JPH02163117A - Wholly aromatic polyester - Google Patents

Abstract

PURPOSE:To obtain the subject polymer having low melt-forming temperature and excellent water-resistance, mechanical properties. chemical resistance, etc., and suitable for fiber, film, container, etc., by copolymerizing a specific aromatic diol and p-hydroxybenzoic acid. CONSTITUTION:The objective polymer can be produced by mixing (A) 30-80mol% of p-hydroxybenzoic acid giving a structural unit of formula I. (B) 1-40mol% of 3,3'-dimethyl-biphenyl giving a structural unit of formula II, (C) 0-20mol% of an aromatic diol such as hydroquinone giving a structural unit of formula III (Ar1 is phenyl, etc.) and (D) 10-40mol% of an aromatic dicarboxylic acid giving a structural unit of formula IV (Ar2 is phenyl, etc.). adding e.g. acetic anhydride to the mixture and subjecting the components to deacetylating polymerization.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to melt-formable wholly aromatic polyesters. More specifically, one song relates to a wholly aromatic polyester that has excellent mechanical properties such as rigidity, tensile strength, and impact resistance, as well as excellent heat resistance and water resistance.

[Conventional technology]

As a wholly aromatic polyester, p-hydroxybenzoic acid polyester is conventionally known.

However, although p-hydroxybenzoic acid polyester has excellent heat resistance, it decomposes markedly due to heat during melting, so it has the disadvantage that it cannot be molded using ordinary melt molding such as injection molding or extrusion molding. have. Further, as an attempt to improve the drawbacks of p-hydroxybenzoic acid polyester, a nine-fully aromatic polyester has been proposed in which a moderate amount of an aromatic dicarboxylic acid component and a number of aromatic diol components are collinear. Japanese Patent Publication No. 47-47870 describes a wholly aromatic polyester obtained by copolymerizing p-hydroxybenzoic acid with 4,4'-dihydroxybiphenyl and terephthalic acid.

[Detailed problem to be solved by the invention]

This polyester melts at a lower temperature than the p-hydroxybenzoin r1 polyester and has improved melt moldability, but from an industrial standpoint, the improvement in FI melt moldability has not been sufficiently improved. Far from being nine. Furthermore, it is difficult to say that it is practically excellent in terms of water resistance.

[Means to solve the problem]

As a result of intensive research in view of this situation, the present inventors found that
A wholly aromatic polyester obtained by reacting an aromatic diol containing a specific aromatic diol with p-hydroxybenzoic acid and a specific aromatic dicarboxylic acid has a low melt molding temperature and good water resistance at high temperatures. It was discovered that it has excellent mechanical properties, chemical resistance, and water resistance.

The present invention has now been completed.

That is, 1 the present invention comprises the following structural units (I) to (IV), in which the structural unit (I) is 30 to 80 mol% of the total, the structural unit 0 is 0 to 20 mol% of the total, and the structural unit (III) is 0 to 20 mol% of the total. A wholly aromatic polyester characterized by containing 1 to 40 mol% of the total amount and 10 to 40 mol% of structural unit (IV).

shows. ) I'm going to waste it with something that provides.

The above structural unit (I) is a structural unit of nine polyesters produced from p-hydroxybenzoic acid. ! Ta.

III4.4-dihydroxybiphenyl and hydroquinone are used as the aromatic diol that provides the aromatic diol residue represented by the structural unit . Structural unit (LID)
d 3.3' as a compound giving a 3,3'-dimethyl-4,4'-dihydroxybiphenyl residue represented by
-dimethyl-4,47-dihydroxypiphenyl is used. Aromatic/zocal represented by structural unit (IV)? As the aromatic dicarboxylic acid that provides the phosphoric acid residue, terephthalic acid, isophthalic acid, and 2,6-naphthalic acid/dicalge acid are used. -10,000, the above structural unit (Il~(IV
) The content ratio of the structural unit (Il is 30 to 80 mol% of the whole, the m molding position is 0 to 20 mol% of the whole, and the structural unit (
m) accounts for 1 to 40 mol% of the total, and structural unit (IV) accounts for 10 to 40 mol% of the total. Among them, the structural unit range is 5~
It is preferable that the content of the structural unit (1) is 15 mol% and the structural unit (1) is 5 to 30 mol%, since a product with excellent melt moldability and heat resistance can be obtained. 3
5 to 65 mol% S structural unit (modeling) is 15 to 35 mol%
It is especially preferable to use it. Ninth, the sum of the number of moles of structural unit I and GfI) and the number of moles of structural unit (IV) are usually preferably substantially equal.

