JPH02153928A - Production of polycarbonate - Google Patents

Abstract

PURPOSE:To obtain a high-molecular weight, colorless and transparent polymer free from chlorine ion without using poisonous phosgene by reacting a dihydric phenol with bis(trichlorophenyl) carbonate under an interfacial polycondensation polymerization condition in the presence of an electron donative amine compound catalyst. CONSTITUTION:A dihydric phenol [e.g. 2,2-bis-(4-hydroxyphenyl)propane] is reacted with bis(2,4,6-trichlorophenyl) carbonate or bis(2,3-dichlorophenyl) carbonate or bis(2-cyanophenyl) carbonate under an interfacial polycondensation polymerization condition of polycarbonate in the presence of a catalyst selected from electron donative amine compounds (e.g. N,N-dimethyl-4-aminopyridine).

Description

Detailed Description of the Invention (Industrial Application Field) The present invention involves interfacial polycondensation of dihydric phenol and bis(2,4,6-trichlorophenyl) carbonate, etc. in the presence of an electron-donating amine compound catalyst. The present invention relates to a method for producing high molecular weight polycarbonate obtained by

PRIOR ART AND PROBLEMS TO BE SOLVED BY THE INVENTION The high molecular weight polycarbonates of the present invention have a wide range of uses, particularly for injection molding or as glass sheets in place of window panes. It is a general-purpose engineering thermoplastic. The interfacial polymerization method is one of the methods used to produce polycarbonate, in the presence of an aqueous alkaline solution containing an alkali or alkaline earth metal hydroxide and an inert organic solvent that is a solvent for the polycarbonate to be produced. It consists of reacting dihydric phenol with bis(2,4,6-)dichlorophenyl) carbonate, bis(2,4-dichlorophenyl) carbonate, or bis(2-cyanophenyl) carbonate. Although the interfacial polycondensation method is generally effective for producing polycarbonate, it has drawbacks such as the use of toxic phosgene and the fact that chlorine ions remain in the polycarbonate produced. In order to eliminate these drawbacks, it was proposed in 1983 that polycarbonate could be produced by an interfacial polycondensation reaction between liquid trichloromethyl chloroformate, which is a dimer of phosgene, and a special dihydric phenol instead of toxic phosgene. -1823
36. However, a special dihydric phenol, 9,9-bis(4-hydroxyphenyl)
There is only a description of fluorenes.

(Means for Solving the Problems) The present inventors have discovered that bis(2,4,
It has been discovered that by reacting dihydric phenol with 6-trichlorophenyl) carbonate, a high molecular weight polycarbonate which does not use toxic phosgene and is essentially free of chlorine ions can be obtained.

The present invention provides (1) interfacial polycondensation conditions of polycarbonate,
Specifically, bisphenol A is dissolved in an alkaline aqueous solution (NaOH aqueous solution, etc.), a solvent (halogenated solvent) that is immiscible with water and dissolves polycarbonate is added, and polycondensation is performed at room temperature of 25°C. dihydric phenol and bis(2,
4,6-)dichlorophenyl)carbonate or bis(
2,4-dichlorophenyl) carbonate or bis(2
- cyanophenyl) carbonate. (2) Dihydric phenol has the general formula (I), (I1), (II1), (I
V) The method for producing the polycarbonate described in (1) above.

(R1, R2, Ra, R4 are hydrogen or have 1 to 8 carbon atoms
is an alkyl group containing a straight chain or branched chain, or a phenyl group, and X is a halogen atom and n=o to 4). (3) Under homogeneous solution polymerization conditions of polycarbonate, in the presence of a catalyst selected from electron-donating amine compounds, 2
phenol and bis(2,4,6-)dichlorophenyl) carbonate or bis(2,4-dichlorophenyl)
A method for producing a polycarbonate oligomer, which comprises reacting with carbonate or bis(2-cyanophenyl) carbonate. (4) Dihydric phenol is the above (2
) The method for producing the polycarbonate oligomer described in ). (5)
The method for producing the polycarbonate copolymer described in (1) or (2) or (3) or (4) above.

Representative examples of electron-donating amine compounds that can be used in the present invention include N,N-dimethyl-4-aminopyridine, 4-
diethylaminopyridine, 4-pyrrolidinopyridine, 4
-Aminopyridine, 2-aminopyridine, 2-hydroxypyridine 2-methoxypyridine 4-methoxypyridine 4-hydroxypyridine 2-dimethylaminoimidazole, 2-methoxyimidazole, 2. Examples include mercaptoimidazole, 2-aminopyridine, aminoquinoline, imidazole, and the like.

