JPS6016962B2 - New and useful aromatic polyesters - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a new and useful aromatic polyester and a method for producing the same, and more particularly to an oxyphenoxybenzoyl polyester obtained from hydroxyphenoxybenzoic acid or a derivative thereof.

Polyesters containing oxybenzoyl structural units as repeating units have been well known for their excellent high-temperature properties and heat resistance.

However, because this polyester has a very high melting point, it tends to thermally decompose more easily than it melts.
Injection molding has the disadvantage that it cannot be molded by commonly used molding methods such as extrusion molding. The production of such oxybenzoyl polyester was conducted in 1986-6.
It is described in Publication No. 796, etc. It is an object of the present invention to provide a new and useful heat-resistant polyester that can be molded by conventional molding methods.

That is, the present invention provides a repeating compound represented by the general formula (1) (wherein and -○-, which does not constitute an ether bond, is bonded to the benzene ring at the para or meta position with respect to the ether bond) The present invention relates to a novel and useful aromatic polyester having a melting point of 25,000 or more.

As a further preferred embodiment of the above novel polyester, it has a repeating unit represented by the general formula (0) and has a melting point of 250 to 4.
There is a new aromatic polyester that is 5000.

Such a new aromatic polyester has a molecular weight of 250 to 600
Since it has a melting point at It is.

If it is less than 25,000, the melting point becomes too low, which is not preferable.

As such a molding material, the above-mentioned novel and useful aromatic polyester preferably has a melting point of 300 to 450q○. The aromatic polyester according to the present invention preferably has an average molecular weight of 3,000 or more or a degree of polymerization of 5 or more.

The aromatic polyester of the present invention has the general formula (m) (where R is selected from the group consisting of hydrogen, an acetyl group, a propionyl group, and a penzoyl group, and R
is selected from the group consisting of hydrogen, phenyl, a phenyl group in which one or more of them is substituted with a halogen or a lower alkyl group, and a lower alkyl group having 1 to 5 carbon atoms, and RO- and -COOR are It can be produced by condensing at least one compound among the compounds represented by (bonded to a benzene ring at the para- or meta-position with respect to the ether bond) at room temperature or higher.

As a preferable embodiment of the above general formula (m), the general formula (
W) (wherein R and R' are as defined in general formula (m)).

A general method for the production of the polyesters of the present invention is to use the monolithic (m) or (W) method described above under high temperature and liquid conditions.
) consists of condensing one or more monomers represented by. This condensation reaction can be carried out in the molten state in the absence of a solvent, but in order to more easily control the condensation reaction, it is advantageous to carry out it in a suitable high-boiling solvent. When using a solvent in the reaction,
Since the maximum temperature of the condensation reaction depends on the boiling point of the solvent used, it is desirable to use a high boiling point solvent.

Specific examples of high boiling point solvents suitable for carrying out the condensation reaction include Yuichi phenyls, polychlorinated polyphenyls such as polychlorinated biphenyls, hydrogenated triphenyls, ethyldiphenyl, jetyldiphenyl, triethyldiphenyl, alkylated diphenyls such as trimethyldiphenyl;
Examples include alkylated naphthalenes such as methylnaphthalene and ethylnaphthalene, diphenyl ether, diphenyl, diphenyl sulfone, benzophenone, and sulfolane.

Although the condensation reaction can sometimes be carried out easily without the use of a catalyst, it is preferable to carry out the reaction in the presence of a catalytic amount of a suitable condensation catalyst.

Many known transesterification catalysts are useful for this, such as tetra-n-butylorthotitanate, sodium alcoholate, lithium hydroxide, para-toluene sulfonic acid, cobalt acetate, zinc acetate, magnesium, titanium sulfate, etc. can be given. The amount of catalyst used is preferably 0.001 to 1.0 mol% based on the raw material. Specific examples of the compounds of the monopronged formula (W), (V) or (W) include p-(p-hydroxyphenoxy)benzoic acid,
p-(p-acetoxyphenoxy)benzoic acid, p-(p
-hydroxyphenoxy) phenyl benzoate, p-(p
-acetoxyphenoxy) phenyl benzoate, p-(p
-acetoxyphenoxy)isobutyl benzoate, p-(
p-penzoyloxyphenoxy) phenyl benzoate,
Ethyl p-(p-acetoxyphenoxy)benzoate, p
-(p-acetoxyphenoxy)benzoic acid m-chlorophenyl, p-(m-acetoxyphenoxy)benzoic acid,
p-(m-acetoxyphenoxy)phenyl benzoate,
phenyl m-(p-acetoxyphenoxy)benzoate,
Examples include phenyl m-(m-acetoxyphenoxy)benzoate.

The temperature at which the condensation reaction is carried out is above room temperature, as long as it is sufficiently high for the condensation to occur, but too low a temperature is not advantageous since the rate of condensation increases with increasing temperature.

