JPS626577B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a new and useful aromatic polyester, and more particularly to an oxyphenoxybenzoyl copolyester obtained using hydroxyphenoxybenzoic acid or a derivative thereof as a raw material. Conventionally, polyesters having oxybenzoyl structural units as repeating units are well known for having excellent high-temperature properties and heat resistance. However, since this polyester has a very high melting point, it tends to be more easily thermally decomposed than melted, and has the disadvantage that it cannot be molded by commonly used molding methods such as injection molding or extrusion molding. The production of such oxybenzoyl polyesters is described in Japanese Patent Publication No. 46-6796. 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 general formulas (), (),
() and () are

【formula】

【formula】

【formula】

It has a repeating unit represented by the formula and has a melting temperature of
Aromatic polyester having a temperature of 220 to 500°C (however, in the formula, R ₁ and R ₂ are hydrogen, a methyl group, or an ethyl group, and may be the same or different from each other, and the general formula () or ( ) is bonded to the oxy group of the unit of general formula (), () or (), and the carbonyl group of the unit of general formula (), () or () is bonded to the oxy group of the unit of general formula (), () or ().
The oxy group of the unit is bonded to the carbonyl group of the unit of the general formula () or (), and p, q, r and s are the repeats represented by the general formula (), (), () and (), respectively. Assuming the number contained in the unit molecule, q=r+s, and p:q=
1:9 to 9:1, r:s=0:100 to 100:0, and in the general formula (),

[Formula] and -O-, which does not constitute an ether bond, is bonded to the benzene ring at the para- or meta-position relative to the ether bond, and in the general formula ()

[Formula] and -O- in the general formula () are mutually bonded to the benzene ring at the para or meta position. Such a novel aromatic polyester is 220~
It has a melting temperature of 500°C, can be molded by commonly used injection molding or extrusion molding methods without decomposition, and is useful as heat-resistant engineering plastics or heat-resistant fibers. The aromatic polyester according to the present invention preferably has an average molecular weight of 3000 or more. The aromatic polyester according to the present invention has the general formula (A) Compounds represented by and B general formula () Aromatic carbonyl compound represented by and C general formula () and/or general formula () It can be produced by condensing an aromatic dioxy compound represented by at room temperature or higher. However, in the general formula (), RaO− and COOR′a
is bonded to the benzene ring at the para or meta position relative to the ether bond, and the two in general formula () are

