorophenyl-4'-cumyl carbonate, 2-chlorophenyl-naphthyl carbonate, 2- Chlorophenyl-4'-methoxyphenyl carbonate, 2-chlorophenyl-4'-ethoxyphenyl carbonate, 2-chlorophenyl-4'-n-butoxyphenyl carbonate, 2-chlorophenyl-4'-t-butoxyphenyl carbonate, 2-chlorophenyl 4'-nonyloxyphenyl carbonate, 2-chlorophenyl-4'-
t-propyloxyphenyl carbonate, 2-chlorophenyl-2'-methoxycarbonylphenyl carbonate, 2-chlorophenyl-4'-methoxycarbonylphenyl carbonate, 2-chlorophenyl-2'-ethoxycarbonylphenyl carbonate, 2-chlorophenyl-4'- 2-chlorophenyl-acrylyl, such as ethoxycarbonylphenyl carbonate, 2-chlorophenyl-2 '-(o-methoxycarbonylphenyl) oxycarbonylphenyl carbonate, 2-chlorophenyl-2'-(o-ethoxycarbonylphenyl) oxycarbonylphenyl carbonate Carbonates; 2-chlorophenylmethyl carbonate, 2-chlorophenyl-ethyl carbonate, 2-chlorophenyl-n-butyl carbonate DOO, 2-chlorophenyl - octyl carbonate, 2-chlorophenyl -i- propyl carbonate, 2-chlorophenyl 2-methoxycarbonylethyl carbonate, 2-chlorophenyl-2-
2-chlorophenyl-alkyl carbonates such as ethoxycarbonylethyl carbonate, 2-chlorophenyl-2- (o-ethoxycarbonylphenyl) oxycarbonylethyl carbonate; 2-methoxycarbonylphenyl-phenyl carbonate; 2-methoxycarbonylphenyl-methylphenyl carbonate 2,2-methoxycarbonylphenyl-ethylphenyl carbonate, 2-methoxycarbonylphenyl-propylphenyl carbonate, 2-methoxycarbonylphenyl-n
-Butylphenyl carbonate, 2-methoxycarbonylphenyl-t-butylphenyl carbonate, 2-methoxycarbonylphenyl-hexylphenyl carbonate, 2-methoxycarbonylphenyl-nonylphenyl carbonate, 2-methoxycarbonylphenyl-dodecylphenyl carbonate, 2-methoxy Carbonylphenyl-hexadecylphenyl carbonate, 2-methoxycarbonylphenyl-di-n-butylphenyl carbonate, 2-methoxycarbonylphenyl-di-tert-butylphenyl carbonate, 2-methoxycarbonylphenyl-dinonylphenyl carbonate, 2-methoxycarbonylphenyl -Cyclohexylphenyl carbonate, 2-methoxycarbonylphenyl-naphthylphenyl carbonate 2-methoxycarbonylphenyl -
Biphenyl carbonate, 2-methoxycarbonylphenyl-cumylphenyl carbonate, 2-methoxycarbonylphenyl-4'-methoxyphenylcarbonate, 2-methoxycarbonylphenyl-4'-ethoxyphenylcarbonate, 2-methoxycarbonylphenyl-4'-n -Butoxyphenyl carbonate, 2-methoxycarbonylphenyl-4'-t-butoxyphenyl carbonate, 2-methoxycarbonylphenyl-
4'-nonyloxyphenyl carbonate, 2-methoxycarbonylphenyl-4'-cumyloxyphenyl carbonate, di (2-methoxycarbonylphenyl) carbonate, 2-methoxycarbonylphenyl-4'-
Methoxycarbonylphenyl carbonate, 2-methoxycarbonylphenyl-2'-ethoxycarbonylphenylcarbonate, 2-methoxycarbonylphenyl
4'-ethoxycarbonylphenyl carbonate, 2-
Methoxycarbonylphenyl-2 '-(o-methoxycarbonylphenyl) oxycarbonylphenyl carbonate, 2-methoxycarbonylphenyl-2'-(o-
2-methoxycarbonylphenyl aryl carbonates such as ethoxycarbonylphenyl) oxycarbonylphenyl carbonate; 2-methoxycarbonylphenyl-methyl carbonate, 2-methoxycarbonylphenyl-ethyl carbonate, 2-methoxycarbonylphenyl-n-butyl carbonate, 2- Methoxycarbonylphenyl-octyl carbonate, 2-methoxycarbonylphenyl-nonyl carbonate, 2-methoxycarbonylphenyl-cetylcarbonate, 2-methoxycarbonylphenyl-lauryl carbonate, 2-
Methoxycarbonylphenyl-2-methoxycarbonylethyl carbonate, 2-methoxycarbonylphenyl-2-ethoxycarbonylethyl carbonate, 2-methoxycarbonylphenyl-2- (o-methoxycarbonylphenyl) oxycarbonylethyl carbonate,
2-methoxycarbonylphenyl-alkyl carbonates such as 2-methoxycarbonylphenyl-2- (o-ethoxycarbonylphenyl) oxycarbonylethyl carbonate; 2-ethoxycarbonylphenyl-phenyl carbonate; 2-ethoxycarbonylphenyl-methylphenyl carbonate; 2-ethoxycarbonylphenyl-ethylphenyl carbonate, 2-ethoxycarbonylphenyl-propylphenyl carbonate, 2-ethoxycarbonylphenyl-n-butylphenylcarbonate, 2-ethoxycarbonylphenyl-
t-butylphenyl carbonate, 2-ethoxycarbonylphenyl-hexylphenyl carbonate, 2-ethoxycarbonylphenyl-nonylphenyl carbonate, 2-ethoxycarbonylphenyl-dodecylphenyl carbonate, 2-ethoxycarbonylphenyl-hexadecylphenyl carbonate, 2-ethoxy Carbonylphenyl-di-n-butylphenyl carbonate, 2
-Ethoxycarbonylphenyl-di-tert-butylphenyl carbonate, 2-ethoxycarbonylphenyl-di-t
-Butylphenyl carbonate, 2-ethoxycarbonylphenyl-dinonylphenyl carbonate, 2-ethoxycarbonylphenyl-cyclohexylphenyl carbonate, 2-ethoxycarbonylphenyl-naphthylphenyl carbonate, 2-ethoxycarbonylphenyl-biphenylcarbonate, 2-ethoxycarbonylphenyl -Cumylphenyl carbonate, 2-ethoxycarbonylphenyl-4'-methoxyphenylcarbonate, 2-ethoxycarbonylphenyl-4'-ethoxyphenylcarbonate, 2-ethoxycarbonylphenyl-4'-n-butoxyphenylcarbonate, 2-
Ethoxycarbonylphenyl-4'-tert-butoxyphenylcarbonate, 2-ethoxycarbonylphenyl-
4'-nonyloxyphenyl carbonate, 2-ethoxycarbonylphenyl-4'-cumyloxyphenyl carbonate, di (2-ethoxycarbonylphenyl) carbonate, 2-ethoxycarbonylphenyl-4'-
Methoxycarbonylphenyl carbonate, 2-ethoxycarbonylphenyl-4'-ethoxycarbonylphenylcarbonate, 2-ethoxycarbonylphenyl
2 '-(o-methoxycarbonylphenyl) oxycarbonylphenyl carbonate, 2-ethoxycarbonylphenyl-2'-(o-ethoxycarbonylphenyl)
2-ethoxycarbonylphenyl-aryl carbonates such as oxycarbonylphenyl carbonate; 2
-Ethoxycarbonylphenyl-methyl carbonate,
2-ethoxycarbonylphenyl-ethyl carbonate, 2-ethoxycarbonylphenyl-n-butyl carbonate, 2-ethoxycarbonylphenyl-octyl carbonate, 2-ethoxycarbonylphenyl-2-
Methoxycarbonylethyl carbonate, 2-ethoxycarbonylphenyl-2-ethoxycarbonylethyl carbonate, 2-ethoxycarbonylphenyl 2- (o
-Methoxycarbonylphenyl) oxycarbonylethyl carbonate, 2-ethoxycarbonylphenyl-2
2-ethoxycarbonylphenyl-alkyl carbonates such as-(o-ethoxycarbonylphenyl) oxycarbonylethyl carbonate; Among these, 2-methoxycarbonylphenyl-phenyl carbonate is excellent in hydrolysis resistance (moisture and temperature resistance) because the terminal is blocked by a phenyl group.