A typical method for producing the wholly aromatic polynisder of the present invention includes, for example, the following method.

(1) Acylated products of oxybenzoic acid such as p-7 acetoxybenzoic acid, diacylated products of aromatic diol compounds such as 4,4'-diacetoxybiphenyl, and 3,3'-dimethyl-4,4'- A method for producing diacetoxybiphenyl and an aromatic dicarnoic acid such as terephthalic acid by deacetic acid polymerization.

(2) p-hydroxybenzoic acid, an aromatic diol such as 4,4'-dihydroxybiphenyl, and 3,3'-dimethyl-4,4'-dihydroxybiphenyl.

A method for producing acetic anhydride and an aromatic dicarpo-7 acid such as terephthalic acid by deacetic acid polymerization.

Although these deacetic acid polycondensation reactions proceed without a catalyst, tin acetate, tetrabutyl titanate, and sodium acetate are used as catalysts when carrying out the polycondensation reactions.

In some cases, it may be preferable to add a metal compound such as potassium acetate, magnesium acetate, antimony oxide, or metallic magnesium.

1. When obtaining the wholly aromatic polyester of the present invention, in addition to the components constituting the above structural units (I) to (IV).

Aromatic oxycarboxylic acids such as m-hydroxybenzoic acid, 2,6-oxynaphthoic acid, chlorhydroquino/
, methylhydroquinone, t-pterno1hydroquinone, phenylhydroquinone, 4.4'-dihydroxydiphenylsulfone, 4.4'-dihydroxydiphenylprotq y S4.4'-dihydroxydiphenylsulfide-4*4'-7hydro? 7 Penzophenone @ 4*4'-dihydroxydiphenyl ether, 2
, 6-hydroxynaphthalene and other aromatic diols, 3
．． Aromatic dicarboxylic acids such as 3'-diphenyldicarboxylic acid, 4.4'-diphenyldicarboxylic acid, and 3.4'-diphenyldicarboxylic acid are further copolymerized in a small proportion that does not impair the purpose of the present invention. I can force it.

All the wholly aromatic polyesters of the present invention have substantially 4
In a single form, the #i above-mentioned unit (I) is added at the end of the polymer chain.
) to QV) may be located at the end of the carboxyl group, in the case of a terminal carboxyl group, use a conventional method to terminate the carboxyl group with a monohydric acid such as methanol, ethanol, isopropropanol, etc. The following are esterified with lower alcohols, or monovalent aromatic hydroxy compounds such as phenol and cresol, and the hydroxy group terminal thereof.

For example, monovalent calcium such as acetic acid, gropionic acid, and benzoic acid? Those esterified with phosphoric acid are also included in the wholly aromatic polyester of the present invention.

The wholly aromatic polyester of the present invention thus obtained exhibits good heat resistance, mechanical properties, and water resistance.

It can be used for ordinary melt molding such as extrusion molding, injection molding, compression molding, blow molding, etc., and can be used for fibers, films, injection molded products, containers, etc. It is possible to process it into eve, etc.

In addition, the wholly aromatic polyester of the present invention includes reinforcing agents such as glass fibers, carbon fibers, metal fibers, and inorganic fibers, fillers, nucleating agents, pigments, antioxidants, stabilizers, lubricating agents, binder agents, Additives such as mold release agents, *flame agents, and other thermoplastic resins can be added to impart desired properties.

Further, by thermally annealing the molded product thus obtained, the mechanical strength can be further increased.

〔Example〕

The present invention will be explained in more detail below using Examples and Comparative Examples.

The performance of fully aromatic polyester was evaluated according to the following method.

Molding: Sumitomo Necool injection molding material Promat 40/
251: Using Sumitomo Heavy Industries (manufactured by (Ten)), fully aromatic polyester was molded under the conditions of cylinder temperature 350°C and mold temperature 30°C, 1/8 inch thickness XI/2 inch width x 5 inch length. test piece and 1/8 inch thick
An impact test piece with a mold notch measuring 21/2×4 width and 21/2×4 width was prepared.

Measurement of physical properties: Using Tensilon UTM-Zoo manufactured by Toyo Goldwin Co., Ltd., this test piece was subjected to strain rate Fl 1 m/
Bending elastic modulus 1 bending strength was measured under the conditions of G and span distance of 50 mm.

Measurement of impact strength: According to ASTM D-256.

Measurement of water absorption: According to ASTM D-570.

