JPS60197724A - Aromatic polyester - Google Patents

Abstract

PURPOSE:An aromatic polyester having excellent heat resistance and good moldability, comprising a repeating aromatic dicarboxylic acid unit and specified two kinds of non-adjacent repeating bisphenol units. CONSTITUTION:An aromatic polyester comprising repeating units of formulas I , II, and III [wherein the carbonyl groups in formula I are meta or para to each other, each O atom in formula II is meta or para to the isopropylidene group, and in formula III, R1-R4 are each H, a 1-8C hydrocarbon group, or a halogen, and a, b, and c are integers satisfying the relationships (b+c)/a=0.90-1.10 and b/c=1.90-0.25], wherein the units of formulas II and III do not adjoin to each other. This aromatic polyester shows excellent heat resistance and good moldability. This polymer can be produced by any well-known polymerization process such as interfacial polymerization, low-temperature solution polymerization, high-temperature solution polymerization, or melt polymerization.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical field to which the invention pertains] The present invention relates to an aromatic polyester I having excellent heat resistance and good moldability.

[Technical background of the invention and its problems]

2. Aromatic polyesters produced from 2-bis(4'-hydroxyphenyl)furopane or its derivatives, terephthalic acid, inphthalic acid, or their derivatives have bending strain recovery properties and impact resistance.

It is known to have excellent performance in mechanical properties such as tensile strength, thermal properties such as heat distortion temperature and mechanical properties at high temperatures, S flammability, and chemical resistance. However, the glass transition temperature of the above-mentioned aromatic polyester is 200℃ or less, and the heat distortion temperature of the molded product is 180υ or less.
Recent high-performance engineering plastics I: Some may or may not fully meet the required heat resistance performance.

On the other hand, 2,2-bis(4'-hydroxypheni'A/)
Nine aromatic polyesters use dihydroxynaphthalene as the bisphenol component instead of propane.

Although it has extremely high heat resistance, it has a major drawback in that it has a melting point of 300° C. or higher, making it difficult to mold, and the molded product is opaque and extremely brittle.

[Purpose of the invention]

The inventors of the present invention have conducted intensive studies to solve the above problems, and as a result, the bisphenol component is expressed by the following formula.

[In the formula (■) Formula I:, the hydroxyl group is at the meta or para position i to the inpro-pylidene group C:. R1-- in formula M represents hydrogen, a hydrocarbon group having 1 to 8 carbon atoms, or a halogen atom, and may be the same or different.

It has been found that by using a mixture of bisphenols represented by the following, the above-mentioned drawbacks can be greatly improved, and an aromatic polyester having good moldability and excellent heat resistance can be produced.

The object of the present invention is to provide a method for producing this aromatic polyester.

[Summary of the invention]

The present invention is based on the general formula [wherein, in the formula (■), the carbonyl groups are at the 52 meta or para position to each other, and in the @ formula, the oxygen atom is at the meta or para position with respect to the inpropylidene group. can be,
(■) In formula I, 8 to R4 represent hydrogen, a hydrocarbon group having 1 to 8 carbon atoms, and a circle represents a halogen atom, which may be the same or different from each other. a, b, and c are each positive integers.

(b+c)/a = 0.90~1.10, b/c
= 19. OS-0,25). @ and (II
I) is characterized by consisting of repeating units that are not adjacent to each other.

Examples of dicarboxylic acid components used in the production of the aromatic polyester of the present invention include inphthalic acid and terephthalic acid, and each can be used alone, but 1
A mixture of both is often used, with the ratio of the inphthalic acid component to the terephthalic acid component being 30:70 to 70:
It is preferable to use a range of 30.

The dicarboxylic acid component is used as a derivative of aromatic dicarboxylic acid such as dichloride or diester, or as the dicarboxylic acid.

The bisphenol component of the present invention includes 2,2-bis(
4'-hydroxyphenyl)propane, 2,2-bis(
3'-hydroxyphenyl)furopane, 2°2-(3'
2,2-bis(hydroxyphenyl)propanes such as -hydroxyphenyl)-(4#-hydroxyphenyl)propane are used. Particularly preferred is 2,2-bis(4'-hydroxyphenyl)propane.

furthermore≦2 In the present invention, dihydroxynaphthalenes are used as the other bisphenols.

Specific examples include 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2゜7-dihydrosinaphthalene. , 2,7-dimethyl-1°5-dihydroxynaphthalene, 7.1,5-dimethyl-2,6-dihydroxynaphthalene, 1,5-dichloro-2,6-dihydroxynaphthalene, and the like.