The aryl carboxylate represented by the above formula (1) -2 includes, for example, 2-benzoic acid
Chlorophenyl, 2-chlorophenyl 4-methylbenzoate 2-chlorophenyl 4-ethylbenzoate, 4-n-
2-chlorophenyl butylbenzoate, 2-chlorophenyl 4-tert-butylbenzoate, 4-nonylbenzoic acid 2-
2-chlorophenyl 4-chlorophenyl, 4-cumylbenzoate, 2-chlorophenyl naphthoate, 2-chlorophenyl 4-methoxybenzoate, 2-chlorophenyl 4-ethoxybenzoate, 2-chlorophenyl 4-n-butoxybenzoate, 4-t- 2-chlorophenyl butoxybenzoate, 2-chlorophenyl 4-nonyloxybenzoate,
2-chlorophenyl 2-cumyloxybenzoate, 2-chlorophenyl 2-methoxycarbonylbenzoate, 2-chlorophenyl 2-methoxycarbonylbenzoate, 2-chlorophenyl 2-ethoxycarbonylbenzoate, 2-chlorophenyl 4-ethoxycarbonylbenzoate, 2- (O
2-methoxyphenylphenyl) oxycarbonylbenzoate 2-chlorophenyl 2- (o-ethoxycarbonylphenyl) oxycarbonylbenzoic acid 2-chlorophenyl ester such as 2-chlorophenyl ester; 2-chlorophenyl acetate, 2-chlorophenyl propionate 2,2-chlorophenylvalerate, 2-chlorophenylperargolate, 2-chlorophenyl-1-methylpropionate, 2-chlorophenyl-2-methoxycarbonylpropionate, 2-chlorophenyl-2
Aliphatic carboxylic acids such as -ethoxycarbonyl butyrate, 2-chlorophenyl 4 '-(2-methoxycarbonylphenyl) oxycarbonyl butyrate, 2-chlorophenyl 4'-(2-methoxycarbonylphenyl) oxycarbonyl butyrate-2- Chlorophenyl ester, (2-methoxycarbonylphenyl) benzoate, 4-methylbenzoyl- (2'-methoxycarbonylphenyl) ester, 4-ethylbenzoyl- (2 '
-Methoxycarbonylphenyl) ester, 4-n-butylbenzoyl- (2'-methoxycarbonylphenyl) ester, 4-tert-butylbenzoyl- (2'-methoxycarbonylphenyl) ester, naphthoic acid-
(2'-methoxycarbonylphenyl) ester, 4-
Nonylbenzoic acid (2'-methoxycarbonylphenyl)
Ester, 4-cumylbenzoic acid (2'-methoxycarbonylphenyl) ester, 4-methoxybenzoic acid (2 '
-Methoxycarbonylphenyl) ester, 4-ethoxybenzoic acid (2'-methoxycarbonylphenyl) ester, 4-n-butoxybenzoic acid (2'-methoxycarbonylphenyl) ester, 4-t-butoxybenzoic acid (2'- Methoxycarbonylphenyl) ester, 4-
Cumyloxybenzoic acid (2'-methoxycarbonylphenyl) ester, 2-methoxycarbonylbenzoic acid (2'-methoxycarbonylphenyl) ester, 4-
Methoxycarbonylbenzoic acid (2'-methoxycarbonylphenyl) ester, 4-ethoxycarbonylbenzoic acid (2'-methoxycarbonylphenyl) ester, 3
-(O-methoxycarbonylphenyl) oxycarbonylbenzoic acid (2'-methoxycarbonylphenyl) ester, 4- (o-methoxycarbonylphenyl) oxycarbonylbenzoic acid (2'-methoxycarbonyl ester) ester, 3- (o- Aromatic carboxylic acids such as ethoxycarbonylphenyl), oxycarbonylbenzoic acid (2'-methoxycarbonylphenyl) ester
(2′-methoxycarbonylphenyl) ester, (2
-Ethoxycarbonylphenyl) benzoate, 4-methylbenzoyl- (2'-ethoxycarbonylphenyl) ester, 4-ethylbenzoyl- (2'-ethoxycarbonylphenyl) ester, 4-n-butylbenzoyl (2'-ethoxycarbonylphenyl) ) Ester, 4-tert-butylbenzoyl- (2'-ethoxycarbonylphenyl) ester, naphthoic acid- (2'-ethoxycarbonylphenyl) ester, 4-nonylbenzoic acid (2'-ethoxycarbonylphenyl) ester, 4
-Cumylbenzoic acid (2'-ethoxycarbonylphenyl) ester, 4-methoxybenzoic acid (2'-ethoxycarbonylphenyl) ester, 4-ethoxybenzoic acid (2'-ethoxycarbonylphenyl) ester, 4-
n-butoxybenzoic acid (2'-ethoxycarbonylphenyl) ester, 4-tert-butoxybenzoic acid (2'-ethoxycarbonylphenyl) ester, 4-nonyloxybenzoic acid (2'-ethoxycarbonylphenyl) ester, 4-cumyloxy Benzoic acid (2'-ethoxycarbonylphenyl) ester, 2-methoxycarbonylbenzoic acid (2'-ethoxycarbonylphenyl) ester, 4-ethoxycarbonylbenzoic acid (2'-ethoxycarbonylphenyl) ester, 3- (o-methoxy Carbonylphenyl) oxycarbonylbenzoic acid (2'-
Ethoxycarbonylphenyl) ester, 4 (o-methoxycarbonylphenyl) oxycarbonylbenzoic acid (2′-ethoxycarbonylphenyl) ester, 3-
and aromatic carboxylic acid- (2'-ethoxycarbonylphenyl) esters such as o-methoxycarbonylphenyl) oxycarbonylbenzoic acid (2'-ethoxycarbonylphenyl) ester.

