JPS6142536A - 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 a terephthalic acid component and an isophthalic acid component and (B) an aromatic diol component comprising 20-98mol% aromatic binuclear bisphenol component of formula I (wherein X is a direct bond, a 1-8C alkylidene, O, CO, S, sulfinyl or sulfonyl) and 2-80mol% aromatic trinuclear bisphenol component of formula II(wherein R<1-8> are each H or a lower alkyl) in a high-boiling solvent (e.g., diphenyl ether) and reacted with each other 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 such as terephthalic acid component units and isophthalic acid component units and various bisphenol component units have been proposed as heat-resistant aromatic polyesters [for example, J, PolymerScience+40+
399 (1959), Visokomol,
5oyed.

No. 834 (1959), Special Publication Show 3B-152
Publication No. 47, British Patent Publication No. 897640, Special Publication No. 1977
See Publication No.-5599, etc.]. However, these aromatic polyesters have a drawback of poor hydrolysis resistance at high temperatures. For example, polyisopropylidene-4,4'-diphenylene isophthalate terephthalate, which is already commercially produced, is easily hydrolyzed in an atmosphere where water is present at high temperatures, such as in boiling water, and its performance is greatly reduced. decreases to As described above, conventional aromatic polyesters have the disadvantage that they have poor hydrolysis resistance at high temperatures and are 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 found that an aromatic polyester consisting of an aromatic dicarboxylic acid component unit having 8 to 16 atoms, an aromatic trinuclear bisphenol component unit, and an aromatic trinuclear bisphenol component unit having a specific structure achieves the above object. , arrived at the present invention.

[Summary of the invention]

To summarize the present invention, (A) an aromatic dicarboxylic acid component unit having 8 to 16 carbon atoms, and [B] a diol component unit, (a) a general formula (I) (in the formula, X is a direct bond or an alkylidene group having 1 to 8 carbon atoms, an oxygen atom, a carbonyl group, a sulfur atom,
at least one selected from the group consisting of sulfinyl group and sulfonyl group] in the range of 20 to 98 mol % of aromatic trinuclear bisphenol component units, and (bl general formula (II) 0, R', R2, R1, R4, R6, R6, R9 and ♂ all represent a hydrogen atom or a lower alkyl group. aromatic diol component unit, and is composed of 60° in pentafluorophenol.
The intrinsic viscosity [η] measured at C is 0.4d1. /a or more, an aromatic polyester characterized by:
is the gist of the invention.

[Means and effects for solving the problems] The aromatic dicarboxylic acid component unit CA) constituting the aromatic polyester of the present invention is an aromatic dicarboxylic acid component unit having 8 to 16 carbon atoms. 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.

Aromatic diol component units (Bl), aromatic trinuclear bisphenol buccal component units (al and aromatic trinuclear bisphenol bone units (b) constituting the aromatic polyester of the present invention)
The composition of the aromatic diol component unit is such that the aromatic dinuclear bisphenol component unit fal is 2.
0 to 98 mol%, preferably 20 to 90 mol%
and the aromatic trinuclear bisphenol component unit [1))
ranges from 2 to 80 mol%.

The aromatic trinuclear bisphenol component unit (a) is a bisphenol component unit represented by the general formula (1), in which X
is a direct bond or at least one member selected from the group consisting of alkylidene groups having 1 to 8 carbon atoms such as methylene group, ethylidene group, propylidene group, oxygen atom, carbonyl group, sulfur atom, sulfinyl group, and sulfonyl group. Indicates the group.

Specific examples of the aromatic trinuclear bisphenol component unit include the following compounds.

4.4'-'; Hydroxydiphenyl, bis(4-hydroxyphenyl)methane, 2.2-bis(4-hydroxyphenyl)propane, 2.2-bis(4-hydroxyphenyl)butane, 4.4'- Cyclohexylidene diphenol, 1-phenyl-1,1-bis(4-hydroxyphenyl)ethane, 4,4'-dihydroxybenzophenone, 4,4'-dihydroxydiphenyl ether, 414'-thiodiphenol, bis(4-hydroxy phenyl) sulfone, and the aromatic trinuclear bisphenol component unit (bl is the general formula (I[
) is a bisphenol component unit represented by R
', R2, R3, R', R town Rb, R' and R8
Each represents 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 cheek 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 The aromatic polyester of the present invention has the aromatic dicarboxylic acid component units and the aromatic diol component arranged alternately. It condenses in this state and increases the molecular weight in a substantially linear manner by forming ester bonds, and the terminal end of the molecule may be a carboxyl group or a hydroxyl group, and the terminal carboxyl group may be esterified by a lower alcohol. or the terminal hydroxyl group may be esterified with a lower carboxylic acid.