Moreover, the following compounds are mentioned as typical examples of dihydric phenols. As a bisphenol classified into general formula (I), 2,2-bis-(4-hydroxyphenyl)
Propane, 2,2-bis-(4-hydroxyphenyl)
Butane, 2,2-bis-(4-hydroxyphenyl)-
4-methylpentane, 2,2-bis-(4-hydroxyphenyl)octane, 4,4'-dihydroxy-2,
2,2-)liphenylethane, 2,2-bis-(3,5
-dibromo-4-hydroxyphenyl)propane and the like. Bisphenols classified into general formula (II) include 2,2-bis-(4-hydroxy-3-methylphenyl)propane, 2,2-bis-(4-hydroxy-3-isopropylphenyl)propane, 2. 2
-bis-(4-hydroxy-3-sec, butylphenyl)propane, 2,2-bis-(3,5-dimethyl-
4-hydroxyphenyl)propane, 2,2-bis-(
Examples include 4,hydroxy-3-tert-butylphenyl)propane. Bisphenols classified into general formula (III) include 1.1'-bis-(4-hydroxyphenyl)-p-diisopropylbenzene, 1
．． Examples include 1'-bis-(4-hydroxyphenyl)-m-diisopropylbenzene. General formula (IV)
As a bisphenol classified as 1,1-bis(4
-hydroxyphenyl)cyclohexane.

Furthermore, general formulas (I), (I1), and (III).

It is also possible to produce a copolymerized polycarbonate in which two or more dihydric phenols selected from (IV) are combined.

The method of the present invention involves converting dihydric phenols such as bisphenol A into bis( 2,4
, 6-trichlorophenyl) carbonate by interfacial polycondensation reaction.

The temperature at which this reaction proceeds ranges from below 0.6°C to about 150°C. Preferably it is in the range of 20°C to 70°C. If the temperature is below 200C, the reaction rate will be slow,
If the temperature is 70°C or higher, side reactions are likely to occur.

The electron-donating amine compound used as a catalyst is required to be used in an amount of 10-1 mol% to 10-3 mol%, preferably 10-2 mol%, based on the dihydric phenol present in the reaction system. If it is less than 10-2 mol%, the catalytic action will be low and the polymerization rate of the polycarbonate will be slow, and if it is more than 10-1 mol%, the proportion remaining as a catalyst in the polycarbonate produced will be high, leading to a decrease in the physical properties of the polycarbonate.

The required amount of bis(2,4,6-)dichlorophenyl)carbonate is equivalent to the mole of dihydric phenol present in the reaction system. Generally, in order to produce a high molecular weight polycarbonate, 1 mole of a carbonate compound and 1 mole of dihydric phenol must react. Bis (2, 4,
When using 6-trichlorophenyl) carbonate,
2,4,6-) dichlorophenol 2 moles are produced by the reaction. These 2 moles of 2.4.6-) dichlorophenol are converted into sodium salt by the phenol acceptor of the alkali or alkaline earth metal hydroxide present and are dissolved in the alkaline aqueous solution.

The present invention will be described below with reference to Examples, but the present invention includes:
The invention is not limited to these examples.

(Example) Example 1 2,2-bis(4-
After completely dissolving 22.8 g (0.1 mol) of hydroxyphenyl)propane, 4-dimethylaminopyridine 0.
．． 122g [2,2-bis(4-hydroxyphenyl)
10−2 mol% based on propane], bis(2,4,6
-trichlorophenyl)carbonate 42.09g (0
, 1 mol), 200 ml of methylene chloride was added, and the mixture was heated at room temperature (
After stirring for 4 hours at 25°C, the aqueous and organic phases were separated to obtain a colorless and transparent organic phase, which was mixed with methanol 51
A white, flaky polycarbonate could be obtained by pouring it into a container and pulverizing it with a homogenizer.

When the viscosity average molecular weight was measured, it was found that Mv = 29,000.

The viscosity average molecular weight was measured by measuring the intrinsic viscosity [r1] of a methylene chloride solution at 20°C using an Ubbelohde viscometer, and calculating the viscosity average molecular weight Mv using the following formula.