As the compound represented by the above formula (1), 2-methoxycarbonylphenylbenzoate, 4-cumylbenzoic acid- (2'-methoxycarbonylphenyl) ester, 2-ethoxycarbonylphenylbenzoate, 4- (o -Methoxycarbonylphenyl) oxycarbonylbenzoic acid (2'-methoxycarbonylphenyl) ester is preferred.

In the method of the present invention, the compound represented by the above formula (1) is added to polycarbonate,

[0049]

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As shown in the above, the terminal OH ( OH) to block the polycarbonate end. In order to carry out terminal blocking quickly and in high yield, it is preferable to carry out while distilling off the formed 2-substituted phenol.

The compound represented by the above formula (1) is added after the aromatic dihydroxy compound and diphenyl carbonate are melt-polycondensed and the intrinsic viscosity of the polycarbonate reaches at least 0.3 dl / g. After the addition, the end blocking of the polycarbonate proceeds rapidly, so that the change in the intrinsic viscosity of the polycarbonate is 0.1 dl /
g.

The compound represented by the above formula (1) is preferably used in an amount of 0.1 to 1 equivalent of the terminal hydroxyl group of the polycarbonate.
It is used at a ratio of 5 to 2 mol, more preferably 0.7 to 1.5 mol, particularly preferably 0.8 to 1.2 mol.

As the aromatic dihydroxy compound used in the present invention, for example, the following formula (4)

[0054]

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R ⁴ and R ⁵ are the same or different and are a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and R ⁶ and R ⁷ are the same or different and are a halogen atom or a hydrocarbon group having 1 to 12 carbon atoms. A compound represented by a hydrogen group is preferred.

In the above formula (4), as the halogen atom, for example, chlorine, bromine and iodine are preferable. Examples of the hydrocarbon group having 1 to 12 carbon atoms include, for example, 1 to 12 carbon atoms.
Or an aromatic hydrocarbon group having 6 to 12 carbon atoms.

The aromatic dihydroxy compound includes:
Specific examples include the following compounds. That is, bis (hydroxy) such as 1,1-bis (4-hydroxy-t-butylphenyl) propane, 2,2-bis (4-hydroxyphenyl) propane, and 2,2-bis (4-hydroxybromophenyl) propane Aryl)
Alkanes, 1,1-bis (4-hydroxyphenyl)
Bis (hydroxyaryl) such as cyclopentane and 1,1-bis (4-hydroxyphenyl) cyclohexane
Dihydroxyaryl ethers such as cycloalkanes, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethylphenyl ether, 4,4'-dihydroxydiphenyl sulfide,
Dihydroxyaryl sulfides such as 4,4'-dihydroxy-3,3'-dimethylphenyl sulfide;
4,4'-dihydroxydiphenylsulfoxide, 4,
Dihydroxyarylsulfoxides such as 4'-dihydroxy-3,3'-dimethylphenylsulfoxide;
4,4'-dihydroxydiphenyl sulfone, 4,4 '
And dihydroxyarylsulfones such as -dihydroxy-3,3'-dimethylphenylsulfone. Of these, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) is particularly preferably used. These aromatic dihydroxyl compounds can be used alone or in combination.

In the melt polycondensation, diphenyl carbonate is used in an excess molar ratio with respect to the aromatic dihydroxy compound, preferably in a ratio of 1.01 to 1.20 mol with respect to 1 mol of the aromatic dihydroxy compound.

In the present invention, the polycarbonate before terminal blocking is preferably condensed using a catalyst comprising (i) an alkali metal compound and / or (ii) a nitrogen-containing basic compound.

The alkali metal compound used as a catalyst includes, for example, hydroxides, hydrocarbons, carbonates, acetates, nitrates, nitrites, sulfites, cyanates, thiocyanates, stearic acids of hydroxides of alkali metals. Salts, borohydride salts, benzoates, hydrogen phosphates, bisphenols, salts of phenols and the like can be mentioned.

As specific examples, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, lithium hydrogen carbonate, sodium carbonate,
Potassium carbonate, lithium carbonate, sodium acetate, potassium acetate, lithium acetate, sodium nitrate, potassium nitrate, lithium nitrate, sodium nitrite, potassium nitrite, lithium nitrite, sodium sulfite, potassium sulfite, lithium sulfite, sodium cyanate, potassium cyanate , Lithium cyanate, sodium thiocyanate,
Potassium thiocyanate, lithium thiocyanate, sodium stearate, potassium stearate, lithium stearate, sodium borohydride, lithium borohydride, potassium borohydride, sodium borohydride, sodium benzoate, potassium benzoate, benzoic acid Lithium, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, disodium salt, dipotassium salt, dilithium salt of bisphenol A, sodium salt, potassium salt, lithium salt of phenol and the like can be mentioned.

The alkali metal compound as a catalyst can be used in a range of 10 ^-8 to 10 ^-5 mol per mol of the aromatic dihydroxy compound. If it deviates from the above use range, it adversely affects various physical properties of the obtained polycarbonate,
Further, there is a problem that the transesterification reaction does not sufficiently proceed and a high molecular weight polycarbonate cannot be obtained.

Examples of the nitrogen-containing basic compound as a catalyst include, for example, tetramethylammonium hydroxide (Me ₄ NOH), tetraethylammonium hydroxide (Et ₄ NOH), tetrabutylammonium hydroxide (Bu ₄ NOH), benzyl Trimethylammonium hydroxide (φ-CH ₂ (Me) ₃ NOH),
Alkyl, aryl, ammonium hydroxides having an alkylaryl group such as hexadecyltrimethylammonium hydroxide, triethylamine,
Tertiary amines such as tributylamine, dimethylbenzylamine, hexadecyldimethylamine, or tetramethylammonium borohydride (Me ₄ NBH
₄ ), tetrabutylammonium borohydride (B
u ₄ NBH ₄ ), tetrabutylammonium tetraphenylborate (Bu ₄ NBPh ₄ ), tetramethylammonium tetraphenylborate (Me ₄ NBPh ₄ )
And the like.