Rc ₁ O− and R′c ₁ O − in [Formula] and general formula () are each bonded to the benzene ring at the para position or meta position. Ra of general formula (), Rc ₁ and R′c ₁ of general formula (), and Rc ₂ and R′c ₂ of general formula ()
is selected from the group consisting of hydrogen, acetylpropionyl and benzoyl, and has the general formula ()
R'a and Rb and R'b in the general formula () are selected from the group consisting of hydrogen, a phenyl group, a substituted phenyl group, and a lower alkyl group having 1 to 5 carbon atoms. In the general formula (), R ₁ and R ₂ are hydrogen, a methyl group, or an ethyl group, and may be the same or different. The general method for producing the polyesters of the invention consists of condensing monomers represented by the above general formulas (), (), () and () under high temperature and liquid conditions. Although this condensation reaction can be carried out in the molten state in the absence of a solvent, it is advantageous to carry out it in a suitable high-boiling solvent in order to more easily control the condensation reaction. When a solvent is used in the reaction, it is desirable to use a high boiling point solvent since the maximum temperature of the condensation reaction depends on the boiling point of the solvent used. Specific examples of high boiling point solvents suitable for carrying out the condensation reaction include terphenyls, polychlorinated polyphenyls such as polychlorinated phenyl, hydrogenated triphenyls, ethyldiphenyl, diethyldiphenyl, triethyldiphenyl, trimethyldiphenyl, etc. Examples include alkylated diphenyls, 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-butyl orthotitanate, sodium alcoholate, lithium hydroxide, paratol sulfonic acid, cobalt acetate, zinc acetate, magnesium, titanium sulfate, etc. can give. The amount of catalyst used is preferably 0.001 to 1.0 mol% based on the raw material. Specific examples of the compound of the above general formula () are:
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-benzoyloxyphenoxy) ) Phenyl benzoate, p-(p-acetoxyphenoxy)ethyl benzoate, p-(p-
Chlorophenyl (acetoxyphenoxy)benzoate, p-(m-acetoxyphenoxy)benzoic acid, p-(m-acetoxyphenoxy)phenyl benzoate, phenyl m-(p-acetoxyphenoxy)benzoate , phenyl m-(m-acetoxyphenoxy)benzoate, and the like. Specific examples of the compound of the above general formula () are:
Terephthalic acid, isophthalic acid, diphenyl terephthalate, diphenyl isophthalate, dimethyl terephthalate, dimethyl isophthalate, di(m-chlorophenyl) terephthalate, isophthalic acid (m-
chlorphenyl), etc. Specific examples of the compound of the general formula () include hydroquinone diacetate, resorcin diacetate, hydroquinone dibenzoate, resorcin dibenzoate, hydroquinone, resorcin, hydroquinone diproonate, resorcin dipropionate, and the like. Specific examples of the compound of the above general formula () are:
Examples include diacetate of bisphenol A, diacetate of bisphenol A, dibenzoate of bisphenol A, bisphenol A, dihydroxyphenylmethane, diacetoxydiphenylmethane, and dibenzoxyphenylmethane. General formula (), (), (), in the present invention
The compounding ratio of the compound () can be selected from various ratios depending on the desired properties of the produced polyester, but usually the number of moles of the compound (), (), (), () is determined by p, q, r. , s, then q=r+s
and p/q=1/9 to 9/1, r/s=0/
Select from 100 to 100/0. 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. Normally 150℃~450
The temperature is preferably 250°C to 400°C. 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 While constantly stirring under a nitrogen gas atmosphere, p-
(p-acetoxyphenoxy)benzoic acid 54.4g,
A mixture of 33 g of terephthalic acid, 62 g of bisphenol A diacetate, and 600 c.c. of a trialkyldiphenyl solvent (Therm-S 800: trade name of Nippon Steel Chemical Industry Co., Ltd.) is then produced at 260 to 280°C for 7 hours. The mixture was heated at 320 to 330°C for 7 hours while distilling off acetic acid. After cooling, the trialkyl biphenyl solvent is removed by washing with acetone to obtain a polyester powder. Dry under reduced pressure at 60℃. Yield: 82g. The obtained polymer is dissolved in chloroform, chlorobenzene, N-methylpyrrolidone, cresol, etc. The reduced viscosity was 0.47 at 30°C in chloroform. The melting temperature of the polymer is
It was 250℃. When the obtained polyester was hydrolyzed with a strong alkaline aqueous solution, p-
(p-hydroxyphenoxy)benzoic acid, terephthalic acid, and bisphenol A were obtained. The infrared absorption spectrum of this polyester is shown in FIG. Example 2 The same compound and amount were used as in Example 1, and the same operation was carried out, except that isophthalic acid was used instead of terephthalic acid. The melting temperature is
The reduced viscosity of the obtained polymer was 0.42 at 30°C in chloroform. When the obtained polyester was hydrolyzed with a strong alkaline aqueous solution, p-(p-hydroxyphenoxy)benzoic acid, isophthalic acid, and bisphenol A were obtained. Example 3 While constantly stirring under a nitrogen gas atmosphere, p-
(p-acetoxyphenoxy)benzoic acid 54.4g,
33g of isophthalic acid, hydroquinone diacetate
A mixture of 39 g, Therm-S 800 (trade name of Nippon Steel Chemical Industry Co., Ltd.) 600c.c., and 0.02 g of tetra(n-butyl orthotitanate) was heated at 260 to 280°C for 8 hours, then at 310 to 330°C for 8 hours. heated for an hour. After cooling, THERM-S 800 is removed by washing with acetone to obtain a polyester powder. Dry under reduced pressure at 60℃. The yield was 6.9 g, and the obtained polymer was soluble in N-methylpyrrolidone, cresol, etc., but not in chloroform, chlorobenzene, etc. Melting temperature is 270-280℃. When the obtained polyester was hydrolyzed with a strong alkaline aqueous solution, p-(p-hydroxyphenoxy)benzoic acid, isophthalic acid, and hydroquinone were obtained. The infrared absorption spectrum of this polyester is shown in FIG. Example 4 In Example 3, orthotitanate tetra(n
The composition and operation were the same as in Example 3, except that -butyl) was not used. Melting temperature is 230~240℃
It was hot. When the obtained polyester was hydrolyzed with a strong alkaline aqueous solution, p-(p-hydroxyphenoxy)benzoic acid, isophthalic acid,
Hydroquinone was obtained. The infrared absorption spectrum of this polyester was similar to that shown in FIG. Example 5 The same procedure as in Example 1 was carried out using a compound having the following composition. p-(p-acetoxyphenoxy)benzoic acid
54.4g Isophthalic acid 33g Resorcin diacetate 39g Hydrogenated triphenyl (Therm-S 900) 600c.c. Yield: 6.4g. The melting temperature of the obtained polymer is 220
It was ~230℃. When the obtained polyester was hydrolyzed with a strong alkaline aqueous solution, p
-(p-hydroxyphenoxy)benzoic acid, isophthalic acid, and resorcinol were obtained. The infrared absorption spectrum of this polyester is shown in FIG. Example 6 The same procedure as in Example 1 was carried out using a compound having the following composition. p-(p-acetoxyphenoxy)benzoic acid
54.4g Terephthalic acid 6.6g Resorcin diacetate 7.8g Tetra(n-butyl) orthotitanate 0.02g Therm-S 800 350c.c. Yield: 52g. The melting temperature of the polymer was 340-350°C. When the obtained polyester was hydrolyzed with a strong alkaline aqueous solution, p-(p-hydroxyphenoxy)benzoic acid, terephthalic acid, and resorcinol were obtained. Table 1 shows the elemental analysis results of the polyesters obtained in Examples 1 to 6.