Usually 150qC~450℃, preferably 25000~4
Perform within the range of 0000. The present invention will be further explained in detail by the examples described below, but the following examples are not intended to limit the present invention. Example 1 P-(p-acetoxyphenoxy)benzoic acid 54. A mixture of 300 g of a trialkylbiphenyl solvent (Thermes 800: Nippon Steel Chemical Industry Co., Ltd. trade name) and 0.01 g of tetra-n-butyl orthotitanate was heated at 240°C for 8 hours, and then the acetic acid produced was distilled off. , and heated at 300-3200C for 8 hours.

After cooling, the trialkylbiphenyl solvent is removed by washing with acetone to obtain a polyester powder. Dry under reduced pressure at 6000 °C.

Yield: 4 males. The infrared absorption spectrum of the obtained product is shown in FIG. As is clear from FIG. 1, absorption of the carbonyl group of the ester bond is seen at the 1760 arc-1.
The raw material p-(p-acetoxyphenoxy)benzoic acid has two carbonyl groups, a carboxyl group and an acetoxy group, and each carbonyl group has 1710 Hada-1
and has absorption in 1760 skin-1. As is clear from Figure 1, there is almost no absorption in 1710 skin-1.
It can be seen that the carboxyl groups of the raw material are consumed.
As a result, Figure 1 supports the structure of paraoxyphenynoxybenzoyl polyester, and when this polyester is hydrolyzed with a strong alkaline aqueous solution, p-(p-hydroxyphenoxy)benzoic acid is obtained. It was done. From these, it is clear that the obtained product is an aromatic polyester having repeating units of.

This product melted at 39,000 ℃ and hardly dissolved in cresol, ethane tetrachloride, and chlorobenzene.

The elemental analysis values were as follows.

Actual value C: 73.12%, H: 3.56%, ○ (remainder): 23.32% Calculated value C: 73.58%, H: 3.
79%, ○: 22.63%Example 2 p-(p-acetoxyphenoxy)benzoic acid 54% while being constantly illuminated under a nitrogen gas atmosphere. A mixture of 300 g of a trialkylbiphenyl solvent (Therm S800: Nippon Steel Chemical Industry Co., Ltd. trade name) was heated at 240°C for 8 hours, and then heated at 300 to 320°C while removing the acetic acid produced.
It was heated for 8 hours.

After cooling, the trialkyl biphenyl solvent was removed by washing with acetone to obtain a polyester powder. Dry under reduced pressure at 60 qo.

The yield was 41 g, and the product obtained melted at 400°C. The infrared absorption spectrum of the obtained product showed a spectrum similar to that of the product of Example 1. When this product was hydrolyzed in the same manner as in Example 1, p-(p-
Hydroxyphenoxy)benzoic acid was obtained. Actual elemental analysis value C: 73.15% H: 3.53%○ (residue)
: 23.32% calculated value C: 73.58% H: 3.7
9% 0:22.51% Example 3 In Example 1, trialkylbiphenyl solvent 30
The desired polyester was obtained using the same composition and conditions as in Example 1, except that 300 g of diphenyl sulfone was used instead of 0 g.

The yield was 38 g and the resulting product melted at 310 qo. The infrared absorption spectrum of this product was similar to that of the product of Example 1, and when hydrolyzed in the same manner as in Example 1, p-(p-hydroxyphenoxy)benzoic acid was obtained. Actual elemental analysis value C: 73.23% H: 3.51%○ (residue)
:23.26% calculated value C:73.58% H:3.7
9% ○: 22.51% Example 4 Same composition and conditions as Example 1 except that 0.01 g of cobalt acetate was used instead of 0.01 g of tetra-n-butyl orthotitanate. The desired polyester was obtained.

The yield was 39 g, and the product obtained melted at 340°C. The infrared absorption spectrum of this product is similar to that of the product of Example 1, and when hydrolyzed by the method of Example 1, p
-(p-hydroxyphenoxy)benzoic acid was obtained.
Actual elemental analysis value C: 73.09% H: 3.59%○ (residue)
: 23.32% calculated value C: 73.58% H: 3.7
9% ○: 22.51% Example 5 In Example 1, trialkylbiphenyl solvent 30
The target polyester was obtained using the same composition and conditions as in Example 1, except that 30 g of a hydrogenated triphenyl solvent (Thermes 900: trade name of Nippon Steel Corporation) was used instead of 0 g.

The yield was 4,000 and the product obtained melted at 40,000. This product showed an infrared absorption spectrum similar to that of Example 1, and when hydrolyzed in the same manner as in Example 1, p-
(p-hydroxyphenoxy)benzoic acid was obtained. Actual elemental analysis values C: 73.27% H: 3.56%○ (residue)
: 23.17% calculated value C: 73.58% H: 3.7
9%0:22.51%Example 6 46g of p-(p-hydroxyphenoxy)benzoic acid, 3 phenyl acetate while maintaining constant candlelight under nitrogen gas atmosphere.
A mixture of 300 g of trialkylpiphenyl solvent and 0.01 g of tetra-n-butyl orthotitanate was added to 19
It was heated for 1 hour at 5qo.

