JPH043408B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel aromatic polyester having excellent heat resistance and moldability. [Prior Art] 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. Polymer
Science, 40 , 399 (1959), Visokomol.Soyed,
1, 834 (1959), Japanese Patent Publication No. 38-15247, British Patent Publication No. 897640, Japanese Patent Publication No. 37-5599, etc.). However, few of these aromatic polyesters have both heat resistance and moldability, and further improvements in these properties are desired. For example, polyisopropylidene-4,4'-diphenylene isophthalate, which is already produced on a commercial scale, is used in electrical fields such as sockets, connectors, bobbins, and switch parts, and in mechanical fields. Its use is limited to relatively small molded products such as watch parts and camera parts, as well as eye drop containers, resin teeth, and sunglass frame combs in the medical and other fields. Therefore, when used in larger-sized blow moldable or wide sheet materials, conventional aromatic polyesters have particular drawbacks in moldability, especially in shape retention of melted products. [Problems to be Solved by the Invention] The present inventors have recognized that the conventionally known heat-resistant aromatic polyesters have the above-mentioned problems, and have further developed an aromatic polyester with excellent heat resistance and moldability. As a result of searching for group polyesters, the number of carbon atoms is 8.
It has been found that an aromatic polyester consisting of 1 to 16 aromatic dicarboxylic acid component units, aromatic dinuclear bisphenol component units, and trifunctional aromatic compound component units having a specific structure achieves the above object, and the present invention reached. [Summary of the Invention] To summarize the present invention, the present invention provides the following features: [A] an aromatic dicarboxylic acid component unit having 8 to 16 carbon atoms, and [B] a polyol component unit, (a) a general formula [] [wherein, Group dinuclear bisphenol component units range from 95 to 99.99 mol%, and (b) general formula [] [In the formula, R′ represents a hydrogen atom or a lower alkyl group] α, α′, α″-tris(4-hydroxyphenyl)1,3,5-triisopropylbenzenes represented by ] [In the formula, R ² represents a lower alkyl group] At least one trifunctional aromatic selected from 2,6-bis(2'-hydroxy-5'-alkylbenzyl)-4-alkylphenols represented by Group compound component unit is 0.01 to 5
An aromatic polyol component unit consisting of an aromatic polyol component unit consisting of an aromatic polyol component unit consisting of an aromatic polyol component unit consisting of an aromatic polyol component unit consisting of an aromatic polyol component unit consisting of an aromatic polyol component unit consisting of an aromatic polyol component unit consisting of an aromatic polyol component unit consisting of an aromatic polyol component unit consisting of an aromatic polyol component unit consisting of an aromatic polyol component unit consisting of The gist of the invention is polyester. [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, isophthalic acid, phthalic acid, 2,6 naphthalene dicarboxylic acid, 4,4
- An aromatic dicarboxylic acid component unit consisting of biphenyl dicarboxylic acid or a mixture of at least two of these components. Among these aromatic dicarboxylic acid component units, terephthalic acid component units,
It is preferably an isophthalic acid component unit or a mixed component thereof, and particularly preferably a mixed component consisting of a terephthalic acid component unit and an isophthalic acid component unit. The aromatic polyol component unit [B] constituting the aromatic polyester of the present invention is composed of an aromatic dinuclear bisphenol component unit (a) and a trifunctional aromatic compound component unit (b). The composition of the aromatic polyol component unit is such that the aromatic dinuclear bisphenol component unit (a) is 95 to 99.99 mol%, preferably 97 to 99.9 mol%, and the aromatic trinuclear bisphenol component unit (b) is 95 to 99.99 mol%. It ranges from 0.01 to 5 mol%, preferably from 0.1 to 3 mol%. The aromatic dinuclear bisphenol component unit (a) has the general formula [] It is a bisphenol component unit represented by
In the formula,