【table】 [Brief explanation of the drawing]

FIG. 1, FIG. 2, and FIG. 3 show infrared absorption spectra of the polyesters obtained in Example 1, Example 3, and Example 5, respectively.

Claims (1)

[Claims] 1 The general formulas (), (), () and () have a repeating unit represented by [Formula] [Formula] [Formula] [Formula] and the melting temperature is
Aromatic polyester having a temperature of 220 to 500°C (however, in the formula, R ₁ and R ₂ are hydrogen, a methyl group, or an ethyl group, and may be the same or different from each other, and the general formula () or ( ) is bonded to the oxy group of the unit of general formula (), () or (), and the carbonyl group of the unit of general formula (), () or () is bonded to the oxy group of the unit of general formula (), () or ().
The oxy group of the unit is bonded to the carbonyl group of the unit of the general formula () or (), and p, q, r and s are the repeats represented by the general formula (), (), () and (), respectively. Assuming the number contained in the unit molecule, q=r+s, and p:q=
1:9 to 9:1, r:s=0:100 to 100:0, and in the general formula (), [formula] and -O- which does not constitute an ether bond are relative to the ether bond. [Formula] of the general formula () and -O- of the general formula () are bonded to the benzene ring at the para or meta position). 2 The repeating unit represented by the general formula () is The aromatic polyester according to claim 1. 3 Claim 1 or 2 in which s is 0
Aromatic polyester as described in section. 4 Claim 1 or 2 in which r is 0
Aromatic polyester as described in section. 5. The aromatic polyester according to claim 1, 2, 3, or 4, wherein in the general formula (), R ₁ and R ₂ are methyl groups.