[r1] = 1.11 X 10-'(Mv)0-8
2 Example 2 Under exactly the same conditions as in Example 1, instead of 4-dimethylaminopyridine, 0.068 g of imidazole [10-2 for 2,2 bis(4-hydroxyphenyl)propane]
mol %] and stirred at room temperature (25°C) for 6 hours, the same treatment as in Example 1 was carried out to obtain white flaky polycarbonate. When the viscosity average molecular weight was measured, it was found that Mv=28,000.

Example 3 2.2-bis(4,hydroxyphenyl)propane 22
．． 8g (0.1 mol), bis(2,4,6-trichlorophenyl)carbonate) 42. ], g (0.1 mol)
, N,N-dimethyl-4-aminopyridine 0.12
2 g [10-2 mol% based on 2,2-bis(4-hydroxyphenyl)propane] in 200 ml of chloroform
In addition, the mixture was heated under reflux for 4 hours. A colorless and transparent loloform solution was gradually added dropwise to 2,000 ml of methanol while stirring with a homogenizer to obtain a white powder. Viscosity average molecular weight Mv = 4,500, Tg = 138°c
Met.

Example 4 2.2-bis(4-hydroxyphenyl)propane 11
．． 4g (50 mol%), 2,2-bis(4-hydroxy-3-tert-butylphenyl)propane 17.0g
(50 mol%).

0.122 g of N,N-dimethyl-4-aminopyridine [
10-2 mol % based on the bisphenol component] was added to 260 ml of dichloromethane and heated under reflux for 4 hours.

The colorless and transparent reaction solution was gradually added dropwise to 2,000 ml of methanol while stirring with a homogenizer to obtain a white powder. Viscosity average molecule iMv=5,600, Tg=12
It was 8°C.

Example 5 2.2-His(4-hydroxyphenyl)propane 2
After dissolving 2.8 g (50 mol%) and 29.0 g (50 mol%) of 4,4'-dihydroxy-2,2,2-)liphenylethane in 200 ml of 1N aqueous sodium hydroxide solution, (2,4,6-trichlorophenyl)carbonate) 42.1g (0.1 mol) and N,N-
Dimethyl-4-aminopyridine [10-2 mol % based on the bisphenol component] and 260 ml of dichloromethane were added and stirred at 250°C for 6 hours. When the reaction solution was separated into a pale yellow aqueous sodium hydroxide solution and a clear colorless dichloromethane solution.

The dichloromethane solution was gradually dropped into 2,000 ml of methanol while stirring with a homogenizer to obtain a white powder. Viscosity average molecular weight Mv=27,000.

Tg=165°C.

Comparative Example A similar treatment was carried out under exactly the same conditions as in Example 1, using 21.4 g (0.1 mol) of diphenyl carbonate instead of bis(2,4,6-trichlorophenyl) carbonate. No polymer was obtained; only raw materials were recovered.

(Effects of the Invention) By using bis(2,4,6-)lichlorophenyl) carbonate, etc., it is possible to obtain a high molecular weight, colorless and transparent polycarbonate that substantially does not contain chlorine ions without using toxic phosgene. Ta.

Claims (5)

[Claims] (1) Dihydric phenol and bis(2,4,6-trichlorophenyl) carbonate or bis(2,4-dichlorophenyl) in the presence of a catalyst selected from electron-donating amine compounds under interfacial polycondensation conditions of polycarbonate. A method for producing polycarbonate, which comprises reacting carbonate or bis(2-cyanophenyl) carbonate. (2) Divalent phenols are (1), (II), (III), (
IV) A method for producing polycarbonate according to claim 1. ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (III) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ( IV) (R_1, R_2, R_3, R_4 are hydrogen or have 1 carbon number
~8 linear or branched alkyl group, or phenyl group, where X is a halogen atom and n = 0 to 4) (3) Dihydric phenol and bis(2,4,6-trichlorophenyl) carbonate or bis(2,4-dichlorophenyl) in the presence of a catalyst selected from electron-donating amine compounds under homogeneous solution polymerization conditions of polycarbonate. A method for producing a polycarbonate oligomer, which comprises reacting with carbonate or bis(2-cyanophenyl) carbonate. (4) A method for producing a polycarbonate oligomer according to claim 2, in which the dihydric phenol is the dihydric phenol. (5) A method for producing a polycarbonate copolymer according to claim 1 or 2 or 3 or 4.