The nitrogen-containing basic compound is preferably used in such a proportion that the amount of ammonium nitrogen atoms in the nitrogen-containing basic compound is 1 × 10 ⁻⁵ to 1 × 10 ⁻³ equivalent per 1 mol of the aromatic dihydroxy compound. A more preferable ratio is a ratio that is 2 × 10 ^{−5 to} 7 × 10 ⁻⁴ equivalents with respect to the same standard.
A particularly desirable ratio is 5 × 10 ^{−5 to} 5 × 1 with respect to the same standard.
0 is a ratio comprised ^-4 equivalents.

In the present invention, if desired, (a) an alkali metal salt of an ate complex of an element of Group 14 of the periodic table or (b) an oxo acid of an element of Group 14 of the periodic table may be used as the alkali metal compound of the catalyst. Can be used. Here, the elements of Group 14 of the periodic table refer to silicon, germanium, and tin.

Use of these alkali metal compounds as catalysts for the polycondensation reaction and the terminal blocking reaction has an advantage that the polycondensation reaction and the terminal blocking reaction can be promptly and sufficiently promoted. Further, undesirable side reactions such as a branching reaction generated during the polycondensation reaction can be suppressed to a low level.

(A) Examples of the alkali metal salt of an ate complex of an element of Group 14 of the periodic table include those described in JP-A-7-268091, specifically, a compound of germanium (Ge); NaGe (OMe) ₅ , NaGe
(OEt) ₃ , NaGe (OPr) ₅ , NaGe (OB
u) ₅ , NaGe (OPh) ₅ , LiGe (OM
e) ₅ , LiGe (OBu) ₅ , LiGe (OPh) ₅
Can be mentioned.

Examples of the tin (Sn) compound include NaSn
(OMe) ₃ , NaSn (OMe) ₂ (OEt), Na
Sn (OPr) ₃ , NaSn (On-C ₆ H ₁₃ ) ₃ ,
NaSn (OMe) ₅ , NaSn (OEt) ₅ , NaS
_{n (OBu) 5, NaSn (} O-n-C 12 H 25) 5, N
aSn (OEt), NaSn (OPh) ₅ , NaSnB
u ₂ (OMe) ₃ .

Examples of the alkali metal salt of oxo acid of Group 14 element of the periodic table (b) include silicic acid (silicic acid).
acid), stannic acid, germanium (II) acid (germanous aci)
d) alkali metal salts, germanium (IV) acid (germani
Alkali metal salts of c acid) can be mentioned as preferred.

The alkali metal salt of silicic acid is, for example, an acidic or neutral alkali metal salt of monosilicic acid or a condensate thereof, such as monosodium orthosilicate, disodium orthosilicate, or the like.
Trisodium orthosilicate and tetrasodium orthosilicate can be mentioned.

The alkali metal salt of stannic acid is, for example, an acidic or neutral alkali metal salt of monostannic acid or a condensate thereof, and examples thereof include disodium monostannate (Na ₂ SnO ₃ .CH _2). O, x =
0-5), tetrasodium monostannate (Na ₄ Sn)
O ₄ ).

Germanium (II) acid (germanous acid)
The alkali metal salt is, for example, an acidic or neutral alkali metal salt of monogermanic acid or a condensate thereof,
An example is monosodium germanate (Na
HGeO ₂ ).

Germanic acid (germanic acid)
Is, for example, an acidic or neutral alkali metal salt of monogermanic acid (IV) acid or a condensate thereof, for example, disodium orthogermanate monolithium acid (LiH ₃ GeO ₄ ) orthogermanate , Ortho-germanic acid tetrasodium salt,
Digermanic acid disodium salt (Na ₂ Ge
₂ O ₅ ), disodium tetragermanate (Na
₂ Ge ₄ O ₉ ) and disodium pentagermanate (Na ₂ Ge ₅ O ₁₁ ).

The above-mentioned polycondensation reaction catalyst is preferably used when the amount of the alkali metal element in the catalyst is 1 × 10 ^{−7 to} 5 × 10 ⁻⁵ equivalent per mole of the aromatic dihydroxy compound. A more desirable ratio is 5 × 10 ^{−7 with} respect to the same standard.
割 合 1 × 10 ⁻⁵ equivalent.

In the polycondensation reaction of the present invention, if necessary, at least one member selected from the group consisting of oxo acids of Group 14 elements of the periodic table and oxides of the same, together with the above catalyst.
Various co-catalysts can be co-present.

By using these cocatalysts in a specific ratio, the terminal block reaction and the polycondensation reaction rate are not impaired, and the branching reaction which is easily generated during the polycondensation reaction and the foreign matter in the apparatus at the time of molding are performed. Undesirable side reactions such as generation and burning can be more effectively suppressed.

The oxo acids of Group 14 elements of the periodic table include, for example, silicic acid, stannic acid and germanic acid.

The oxides of Group 14 elements of the periodic table include:
Mention may be made of silicon monoxide, silicon dioxide, tin monoxide, tin dioxide, germanium monoxide, germanium dioxide and condensates thereof.

The co-catalyst should be present in a proportion such that the metal element of Group 14 of the periodic table in the co-catalyst is not more than 50 mol (atoms) per 1 mol (atom) of the alkali metal element in the polycondensation reaction catalyst. preferable. If the co-catalyst is used in a proportion of more than 50 moles (atoms) of the same metal element, the rate of the polycondensation reaction is undesirably reduced.

The cocatalyst is present in such a ratio that the metal element of Group 14 of the periodic table of the cocatalyst is 0.1 to 30 mol (atoms) per 1 mol (atom) of the alkali metal element of the polycondensation reaction catalyst. Is more preferred.

According to the study of the present inventor, the use of the specific catalyst neutralizing agent described below makes it possible to effectively and sufficiently neutralize the catalyst remaining in the polymer whose terminal is sufficiently blocked. It is possible to provide a stabilized polymer having good hue even after the catalyst is neutralized.

In the present invention, after blocking the terminal of the polymer, at least one compound selected from the group represented by the following general formulas (I) to (IV) is added to the polycarbonate produced while the polymer is in a molten state. It is preferably added as a catalyst neutralizing agent at a concentration of 0.01 to 500 ppm.

[0083]

Embedded image

Here, A ¹ is an m-valent hydrocarbon group which may have a substituent, Y ¹ is a single bond or an oxygen atom, and X ¹ is a secondary or tertiary monovalent hydrocarbon group. Hydrocarbon group, 1
An equivalent amount of a metal cation, an ammonium cation or a phosphonium cation, and m is an integer of 1 to 4. However, when Y ¹ is a single bond, all of m X ¹ are not one equivalent of metal cation.