Example 1 40 mol% p-h drooxybenzoic acid units, 3.3'-
30 dimethyl-4,4'-dihydroxydiphenyl units
A wholly aromatic polyester containing 30 mol% of terephthalic acid units was synthesized as follows. 500TPL
p-acetoxybenzoic acid 72.9 (0,4
mol), 3.3'-dimethyl-4,4'-diacetoxydiphenyl 68.5 N (0.23 mol), 4.4'
- 18.9 N (0.07 mol) of diacetoxydiphenyl and 49.81 (0.3 mol) of terephthalic acid were charged and reacted at 275°C for 1 hour with stirring, and acetic acid was distilled out for 1 and then 2 hours. The temperature was raised to 350°C, and then 35
9. React for 1 hour at 0°C and 0.5y+zHg. A test piece was made by injection molding the obtained polyester, and the heat distortion temperature was 280°C.

Nine, when we measured the bending strength, bending elastic modulus, and Izot impact strength at room temperature using the same test piece, we found that each of them was 2.
00 to 9mm 2.72,000yu Ano, 15 lil 6 and it's nen. Furthermore, when the water absorption rate of this polyester was measured, it showed a low value of 0.01%.

Examples 2 to 5 and Comparative Example 1 The reaction was carried out in the same manner as in Example 1, except that the raw material monomer compositions shown in Table 1 were used.

The physical properties of the obtained wholly aromatic polyester were measured in the same manner as in Example 1. The results are shown in Table 2.

Comparative Example 2 A wholly aromatic polyester comprising 40 mol% of p-hydroxybenzoic acid units, 30 mol% of 4.4'-dihydroxydiphenyl units, and 30 mol% of terephthalic acid units was synthesized as follows. p-acetoxybenzoic acid 7219 (0.4 mol) in a 500 g reactor.

4.4'-Diacetoxydiphenyl 81゜0li (0,
3 mol), terephthalic acid 49.8 II (0.3 mol)
was charged and reacted at 275°C for 1 hour with stirring to distill off acetic acid.

Next, the temperature was raised to 400°C over 2 hours, and the reaction was carried out for 1 hour at 0.5 nHg.

When an attempt was made to injection mold the obtained polyester, the viscosity of the polyester was so high that molding could not be performed.

/ / Example 6 The fully aromatic polyester obtained in Example 3 was tested with a nozzle diameter of 0 using a melt tensile tester manufactured by Toyo Seiki.
．． A cylindrical die with a diameter of 2 m and a nozzle length of 1 fi was used to spin fibers of 28 f neel at a spinning temperature of 380°C. The spun yarn was wound onto a roll using a conventional variable speed motor. After heat-treating the wound yarn at 300°C and 1 kg Hg for 24 hours, the physical properties were measured and the elastic modulus was 501/s.
d1 strength 25 N/d.

The following shows a value of elongation of 4.5%.

〔Effect of the invention〕

The wholly aromatic polyester of the present invention can be subjected to ordinary melt molding such as injection molding, has good heat resistance, and also has excellent mechanical properties, chemical resistance, and water resistance.

Agent Patent Attorney Katsutoshi Takahashi

Claims (1)

[Claims] 1. The following structural units (I) to (IV) are combined into structural units (I)
is 30 to 80 mol% of the total, and the structural unit (II) is 0 of the total
20 mol %, structural unit (III) in a proportion of 1 to 40 mol %, and structural unit (IV) in a proportion of 10 to 40 mol %. ▲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) ▲Mathematical formulas , there are chemical formulas, tables, etc. ▼...(IV) (However, Ar_1 in the formula is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, A
r_2 has ▲mathematical formulas, chemical formulas, tables, etc.▼, ▲mathematical formulas,
Indicates ▼There are chemical formulas, tables, etc. or ▲There are mathematical formulas, chemical formulas, tables, etc.▼. ) 2. Claim 1, wherein the proportion of structural unit (II) is 5 to 15 mol%, and the proportion of structural unit (III) is 5 to 30 mol%.
Fully aromatic polyester as described. 3. Structural unit (I) 35 to 65 mol% of the total, structural unit (II) 5 to 15 mol% of the total, structural unit (III)
5 to 30 mol% of the total and 15 to 30% of the structural unit (IV)
Contains a proportion of 35 mol%, and contains structural unit (II) and (
The wholly aromatic polyester according to claim 1, wherein the sum of the moles of III) and the mole number of the structural unit (IV) are substantially equal. )