After cooling, the trialkylbiphenyl solvent was removed by washing with acetone to obtain a polymer powder. It was dried at 60°C and the yield was 38g.

The obtained product showed a similar infrared absorption spectrum to the product of Example 1 and melted at 380°C. This product was hydrolyzed in the same manner as in Example 1 to yield p-(p-hydroxyphenoxy)benzoic acid. Actual elemental analysis value C: 73.10% H: 3.63%○ (residue)
: 23.27% calculated value C: 73.58% H: 3.7
9% 0:22.51% Example 7 46 g of p-(p-penzoyloxyphenoxy)benzoic acid, 300 g of trialkylbiphenyl solvent, and tetofu-n-butyl were added under a nitrogen gas atmosphere while keeping the temperature constant. A mixture of 0.01 g of orthotitanate was heated at 240 qo for 8 hours, then at 300-320 oo for 8 hours.

After cooling, the trialkylbiphenyl solvent was removed by washing with acetone, and the target polyester powder was obtained by drying under reduced pressure at 6,000 °C. Yield is 20
g, and the obtained product showed an infrared absorption spectrum similar to that of the polymer of Example 1. Further, when hydrolyzed in the same manner as in Example 1, p-(p-hydroxyphenoxy)benzoic acid was obtained. Actual elemental analysis value C: 73.44% H: 3.61%○ (residue)
: 22.95% calculated value C: 73.58% H: 3.7
9%○:22.51%Example 8 Phenyl p-(p-hydroxyphenoxy)benzoate61. 220 to 2400 of a mixture of 0.01 g of tetra-n-butylorthotitanate, 30 pieces of trialkyl biphenyl solvent (Thermes 800: Nippon Steel Chemical Industry ■ trade name)
The mixture was heated at 300 to 320 pm for 8 hours, and then heated at 300 to 320 pm for 8 hours while distilling off the produced phenol.

After cooling, the trialkylbiphenyl solvent was removed by washing with acetone, and the product was dried under reduced pressure at 6000° C. to obtain the desired polyester powder. The yield was 39g,
The obtained product showed an infrared absorption spectrum similar to that of the polymer of Example 1. This product was hydrolyzed by the same method as in Example 1 to obtain p-(p-hydroxyphenoxy)benzoic acid. Actual elemental analysis value C: 73.38% H: 3.59%○ (residue)
: 23.03% calculated value C: 73.58% H: 3.7
9% ○: 22.51% Example 9 While constantly moving under a nitrogen gas atmosphere, 69.6 g of phenyl p-(p-acetoxyphenoxy)benzoate, trialkylbiphenyl solvent (Thermes 800: Nippon Steel) Chemical industry (trade name) 300g, tetra-n-butylorthotitanate 0.01g mixture at 22,000~
The mixture is heated at 24,000 for 8 hours, and then heated to 300 to 32,000 while removing the phenyl acetate produced.

After cooling, the trialkylbiphenyl solvent was removed by washing with acetone, and the mixture was dried under reduced pressure at 60° C. to obtain the desired polyester powder. The yield was 41 g, and the resulting product showed an infrared absorption spectrum similar to that of the polymer of Example 1. Hydrolysis was carried out in the same manner as in Example 1 to obtain p-(p-hydroxyphenoxy)benzoic acid.
Actual elemental analysis values C: 73.36% H: 3.57%
○(Remaining portion): 23.07% Calculated value C: 73.58%
H: 3.79% ○: 22.51% Example 10 p-(m-acetoxyphenoxy)benzoic acid 54. A mixture of 300 g of hydrogenated triphenyl (Therm S900) was heated to 2400 g.
0 for 8 hours, then 30 hours while distilling off the acetic acid produced.
Heated at 0-32000 for 8 hours.

After cooling, hydrogenated triphenyl is removed by washing with acetone to obtain a polyester powder.
Dry under reduced pressure at 6000 °C.

The yield was 38 g, and the infrared absorption spectrum of the obtained product supported the structure of oxyphenoxybenzoyl polyester. The resulting polymer melted at 310-32,000. This product was hydrolyzed in the same manner as in Example 1 to obtain p-(m-hydroxyphenoxy)benzoic acid. Actual elemental analysis value C: 73.21% H: 3.51%○ (residue)
: 23.28% calculated value C: 73.58% H: 3.7
9%○: 22.51%

[Brief explanation of the drawing]

FIG. 1 shows the infrared absorption spectrum of the polyester according to the present invention obtained in Example 1. Tsutomu diagram

Claims (1)

[Claims] 1 General formula ▲ Numerical formula, chemical formula, table, etc. A novel and useful aromatic polyester having a repeating unit represented by 2. A novel and useful aromatic polyester according to claim 1, in which the repeating unit is represented by the formula ▲A mathematical formula, a chemical formula, a table, etc.▼. 3 Claim 1 having a melting point of 300 to 450°C
A novel and useful aromatic polyester according to item 1 or 2.