[0085]

Embedded image ^{+ X 2 -A 2 -Y 1 -SO} 3 - ... (II) wherein, A ² is a divalent hydrocarbon group, ⁺ X ² is 2
It is a quaternary ammonium cation or a quaternary phosphonium cation, and the definition of Y ¹ is the same as described above.

[0086]

Embedded image

Here, A ³ is an n-valent hydrocarbon group,
⁺ X ³ is a secondary or quaternary ammonium cation or 2 to 4
And R is a monovalent hydrocarbon group, n is an integer of 2 to 4, and the definition of Y ¹ is the same as described above.

[0088]

Embedded image

[Where A ⁵ is a monovalent or divalent hydrocarbon group, A ⁴ is a divalent hydrocarbon group, and Ad ¹ and Ad ² are the same or different, and are represented by —SO ² —O—SO ^{2 Two}
-, -SO ² -O-CO- or -CO-O-SO ^2-
And k is 0 or 1. Provided that when k is 0,-(Ad ² -A ⁵ ) _k represents a hydrogen atom or a bond connecting A ⁴ and A ⁵ (in this case, A ⁵ is a divalent hydrocarbon group Or a single bond).

Specific examples of the compound represented by the above formula (I) include the following compounds:
2-phenyl-2-propyl dodecylbenzenesulfonate, 2-phenyl-2-butyl dodecylbenzenesulfonate, tetrabutylphosphonium octylsulfonate, tetrabutylphosphonium decylsulfonate, tetrabutylphosphonium benzenesulfonate, dodecylbenzene Tetraethyl phosphonium sulfonate, Tetrabutyl phosphonium dodecylbenzene sulfonate, Tetrahexyl phosphonium dodecylbenzene sulfonate, Tetraoctyl phosphonium dodecylbenzene sulfonate, Decyl ammonium butyl sulfate, Decyl ammonium decyl sulfate, Dodecyl ammonium methyl sulfate, Dodecyl ammonium Ethyl sulfate, dodecyl methyl ammonium methyl sulfate, Sill dimethyl ammonium tetradecyl sulfate, tetradecyl dimethyl ammonium methyl sulfate, tetramethylammonium hexyl sulfate, decyltrimethylammonium hexadecyl sulfate, tetrabutylammonium dodecylbenzyl sulfate, tetraethylammonium dodecylbenzyl sulfate, tetramethylammonium dodecylbenzyl sulfate.

Specific examples of the compound represented by the above formula (II) include the following compounds:

[0092]

Embedded image

Specific examples of the compound represented by the above formula (III) include the following compounds:

[0094]

Embedded image

Specific examples of the compound represented by the above formula (IV) include the following compounds:

[0096]

Embedded image

[0097]

Embedded image

Among the neutralizing agents of the above formulas (I) to (IV), the neutralizing agents of the phosphonium or ammonium salt type are particularly stable even at 200 ° C. or higher. Then, when the neutralizing agent is added to the polymer, the polycondensation reaction catalyst can be immediately neutralized to obtain a target polymer.

In the method of the present invention, at least one compound selected from the group consisting of the compounds represented by the above formulas (I) to (IV)
The kind of neutralizing agent is used in a proportion of preferably 0.01 to 500 ppm, more preferably 0.01 to 300 ppm, particularly preferably 0.01 to 100 ppm, based on the polycarbonate produced after the polymerization sealing reaction. You.

The neutralizing agent is used in an amount of 0.5 to 5 per mole of the polycondensation reaction catalyst.
It is preferably used in a proportion of 0 mol.

The method for adding the neutralizing agent to the polymer after terminal blocking is not particularly limited. For example, these may be added while the polycarbonate as a reaction product is in a molten state, or may be added after pelletizing the polycarbonate once and then re-melting.

In the former, while the polycarbonate, which is a reaction product in the molten reactor or extruder obtained after completion of the end-blocking reaction, is in the molten state,
After adding these to form a polycarbonate, it may be pelletized through an extruder, or while the polycarbonate obtained by the polymerization sealing reaction is pelletized from the reactor through the extruder, a neutralizing agent may be added. The polycarbonate can be obtained by adding and kneading.

Further, in the present invention, at least any of before, during and after the end-blocking,
It is preferable to add various known stabilizers before the reaction in the molten state. Examples of the stabilizer include a sulfur-containing acidic compound and / or a derivative formed from the acidic compound,
Phenolic stabilizers, thioether stabilizers, phosphorus stabilizers, hindered amine stabilizers, epoxy stabilizers,
Salicylic acid-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers and the like can be mentioned. These stabilizers can be used alone or in combination.

The production of a polymer by a polycondensation reaction between an aromatic dihydroxy compound and diphenyl carbonate can be carried out under the same conditions as those of a conventionally known ordinary method.

More specifically, the first-stage reaction was carried out at 80 to 25.
At a temperature of 0 ° C., preferably 100 to 230 ° C., more preferably 120 to 190 ° C., 0.5 to 5 hours, preferably 1 to 4 hours, more preferably 1.5 to 3 hours, under reduced pressure, aromatic The dihydroxy compound is reacted with diphenyl carbonate. Next, the reaction temperature was increased while increasing the vacuum system of the reaction system, and the reaction between the aromatic dihydroxy compound and diphenyl carbonate was carried out.
under a reduced pressure of not more than 1 Torr,
A polycondensation exchange reaction between an aromatic dihydroxy compound and diphenyl carbonate is performed at a temperature of up to 320 ° C.

In the present invention, it is preferable to control the hydroxyl terminal of the polycarbonate before adding the terminal blocking agent to at least 20 mol%, preferably at least 30 mol%, more preferably at least 40 mol%, based on all terminals. By doing so, a specific terminal group can be introduced at a high ratio, and the effect of modifying the polymer can be enhanced. Usually, the present invention can be advantageously carried out in the range of 30 to 95 mol% of hydroxyl groups among all terminals. Here, the number of moles of terminal hydroxyl groups in a certain amount of the polymer can be determined by 1H-NMR by a conventional method. Further, the ratio of the hydroxyl group terminal of the polymer can also be controlled by the charging ratio of the aromatic dihydroxy compound and the diphenyl carbonate as the raw materials.

In the present invention, there are no particular restrictions on the feeder to which the terminal blocking agent is supplied and the reactor for performing the terminal blocking reaction.

The method for adding the terminal blocking agent is not particularly limited, and it may be added as a solid or after being dissolved in various solvents. Also, after the intrinsic viscosity of the polymer reaches 0.3, the terminal blocking agent may be added all at once, or may be added separately depending on the degree of difficulty.

That is, the terminal blocking agent is added after the intrinsic viscosity of the polymer reaches at least 0.3 dl / g.

In the present invention, the amount of free chlorine not covalently bonded to the polymer contained in the polycarbonate (prepolymer) before the terminal is blocked is reduced, preferably to 50 ppm or less, more preferably to 5 ppm or less. Is advantageous.

