JPS6142532A - Aromatic polyester - Google Patents

Abstract

PURPOSE:The titled polyester excellent in heat and hydrolysis resistances, comprising units of an 8-16C aromatic dicarboxylic acid component and units of a specified aromatic diol component. CONSTITUTION:An aromatic polyester of an intrinsic viscosity >=0.4dl/g (as measured in pentafluorophenol at 60 deg.C) is obtained by dissolving (A) at least two 8-16C aromatic dicarboxylic acid components such as a mixture of 5- 95mol% terephthalic acid component and 95-5mol% isophthalic acid component and (B) an aromatic diol component comprising 80-100mol% aromatic trinuclear bisphenol component of the formula (wherein R<1-8> are each H or a lower alkyl) and other aromatic diol components (e.g., resorcinol) in a high-boiling solvent (e.g., diphenyl ether) and condensed at a high temperature in the presence of, optionally, a basic compound (e.g., N-methylpyrrolidone).

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel aromatic polyester having excellent heat resistance and hydrolysis resistance.

[Conventional technology]

Conventionally, aromatic polyesters consisting of aromatic dicarboxylic acid component units, aromatic dicarboxylic acid component units such as isophthalic acid component units, and various bisphenol component units have been proposed as heat-resistant aromatic polyesters [for example, J, Polymer 5science,
40 + 399 (1959) + Visokomo
1, 5oyed + supra, 834 (1959), Japanese Patent Publication No. 3B-15247, British Patent No. 897640, Japanese Patent Publication No. 37-5599, etc.). but,
These aromatic polyesters have the disadvantage of poor hydrolysis resistance at high temperatures. For example, polyisopropylidene-4,4'-diphenylene isophthalate teleclate, which is already commercially produced, easily undergoes hydrolysis in the presence of water at high temperatures such as boiling water. Performance will drop significantly. In this way, conventional aromatic polyesters have poor hydrolysis resistance at high temperatures;
It has the disadvantage of being susceptible to hydrolysis during molding or use under high temperature conditions.

[Problem that the invention seeks to solve]

The present inventors recognized that the previously known heat-resistant aromatic polyesters had the above-mentioned problems, and as a result of searching for aromatic polyesters with excellent heat resistance and hydrolysis resistance, they discovered that carbon It has been discovered that an aromatic polyester whose main components are an aromatic dicarboxylic acid component unit having 8 to 16 atoms and an aromatic trinuclear bisphenol component unit having a specific structure can achieve the above object, and the present invention has been achieved. .

[Summary of the invention]

To summarize the present invention, the present invention comprises (A) an aromatic dicarboxylic acid component unit having 8 to 16 carbon atoms, and [B] general formula (1) [wherein R1, R2, R3, R4, R', R', R7
and R8 each represent a hydrogen atom or a lower alkyl group.
The gist of the invention is an aromatic polyester characterized by an intrinsic viscosity [η] of 0.4 dl/g or more as measured by C.

[Means and effects for solving the problems] The aromatic dicarboxylic acid component unit (A) constituting the aromatic polyester of the present invention is an aromatic dicarboxylic acid component unit having 8 to 16 carbon atoms, and more specifically Specifically, terephthalic acid,
It is an aromatic dicarboxylic acid component unit consisting of isophthalic acid, phthalic acid, 2,6-naphthalene dicarboxylic acid, 4,4-biphenyl dicarboxylic acid, or a mixture of at least two of these. Among these aromatic dicarboxylic acid component units, terephthalic acid component units, isophthalic acid component units, and mixed components thereof are preferable, and in particular, a mixed component consisting of terephthalic acid component units and isophthalic acid component units is preferable. preferable. When the aromatic dicarboxylic acid component unit is the mixed component, the composition is usually 5 to 95 mol% of the terephthalic acid component unit.
, preferably 10 to 90 mol % and isophthalic acid component units usually 5 to 95 mol %, preferably 10
The content ranges from 90% to 90% by mole.

The aromatic trinuclear bisphenol component unit (B), which is the main component unit of the aromatic diol component unit constituting the aromatic polyester of the present invention, is a bisphenol buccal component unit represented by the general formula, where R', R2, R3, R4, R5,
R6, R7 and R8 all represent a hydrogen atom or a lower alkyl group such as a methyl group, an ethyl group or an isopropyl group. Specific examples of the aromatic trinuclear bisphenol component unit include the following compounds.

1.3-bis(4-hydroxycumyl)benzene, 1.
4-bis(4-hydroxycumyl)benzene, 1.3-
Bis(3,5-dimethyl-4-hydroxycumyl)benzene, 1.4-bis(3,5-dimethyl-4-hydroxycumyl)benzene, 1.3-bis(3,5-dimethyl-4- hydroxycumyl)benzene, 1,4-bis(3,5-dimethyl-4-hydroxycumyl)benzene, and other aromatic diol component units that may be present in small amounts together with the aromatic trinuclear bisphenol component units. hydroquinone, dihydric phenols such as resorcinol, 4,4'-dihydroxydiphenyl, bis(4
-hydroxyphenyl)methane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane, 4,4'-cyclohexylidene diphenol, 1-phenyl-1,1 Examples include bisphenols such as -bis(4-hydroxyphenyl)ethane, 4.4'-dihydroxybenzophenone, 4.4'-dihydroxydiphenyl ether, 4.4'-thiodiphenol, and bis(4-hydroxyphenyl)sulfone. can do.