It represents at least one group selected from the group consisting of a sulfur atom, a sulfinyl group, and a sulfonyl group. Specific examples of the aromatic dinuclear bisphenol component unit include the following compounds. 4,4'-dihydroxydiphenol, 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, 4,4'-dihydroxy diphenylthioether, bis(4-hydroxyphenyl)sulfone, and aromatic trinuclear bisphenol component unit (b),
General formula [] α, α′, α″-tris(4-hydroxyphenyl) 1,3,5-triisopropylbenzenes represented by the formula [wherein R′ represents a hydrogen atom or a lower alkyl group], and the general formula [ ] At least one trifunctional aromatic selected from 2,6-bis(2'-hydroxy-5'-alkylbenzyl)-4-alkylphenols represented by [wherein R ² represents a lower alkyl group] It is a group compound component unit. Specific examples of the trifunctional aromatic compound component unit include the following compounds. α,α′,α″-Tris(4-hydroxyphenyl)1,3,5-triisopropylbenzene α,α′,α″-Tris(3,5-dimethyl-4-
hydroxyphenyl)1,3,5-triisopropylbenzene, α,α′,α″-tris(3,5-diethyl-4-
hydroxyphenyl) 1,3,5-triisopropylbenzene, α, α′, α″-tris(3,5-di-n-propyl-4-hydroxyphenyl) 1,3,5-triisopropylbenzene, α , α′, α″-tris(3,5-diisopropyl-4-hydroxyphenyl) 1,3,5-triisopropylbenzene, α, α′, α″-tris(3,4-di-n-butyl-
4-hydroxyphenyl)1,3,5-triisopropylbenzene, 2,6-bis(2-hydroxy-5-methylbenzyl)4-methylphenol, 2,6-bis(2-hydroxy-5-ethylbenzyl) ) 4-ethylphenol, 2,6-bis(2-hydroxy-5-isopropylbenzyl) 4-isopropylphenol, among these, α, α′, α″-tris(4-hydroxyphenyl) 1,3 , 5-triisopropylbenzene or 2,6-bis(2-hydroxy-
5-methylbenzyl)4-methylphenol is preferred. The aromatic polyester of the present invention has a high molecular weight due to the condensation of the aromatic dicarboxylic acid component and the aromatic polyol component arranged in an alternating manner to form ester bonds, and its structure is based on the trifunctional aromatic polyester. The compound component unit has a branched structure. 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 a lower carboxylic acid. Therefore, it may be esterified. Intrinsic viscosity [η] of the aromatic polyester of the present invention
(Value measured at 50℃ in P-chlorophenol)
is in the range of 0.4 dl/g or more, preferably 0.5 dl/g or more. Further, the glass transition temperature of the aromatic polyester is usually 130 to 280°C, preferably
The temperature ranges from 150 to 260°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 A method in which the aromatic dicarboxylic acid or its ester-forming derivative and the aromatic polyol or its ester-forming derivative are reacted in the melt at a high temperature, and the low-boiling compound produced by the reaction is operated under reduced pressure. A method of producing an aromatic polyester by distilling it out of the reaction system by a method such as Solution polymerization method The aromatic dicarboxylic acid or its ester-forming derivative or its acid halide and the aromatic polyol are dissolved in a high boiling point solvent such as diphenyl ether, benzophenone, metaterphenyl, biphenyl chloride, or naphthalene bromide. or its ester-forming derivative is dissolved to form a solution and reacted at high temperature, or if necessary, to accelerate the reaction, 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 both solutions are brought into contact. Therefore, a method of producing an aromatic polyester by reacting the acid halide and the salt of the aromatic diol at the interface. [Effects of the Invention] Compared to conventional aromatic polyesters, the aromatic polyester of the present invention has better heat resistance and moldability, especially better melt flowability and shape retention, so it can be used for large molded products. It is suitable for manufacturing, and has the advantage that the molding cycle during molding can be shortened compared to conventional methods. In terms of physical properties, it also has the advantage of being excellent in dimensional stability, creep resistance, chemical resistance, etc. [Example] Next, the aromatic polyester of the present invention will be specifically explained with reference to 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. The melt index, which is a measure of the melt fluidity of the melt of the aromatic polyester, was measured using a melt indexer manufactured by Toyo Seiki Co., Ltd. at 320°C, and the melt tension, which is a measure of the shape retention of the melt, was measured using a melt indexer manufactured by Toyo Seiki Co., Ltd. using a melt tension tester manufactured by Toyo Seiki Co., Ltd.