If the amount of free chlorine is larger than this, the catalytic activity involved in the terminal blocking reaction tends to decrease, and it is difficult to achieve the terminal blocking quickly and sufficiently, which is not preferable.

Further, a large amount of chlorine is not preferable because it adversely affects the hue and stability of the obtained polymer.

Controlling the amount of chlorine contained in the prepolymer to a low level can be achieved by controlling the amount of chlorine contained in the raw material to a low level.

In the present invention, it is advantageous that the amount of iron contained in the polycarbonate before the terminal is blocked is also low, for example, 1 ppm or less, more preferably 0.7 ppm or less.

If the amount of iron is larger than this, the activity of the catalyst involved in the terminal reforming reaction is liable to decrease, and it is difficult to achieve the terminal blocking quickly and sufficiently, which is not preferable. On the other hand, a large amount of iron is not preferred because it adversely affects the hue and stability of the obtained polymer.

Reducing the amount of iron contained in the prepolymer to a low level can be achieved by keeping the amount of iron contained in the raw material at a low level and preventing the contamination of iron throughout the production process. .

After the addition of the terminal blocking agent, the pressure is preferably reduced so as to remove at least phenols formed by the reaction. Specifically, it is 50 Torr or less, more preferably 10 Torr or less. Usually 0.01-100T
It is preferable to carry out in the range of orr.

The reaction temperature after the addition of the terminal blocking agent is usually 25.
0-360 ° C., preferably 260-340 ° C., below which the polymer does not melt,
At temperatures higher than this range, the polymer decomposes and discolors,
Not preferred. The reaction time is generally 1 to 30 minutes, preferably 1 to 20 minutes, and may be 1 to 15 minutes if desired.

In the present invention, residual phenols contained in the polymer after terminal blocking can be suppressed to a low level.

The concentration of the residual phenols in the polymer after the end-blocking reaction is 300 ppm or less, more preferably 200 ppm or less. If the amount of residual phenols is higher than this concentration, the molecular weight is likely to be reduced or colored,
Not preferred.

The above-mentioned polycondensation reaction may be carried out continuously or batchwise. The reaction apparatus used for performing the above reaction may be a tank type, a tube type, or a tower type.

In the present invention, the polycarbonate obtained by the end-blocking reaction has ordinary heat stability, an ultraviolet absorber, a releasing agent, a coloring agent, an antistatic agent, a lubricant, an antifogging agent as long as the object of the present invention is not impaired. Natural oils, synthetic oils, waxes, organic fillers, inorganic fillers and the like may be added.

According to the study of the present inventor, certain compounds including a specific compound among the compounds represented by the above formula (1) are obtained by blocking two molecules of polycarbonate by one molecule, preferably by end-blocking. As a result, it was revealed that an effect of remarkably improving the degree of polymerization of the polycarbonate, that is, an effect of accelerating polymerization was obtained.

Therefore, according to the present invention, secondly, in a method for producing a polycarbonate by melt-polycondensing an aromatic dihydroxy compound and diphenyl carbonate, the inherent viscosity of the polycarbonate is at least 0.3 dl.
/ G, the following equation (2)

[0125]

Embedded image

Here, R ¹ is a chlorine atom, methoxycarbonyl or ethoxycarbonyl, and X is an oxygen atom or the following formula: —R—COO— wherein R is an alkylene group having 1 to 30 carbon atoms or a carbon atom having 6 carbon atoms. And R ³ is a chlorine atom, methoxycarbonyl or ethoxycarbonyl, and the compound has a viscosity of more than 0.1 from the intrinsic viscosity at the time of addition. There is also provided a process for producing a polycarbonate having an increased intrinsic viscosity, characterized in that it produces a polycarbonate having a high intrinsic viscosity.

In the above formula (2), R ¹ is a chlorine atom,
Methoxycarbonyl or ethoxycarbonyl,
X is an oxygen atom or a group represented by the formula: -RCOO- (where R is an alkylene group having 1 to 30 carbon atoms or an arylene group having 6 to 30 carbon atoms), and R ³ is a chlorine atom, methoxycarbonyl Or ethoxycarbonyl.

As the alkylene group having 1 to 30 carbon atoms and the arylene group having 6 to 30 carbon atoms, the same as those described above for the formula (1) can be exemplified.

As the compound represented by the above formula (2), for example, di (2-chlorophenyl) carbonate,
2-chlorophenyl-2'-methoxycarbonylphenyl carbonate, di (2-methoxycarbonylphenyl) carbonate, 2-methoxycarbonylphenyl
Diallyl carbonates such as 2'-ethoxycarbonylphenyl carbonate and di (2-ethoxycarbonylphenyl) carbonate; di (2-chlorophenyl)
Malonate, 2-chlorophenyl-2'-methoxycarbonylphenylmalonate, 2-chlorophenyl-2 '
-Ethoxycarbonylphenylmalonate, di (2-methoxycarbonylphenyl) malonate, 2-methoxycarbonylphenyl-2'-ethoxycarbonylphenylmalonate, di (2-ethoxycarbonylphenyl)
Malonate, di (2-chlorophenyl) succinate,
Di (2-methoxycarbonylphenyl) succinate,
Di (2-ethoxycarbonylphenyl) succinate,
Di (2-chlorophenyl) glutanate, di (2-methoxycarbonylphenyl) glutanate, di (2-ethoxycarbonylphenyl) glutanate, di (2-chlorophenyl) adipate, di (2-methoxycarbonylphenyl) adipate, di (2- (Ethoxycarbonylphenyl) azinate, di (2-chlorophenyl) pimelinate, di (2-methoxycarbonylphenyl) pimelinate, di (2-ethoxycarbonylphenyl) pimelinate, di (2-chlorophenyl) suberinate, di (2-methoxycarbonylphenyl) Suberinate, di (2-ethoxycarbonylphenyl) suberinate, di (2-chlorophenyl) azelate, di (2-methoxycarbonylphenyl) azelate, di (2-ethoxycarbonylphenyl) Zereto, di (2-chlorophenyl) sebacate, di (2-methoxycarbonylphenyl) sebacate, di (2-ethoxycarbonyl-phenyl) sebacate, di (2-chlorophenyl) decane -
1,10-dicarboxylate, di (2-methoxycarbonylphenyl) decane-1,10-dicarboxylate, di (2-methoxycarbonylphenyl) hexadecane-1,10-dicarboxylate, di (2-methoxycarbonyl) Phenyl) aicosan-1,20-dicarboxylate, di (2-methoxycarbonylphenyl) pentacosan-1,25-dicarboxylate, di (2-
Methoxycarbonylphenyl) triacontan-1,3
Diaryl esters of aliphatic dicarboxylic acids such as 0-dicarboxylate; di (2-chlorophenyl) terephthalate, di (2-methoxycarbonylphenyl) terephthalate, di (2-ethoxycarbonylphenyl) terephthalate, 2-chlorophenyl-2'- Methoxycarbonylphenyl terephthalate, di (2-chlorophenyl) isophthalate, di (2-methoxycarbonylphenyl) isophthalate, di (2-ethoxycarbonylphenyl) isophthalate, di (2-chlorophenyl) terephthalate, di (2-methoxycarbonyl) Phenyl)
Terephthalate, di (2-ethoxycarbonylphenyl) terephthalate, di (2-chlorophenyl) naphthylenedicarboxylate, di (2-methoxycarbonylphenyl) naphthalenedicarboxylate, di (2-ethoxycarbonylphenyl) naphthalenedicarboxylate, di (2-methoxycarbonylphenyl) biphenyldicarboxylate, di (2-methoxycarbonylphenyl) toluenedicarboxylate, di (2-methoxycarbonylphenyl) cumenedicarboxylate, di (2-methoxycarbonylphenyl) anthracenedicarboxylate And diaryl esters of aromatic dicarboxylic acids.