The composition of the aromatic trinuclear bisphenol component units relative to the wholly aromatic diol component units is preferably in the range of 100 to 100% by mole.

The aromatic polyester of the present invention condenses in a closed state in which the aromatic dicarboxylic acid component units and the aromatic diol component whose main component is the aromatic trinuclear bisphenol component are arranged alternately to form an ester bond, resulting in a substantially linear shape. It has a high molecular weight, and the terminal end of the molecule may be a carboxyl group, or a hydroxyl group, or the terminal carboxyl group may be esterified with a lower alcohol, or the terminal hydroxyl group may be esterified with a lower alcohol. may be esterified with a lower carboxylic acid.

The intrinsic viscosity [η] (value measured at 60°C in pentafluorophenol) of the aromatic polyester of the present invention is 0.4a
/g or more, preferably 0.5Ct1/g or more. Further, the glass transition temperature of the aromatic polyester is usually 130 to 300°C, preferably 150 to 2°C.
It is in the range of 80°C.

The aromatic polyester of the present invention can be produced by the same method as conventionally known aromatic polyesters. For example, the following method can be exemplified.

Melt polymerization method The aromatic dicarboxylic acid or its ester-forming derivative and the aromatic trinuclear bisphenol-based aromatic diol or its ester-forming derivative are reacted at high temperature while melting, and a low boiling point product is produced by the reaction. A method of producing aromatic polyester by distilling the compound out of the reaction system by operating under reduced pressure or other methods.

Solution polymerization method The aromatic dicarboxylic acid or its ester-forming derivative or its acid halide and the aromatic An aromatic diol containing trinuclear bisphenol as a main component or its ester-forming derivative is dissolved to form a solution and reacted at high temperature, or if necessary, a tertiary amine, N-
A method of producing aromatic polyester by reacting in the presence of a basic compound such as methylpyrrolidone.

〔Effect of the invention〕

Since the aromatic polyester of the present invention has superior heat resistance and hydrolysis resistance compared to conventional aromatic polyesters, deterioration during melt molding and use at high temperatures is prevented.

〔Example〕

Next, the aromatic polyester of the present invention will be specifically explained using Examples.

In the Examples and Comparative Examples, the amounts of raw materials, solvents, catalysts, etc. used are expressed in parts by weight. It was also determined by measuring with a mold calorimeter. Furthermore, the hydrolysis resistance of the aromatic polyester is determined by the retention rate (%) of the initial value of the intrinsic viscosity [η] after immersing the molded product in boiling water for 10 days.
It was shown in

Example 1 83 parts of terephthalic acid, 83 parts of isophthalic acid, 430 parts of 1,3-bis(4-acetoxycumyl)benzene, 0.33 parts of triphenyl phosphate and 0.1 part of tetrabutoxy titanate were charged into a reactor and nitrogen gas was added. After the reaction was carried out at normal pressure for about 2 hours while stirring in an atmosphere and distilling off the acetic acid produced at 250°C to 270°C, the reaction was continued for about 2 hours.
The pressure of the reaction system was gradually reduced and the temperature was increased over time, and finally the pressure was brought to Q, 7ml, 111g, and the temperature was raised to 350°C. The aromatic polyester thus obtained had an intrinsic viscosity [η] of 0.14 a/g and a glass transition temperature of 225°C. Further, the retention rate of the intrinsic viscosity [η] after immersing the press-formed product in boiling water for 10 days was 96%, indicating excellent hydrolysis resistance.

Comparative Example 1 Example 1 except that 312 parts of 2,2-bis(4-acetoxyphenyl)propane was used instead of 1,3-bis(4-acetoxycumyl)benzene.
An aromatic polyester was produced in the same manner as above.

The intrinsic viscosity [η] of the obtained aromatic polyester is 0.6
8 dl/g, and its glass transition temperature was 186°C. Furthermore, the hydrolysis resistance of this aromatic polyester was 48%.

Examples 2 to 6 Aromatic polyesters were produced in the same manner as in Example 1, except that aromatic dicarboxylic acids and diacetates of aromatic trinuclear bisphenols were used as shown in Table 1, respectively.

The intrinsic viscosity [η], glass transition temperature, and hydrolysis resistance of the obtained aromatic polyester were as shown in Table 1.

Claims (1)

[Claims] (1) [A] Aromatic dicarboxylic acid component unit having 8 to 16 carbon atoms, and [B] General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼[I] [In the formula, R^1 , R^2, R^3, R^4, R^5, R
^6, R^7 and R^8 all represent a hydrogen atom or a lower alkyl group] An aromatic diol component unit whose main component is an aromatic trinuclear bisphenol component unit, and 60°C in pentafluorophenol.
An aromatic polyester characterized by having an intrinsic viscosity [η] of 0.4, dl/g or more, as measured by .