The intrinsic viscosity [η] of the aromatic polyester of the present invention (value measured at 60°C in pentafluorophenol) is 0.4
di/g or more, preferably 0.5 di/g or more. Further, the glass transition temperature of the aromatic polyester is usually in the range of 130 to 300°C, preferably 150 to 280°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 diol or its ester-forming derivative are reacted in the melt at a high temperature, and the low boiling point compound produced by the reaction is operated under reduced pressure. A method of producing aromatic polyester by distilling it out of the reaction system.

The aromatic dicarboxylic acid or its ester-forming derivative or its acid halide and the aromatic diol or The 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.

Interfacial polymerization method The acid halide of the aromatic dicarboxylic acid is dissolved in an organic solvent, while the aromatic diol is dissolved in water as a metal salt such as a sodium salt, and then the two warm liquids are brought into contact. A method of producing an aromatic polyester by reacting the acid halide and the salt of the aromatic diol at an interface.

〔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. Further, the glass transition temperature of the aromatic polyester was determined by measuring with a differential scanning calorimeter. Furthermore, the hydrolysis resistance of the aromatic polyester was expressed as the retention rate (%) of the initial value of the intrinsic viscosity [η] after the molded product was immersed in boiling water for 10 days.

Example 1 83 parts of terephthalic acid, 83 parts of isophthalic acid, 156 parts of 2.2-bis(4-acetoxyphenyl)propane, 1.
4-bis(3,5-dimethyl-4-acetoxycumyl)
243 parts of benzene, 0.33 parts of triphenyl phosphate
1 part and 0.1 part of tetrabutoxy titanate were charged into a reactor and heated at 250°C to 27°C while stirring under nitrogen atmosphere.
After the reaction was carried out at normal pressure for about 2 hours while distilling off the acetic acid produced at 0°C, the pressure of the reaction system was gradually reduced over about 2 hours and the temperature was raised, and finally the pressure was reduced to Q, 7mm11.
g and the temperature was raised to 350°C. Intrinsic viscosity of the aromatic polyester thus obtained [
η] was 0.75 a/g, and its glass transition temperature was 232°C'.

Furthermore, the hydrolysis resistance of this aromatic polyester is 96
%, which was an excellent value.

Comparative Example 1 In Example 1, 1,4-bis(3,5-dimethyl-
4-acetoxycumyl) without benzene, 2.2-
An aromatic F-rester was produced in the same manner as in Example 1 except that <7312 parts of bis(4-acetoxyphenyl)pro) were used. The aromatic 1-mylyester obtained had an intrinsic viscosity [η] of 0.68 dl/g and a force transition temperature of 186°C. Furthermore, the hydrolysis resistance of this aromatic polyester was 48%.

Examples 2 to 8 Example 1 except that aromatic dicarboxylic acid, diacetate of aromatic trinuclear bisphenol, and diacetate of aromatic trinuclear bisphenol were used as shown in Table 1, respectively.
An aromatic polyester was produced in the same manner as above. 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] Diol component unit, (a) General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼[I [In the formula, X represents a direct bond or at least one member selected from the group consisting of an alkylidene group having 1 to 8 carbon atoms, an oxygen atom, a carbonyl group, a sulfur atom, a sulfinyl group, and a sulfonyl group] (b) General formula [II] ▲ Numerical formula, chemical formula, table, etc. ▼ [II] [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 consisting of 2 to 80 mol% of aromatic trinuclear bisphenol component units. consisting of component units, and heated at 60°C in pentafluorophenol.
An aromatic polyester characterized by having an intrinsic viscosity [η] of 0.4 dl/g or more as measured by