Of these, di (2-methoxycarbonylphenyl) terephthalate, di (2-methoxycarbonylphenyl) isophthalate, di (2-methoxycarbonylphenyl) terephthalate and di (2-ethoxycarbonylphenyl) isophthalate are preferred. .

The polymerization accelerator represented by the above formula (2) is
It is added to a polycarbonate having an intrinsic viscosity of at least 0.3 dl / g, giving a polycarbonate having an intrinsic viscosity of more than 0.1 dl / g greater than the intrinsic viscosity of the polycarbonate at the time of addition.

The polymerization accelerator represented by the above formula (2) is
Preferably, about 0.3 to about 1 equivalent of terminal hydroxyl group at the time of addition.
It is added in a ratio of about 0.7 mol, more preferably about 0.4 to about 0.6 mol, particularly preferably about 0.45 to about 0.55 mol.

The polymerization accelerator is added to the polycarbonate and has the following reaction formula

[0134]

Embedded image

As represented by the formula, the terminal OH ( OH) to couple two molecules of polycarbonate.

The reaction is carried out as shown in the above reaction scheme.
Since two molecules of the 2-substituted phenol are produced, it is preferable that the produced 2-substituted phenol is distilled off in order to carry out the coupling quickly and in a high yield.

Upon completion of the coupling, a polycarbonate having an intrinsic viscosity of preferably more than 0.4 and less than 1.0 dl / g, more preferably 0.41 to 0.8 dl / g, is produced. .

Regarding the above-mentioned method of the present invention using a polymerization accelerator, for items not described herein such as a polycondensation catalyst, a neutralizing agent, and polycondensation conditions, the description of the above method using a terminal blocking agent is applied as it is. Should be understood.

[0139]

According to the present invention, the end-blocking reaction is rapidly carried out, and a polycarbonate containing less unreacted phenol can be obtained. Such a polycarbonate is characterized by being excellent in stability such as hue and hydrolysis resistance, and also excellent in releasability.

[0140]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In the examples, polymer physical properties were measured by the following methods.

(I) Intrinsic viscosity [η]: 2 in methylene chloride
It was measured at 0 ° C. with an Ubbelohde viscometer. (Ii) Terminal hydroxyl group concentration: 0.02 g of sample was 0.4 m
After dissolving in 1 l of chloroform, the terminal hydroxyl group and the terminal phenyl group were measured using 1H-NMR (EX-270, manufactured by JEOL Ltd.) at 20 ° C., and the terminal hydroxyl group concentration was measured by the following formula. Terminal hydroxyl group concentration (%) = (terminal hydroxyl group concentration / total number of terminals)
× 100 (iii) Residual phenols: A sample (1.0 g) was dissolved in methylene chloride and added to a 10-fold amount of methanol. The insoluble matter was put into a Soxhlet extractor, and residual phenols were extracted for 12 hours using methanol as an extraction solvent. The precipitation solvent methanol and the extraction solvent methanol were combined, and residual phenols contained in the solution were quantified by high performance liquid chromatography. The amount of residual phenol was indicated by the residual concentration (ppm) in the polymer.

(Iv) Residual Cl content and Fe content: quantified by elemental analysis.

(V) Hue: Evaluated visually.

(Vi) Stability of polymer: IV after heat aging
The evaluation was made based on the change rate (%) and the hue change. Thermal aging was performed by heating the polymer at 340 ° C. for 15 minutes.

(Vii) Releasability from metal surface: An injection molding machine (Meiki M50-B)
340 ° C., mold temperature 70
Injection molding was performed under the conditions of ° C, an injection time of 10 seconds, and a cooling time of 40 seconds. The mold used was a business card size capable of forming a flat plate having a thickness of 2 mm. The releasability of the molded plate after 100 shots of injection molding was determined by the following evaluation method.

◎: extremely good (no problem at all) ○: good (there was a shot that was hard to separate from the mold, but there was no major problem) Δ: somewhat poor (separated from the mold several times, Poor (many times peeled off by hand) (viii) Wet heat stability of polymer end: The wet heat stability of polymer end is maintained at 120 ° C for 15 hours under saturated vapor pressure. After that, the terminal hydroxyl group of the polymer was measured in the same manner as in (ii).

Examples 1 to 18 Bisphenol A22
8 parts, 220 parts of diphenyl carbonate and Tables 1 to 9
Was charged into a reaction tank equipped with a stirrer, a distiller and a decompression device, and was replaced with nitrogen. After stirring for 30 minutes, the internal temperature was raised to 180 ° C,
The reaction was carried out at 100 mmHg for 30 minutes, and the formed phenol was distilled off.

Next, the pressure was gradually reduced while increasing the temperature to 200 ° C.
The reaction was carried out at 0 mmHg for 30 minutes while distilling off phenol. Further, the temperature was gradually increased and reduced to 220 ° C. and 30 mmHg, and the temperature and pressure were reduced to the same temperature and pressure for 30 minutes.
Hg, 260 ° C, 1mmHg, 270 ° C, 1mmHg or less, the temperature was repeatedly increased and reduced by the same procedure as above, and the reaction was continued.

Finally, polymerization was carried out at the same temperature and pressure for 1 hour.
When the intrinsic viscosity of the polycarbonate resin reached about 0.35, a part of the polymer was collected, and the types and amounts of the terminal modifiers shown in Tables 1 to 9 were added. Then, at 270 ° C, 1
The reaction was continued at 5 mmHg or lower for 5 minutes to perform a terminal modification reaction. Next, in the molten state, the type and amount of catalyst neutralizing agent shown in Tables 1 to 9 were added. Then, 270 ° C, 10mm
The reaction was continued for 10 minutes at or below Hg.