These can be used alone or as a mixture of two or more. Among these, particularly preferred are 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, and 27-dihydroxynaphthalene.

In the present invention C2, the molar ratio of the bisphenols represented by the @ formula and the (ffl) formula to the dicarboxylic acid component represented by the formula (1) is in the range of 0.90 to 1.10.

There are no particular restrictions on the method for producing the polymer of the present invention.

Interfacial polymerization method, low temperature solution polymerization method, high temperature solution polymerization method.

Any known method such as melt polymerization can be applied.

The polymers of the present invention contain, in addition to the components already mentioned.

It can contain 111 or more reactive components or mixed components such as monohydric phenols and alcohols as molecular weight regulators or terminal stabilizers, and phosphorous acids as oxidation stabilizers.

〔Effect of the invention〕

According to the lid of the present invention, an aromatic polyester having excellent heat resistance (C2) and good molding processability (JL) can be easily manufactured.

[Embodiments of the invention]

Example 1゜ Put 100 mJ of water and 25.6 m of 5N NaOH aqueous solution into a reaction flask, and add 6.62 F of 2.2-bis(4'-hydroxyphenyl)propane and 4.65 t of 2.7-hydroxynaphthalene. After stirring and dissolving, 0.1 F of cetyltrimethylammonium bromide was added, dissolved, and cooled on ice. To this solution, a solution prepared by dissolving 11.77 f of an equimolar mixture of inphthaloyl chloride and terephthaloyl chloride in 200 m/dichloromethane was added dropwise at once under rapid stirring. After the dropwise addition was completed, the mixture was further stirred for 21 hours, 1.02 m4 of concentrated hydrochloric acid (11,4N) was added, and 200 tn of neutralized water was added, stirred and allowed to stand. The separated aqueous layer was discarded and the reaction mixture was dissolved in ethanol 41. was added to the solution while stirring vigorously. The polymer obtained by filtration was pulverized with a mixer, washed with water and ethanol, and then dried in vacuum.

A colorless polymer of 18.7F (99.4%) was obtained. Phenol and 1,1,2,2-tetrachlorethane (
The intrinsic viscosity was 1.92 when measured at 30° C. using 1:1 solvent (weight ratio 4:6).

Heat content 1? The glass transition temperature of the polymer with two strands is 23
6°C, melting point t2309°C. This polymer is 28
By compression molding at 0°C and 100 Kg/t:s/I, a colorless, transparent and tough molded product was obtained.

Comparative Example 1 C2,2-bis(4'-hydroxyphenyl)propane was used in place of 4,4'-dihydroxybenzophenone in Example 1. The intrinsic viscosity of the obtained polymer was 1°5
1, the glass transition temperature was 193°C, and the melting point was 260°C.

Comparative Example 2゜2.2-bis(4'-hydroxyphenyl) of Example 1
C2,7-dihydroxynaphthalene was used instead of probon.

The obtained polymer was insoluble in a mixture of phenol and tetrachloroethane, had a melting point of 330°C or higher, and when compression molded at 300°C, it was opaque and only a brittle molded product with many pieces was obtained.

Example 2゜In place of 2,7-dihydroxynaphthalene in Example 1, 2
, 6-dihydroxynaphthalene was used.

The intrinsic viscosity of the obtained polymer was 1.73. The glass transition temperature was 226°C and the melting point was 286°C. This polymer was compression molded at 250°C (a pale orange, transparent and tough molded product was obtained).

Example 3 1,5-dihydroxynaphthalene was used in place of 2,7-dihydroxynaphthalene in Example 1.

The obtained polymer had an intrinsic viscosity of 1.58 and was compression molded.
A more transparent and tougher molded product can be obtained.

Representative patent attorney Kensuke Norichika (and one other person)

Claims (1)

[Scope of Claims] General formula [wherein, in the formula (I), the carbonyl groups are in the (: meta or para position), and (2) the oxygen atom at the Meta position or no paddle position C
In formula 6 (■), ``-'' in ``2'' represents hydrogen, and ``9'' in the hydrocarbon group having 1 to 8 carbon atoms represents a halogen atom, which may be the same or different from each other. a, b, c are the above integers, (b+c)/a” 0.90 to 1.10
, b/c=19.0-0.25). An aromatic polyester characterized by consisting of i repeating units in which @ and (l[[) are not adjacent to each other.