Measured at 320°C. Example 1 82.8 parts of caustic soda, 2 parts of sodium hydrosulfite, 1.8 parts of triethylbenzylammonium bromide, 224.5 parts of 2,2-bis(4-hydroxyphenyl)propane, and α, α′,
α″-tris(4-hydroxyphenyl) 1,3,
An aqueous solution of 5.6 parts of 5-triisopropylbenzene dissolved in 5000 parts of water and terephthalic acid dichloride.
101.5 parts and a solution of 101.5 parts of isophthalic acid dichloride dissolved in 3000 parts of methylene chloride,
Interfacial polymerization was carried out by contacting the mixture with high speed stirring at a temperature of 0.degree. C. to 20.degree. C., and then acetone was added to precipitate the resulting aromatic polyester, which was isolated and recovered. The aromatic polyester thus obtained had an intrinsic viscosity [η] of 0.69 dl/g and a glass transition temperature of 190°C. In addition, the melt index of this aromatic polyester is 40g/10min, and the melt tension is
It was 1.9g. Comparative Example 1 In Example 1, α, α′, α″-tris(4-
Hydroxyphenyl) 1,3,5-triisopropylbenzene is not used, and 2,2-bis(4
An aromatic polyester was synthesized in the same manner as in Example 1 except that 228 parts of -hydroxyphenyl)propane was used. Intrinsic viscosity of the obtained aromatic polyester [η]
was 0.75 dl/g, and the glass transition temperature was 188°C. Further, the melt index of this aromatic polyester was 1.3 g/10 min, and the melt tension was 0.4 g. Examples 2, 3 Use of 2,2-bis(4-hydroxyphenyl)propane and α,α′,α″-tris(4-hydroxyphenyl)1,3,5-triisopropylbenzene in Example 1 An aromatic polyester was produced in the same manner as in Example 1, except that the amounts listed in Table 1 were used. Intrinsic viscosity [η] of the obtained aromatic polyester; glass transition temperature, melt index, and melt tension were as shown in Table 1. [Table] Comparative Example 2 In Example 1, 207.5 parts of 2,2-bis(4-hydroxyphenyl)propane and α, α′,
α″-tris(4-hydroxyphenyl) 1,3,
An aromatic polyester was produced in the same manner as in Example 1 except that 33.8 parts of 5-triisopropylbenzene was used. The obtained aromatic polyester did not dissolve in P-chlorophenol and was a gelled polymer. Examples 4 to 6 Aromatic polyesters were produced in the same manner as in Example 1, except that aromatic dicarboxylic acid dichloride and aromatic diol were used as shown in Table 2. Intrinsic viscosity [η] of the obtained aromatic polyester,
The glass transition temperature, melt index and melt tension were as shown in Table 2. [Table] Example 7 In Example 1, 2,6-bis(2-hydroxy-5- An aromatic polyester was produced in the same manner as in Example 1 except that 3.5 parts of methylbenzyl)-4-methylphenol was used. Intrinsic viscosity [η] of the obtained aromatic polyester
is 0.65dl/g, and its glass transition temperature is
It was 190℃. Further, the melt index of this aromatic polyester was 3.6 g/min, and the melt tension was 1.8 g.

Claims (1)

[Scope of Claims] 1 [A] An aromatic dicarboxylic acid component unit having 8 to 16 carbon atoms, and [B] a polyol component unit, (a) General formula [] [In the formula, X represents a direct bond or at least one member selected from the group consisting of a lower alkylidene group having 1 to 8 carbon atoms, an oxygen atom, a carbonyl group, a sulfur atom, a sulfophile group, and a sulfonyl group] aromatic dinuclear bisphenol component units in the range of 95 to 99.99 mol%, and (b) general formula [] α, α′, α″-tris(4-hydroxyphenyl) 1,3,5-triisopropylbenzenes represented by the formula [wherein R′ represents a hydrogen atom or a lower alkyl group], and the general formula [ ] ^2,6 -bis(2'-hydroxy-
P- An aromatic polyester characterized by an intrinsic viscosity [η] of 0.4 dl/g or more as measured in chlorophenol at 50°C.