The intrinsic viscosity [η], terminal hydroxyl group concentration, unreacted residual phenol of the polymer obtained by the above operation before terminal modification (before addition) and after neutralization of the catalyst after terminal modification (after addition). The hues, the stability and the releasability were checked by measuring the kind concentration, the Cl content and the Fe content.

For the polymer after neutralizing the catalyst,
Furthermore, the stability of the polymer was evaluated. In Examples 13 to 18, the releasability was evaluated. The physical properties of these polycarbonate resins are shown in Tables 1 to 9 below.

The abbreviations in the table have the following meanings.

BPA-Na: Na salt of bisphenol A TMAH: Tetramethylammonium hydroxide BPA: Bisphenol A

[0154]

[Table 1]

[0155]

[Table 2]

[0156]

[Table 3]

[0157]

[Table 4]

[0158]

[Table 5]

[0159]

[Table 6]

[0160]

[Table 7]

[0161]

[Table 8]

[0162]

[Table 9]

[Examples 19 to 21] Polymerization was carried out in exactly the same manner as in the examples, and when the intrinsic viscosity of the polycarbonate resin became 0.45, a part of the polymer was sampled.
The types and amounts of the polymerization accelerators shown in 0 and 11 were added. Thereafter, the reaction was continued at 270 ° C. and 1 mmHg or less for 5 minutes to perform a polymerization promoting reaction.

Next, in the molten state, the type and amount of the catalyst neutralizing agent shown in Tables 10 and 11 were added. Then 270
The reaction was continued at a temperature of 10 ° C. or less at 10 ° C. for 10 minutes.

The intrinsic viscosity [η], the concentration of terminal hydroxyl groups, the concentration of residual phenols, the C
The l content and Fe content were measured to check the hue and stability.

For the polymer after neutralizing the catalyst,
Furthermore, the stability of the polymer was evaluated. Table 1 shows the results
Indicated at 0 and 11.

[0167]

[Table 10]

[0168]

[Table 11]

 ──────────────────────────────────────────────────続 き Continuing on the front page (31) Priority claim number Japanese Patent Application No. Hei 8-70050 (32) Priority date Hei 8 (March 26, 1996) (33) Priority claim country Japan (JP) (31) Priority Claim No. Japanese Patent Application No. 8-91000 (32) Priority Date Hei 8 (1996) April 12 (33) Priority Claiming Country Japan (JP) (31) Priority Claim No. Japanese Patent Application No. 8-123225 (32) Priority Japan, Japan (JP) (31) Priority claim number Japanese Patent Application No. 8-128232 (32) Priority day Hei 8 (1996) May 23 (33) ) Priority country Japan (JP)

Claims (8)

[Claims] 1. A method for producing an aromatic polycarbonate by melt-polycondensing an aromatic dihydroxy compound and diphenyl carbonate, wherein after the intrinsic viscosity of the polycarbonate reaches at least 0.3 dl / g, the following formula (1): Formula 1 Wherein R ¹ is a chlorine atom, a methoxycarbonyl group or an ethoxycarbonyl group, and R ² is
Alkyl group having 30 to 30 carbon atoms, alkoxyl group having 1 to 30 carbon atoms, aryl group having 6 to 30 carbon atoms or 6 to 30 carbon atoms
Wherein the alkyl group having 1 to 30 carbon atoms and the alkoxyl group having 1 to 30 carbon atoms are methoxycarbonyl, ethoxycarbonyl, (o-methoxycarbonylphenyl) oxycarbonyl or (o-
Ethoxycarbonylphenyl) oxycarbonyl, and an aryl group having 6 to 30 carbon atoms and an aryloxy group having 6 to 30 carbon atoms may be methoxycarbonyl, ethoxycarbonyl, (o-methoxycarbonylphenyl) oxycarbonyl, It may be substituted by (o-ethoxycarbonylphenyl) oxycarbonyl, alkyl having 1 to 30 carbons, or alkoxyl having 1 to 30 carbons. And the change in the intrinsic viscosity is 0.1 dl / g based on the intrinsic viscosity at the time of addition.
A method for producing an end-capped polycarbonate, which comprises producing an end-capped polycarbonate that is within. 2. The compound represented by the formula (1) is represented by the following formula (1) -1 [Wherein the definition of R ¹ is the same as in formula (1), and R ²¹ is an alkyl group having 1 to 30 carbon atoms or 6 to 3 carbon atoms.
0 aryl groups, which may be substituted by the substituents defined in claim 1. The method according to claim 1, which is represented by the following formula: (3) [Wherein, the definition of R ¹ is the same as in formula (1), and R ²² is an alkyl group having 1 to 30 carbon atoms or 6 to 3 carbon atoms.
0 aryl groups, which may be substituted by the substituents defined in claim 1. The method according to claim 1, which is represented by the following formula: 4. The compound represented by the above formula (1) is added in an amount of 0.5 to 1 equivalent of terminal hydroxyl group at the time of addition of polycarbonate.
The method according to claim 1, wherein ~ 2 mol is added. 5. The compound represented by the formula (1) is added, and then the compound represented by the following formula (3) is added. [Here, the definition of R ¹ is the same as in the above formula (1). ]
2. The method according to claim 1, wherein the polycarbonate is capped while distilling off the phenol compound represented by the formula (1). 6. A method for producing a polycarbonate by subjecting an aromatic dihydroxy compound and diphenyl carbonate to melt polycondensation, wherein after the intrinsic viscosity of the polycarbonate reaches at least 0.3 dl / g, the following formula (2): ] [Where R ¹ is a chlorine atom, methoxycarbonyl or ethoxycarbonyl, X is an oxygen atom or the following formula: —R—COO— (where R is an alkylene group having 1 to 30 carbon atoms or 6 to 30 carbon atoms) And a compound represented by the formula: wherein R ³ is a chlorine atom, methoxycarbonyl or ethoxycarbonyl, and 0.1 dl / g is determined from the intrinsic viscosity at the time of addition. A process for producing a polycarbonate exhibiting an increased intrinsic viscosity, characterized by producing a polycarbonate exhibiting an inherently higher intrinsic viscosity. 7. A compound represented by the above formula (1) is added in an amount of 0.3 to 1 equivalent of terminal hydroxyl group at the time of addition of polycarbonate.
The method according to claim 6, wherein -0.7 mol is added. 8. After adding the compound represented by the formula (2), the compound represented by the following formula (3) is added. [Here, the definition of R ¹ is the same as that of the above formula (2).] The method according to claim 6, wherein the intrinsic viscosity of the polycarbonate is increased while distilling off the phenol compound represented by the following formula.