JPS63223038A - Chlorine-containing copolymerized polyester having high fluidity - Google Patents

Abstract

PURPOSE:To obtain the titled polyester composed of plural structural units, moldable by melt-molding and suitable for the molding of thin-walled parts and precision parts, etc., by copolymerizing a specific amount of a hydroxycarboxylic acid. CONSTITUTION:The objective polyester containing 30-90mol.% of a structural unit of formula I (X is bivalent benzene ring, etc.), formula II (Y is bivalent benzene ring, etc.) and formula III (Y is bivalent benzene ring, etc.) at a ratio [II/(II+III)] of 10-100mol.% and having a melt viscosity of preferably 100-1,500 poise can be produced by mixing (A) an aromatic dicarboxylic acid such as 1,2-bis(2-chlorophenoxy)ethane-4,4'-dicarboxylic acid with e.g. an acylated product of (B) p-hydroxybenzoic acid and/or 6-hydroxy-2-naphthoic acid and (C) a dioxy compound (e.g. hydroquinone) and subjecting the mixture to deacetylating polycondensation reaction.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a chlorine-containing copolymerized polyester that can be melt-molded at 400° C. or lower and can give molded articles with excellent fluidity.

<Conventional technology> In recent years, the demand for higher performance plastics has been increasing, and many polymers with various new performances have been developed and put on the market. Optically anisotropic liquid crystal polymers have attracted attention because of their excellent mechanical properties.

Fully aromatic polyester is widely known as this liquid crystal polymer.

However, the melting point of the homopolymer of p-hydroxybenzoic acid is too high to be melt-molded, and a method of lowering the melting point by copolymerizing various components with p-hydroxybenzoic acid has been investigated. A method of copolymerizing a dioxy compound such as -dihydroxybiphenyl or hydroquinone with an aromatic dicarboxylic acid such as terephthalic acid or isophthalic acid is described in Japanese Patent Publication No. 47-4787.

On the other hand, various aromatic dioxy compounds and 1,2-bis(2
-Chlorphenoxy)ethane-4,4-dicarboxylic acid-containing polyester is disclosed in JP-A-59-413.
No. 31 and Japanese Patent Application Laid-Open No. 60-188420.

In addition, polyester from ethylene glycol, 1,2-bis(2-chromephenoxy)ethane-4,4°-dicarboxylic acid, and oxycarboxylic acid is disclosed in Japanese Patent Application Laid-Open No. 60-4529.
JP-A-60-67530.

<Problems to be Solved by the Invention> However, the polyester described in the above-mentioned Japanese Patent Publication No. 47-4787 has poor fluidity, and it is impossible to obtain a highly polymerized polymer only by melt polymerization. It was found that when using , the melting point was high and the fluidity was poor.

On the other hand, the above-mentioned JP-A-59-41331, JP-A-60
It has been found that when hydroquinone is used as the dioxy compound in the polymer described in Japanese Patent No. 188420, a polymer with good fluidity cannot be obtained.

Also, Japanese Patent Application Laid-Open No. 80-4529, 60-67530
Since the polymers described in the above publication use ethylene glycol as a dioxy compound, it was found that many of them had glass transition temperatures of 100''C and thus had insufficient heat resistance.

An object of the present invention is to improve the fluidity of a polyester composed of hydroquinone and 1,2-bis(2-chlorophenoxy)ethane-4,4-dicarboxylic acid.

Means for Solving the Problems〉 As a result of intensive study by the present inventors to solve the above problems,
The inventors have discovered that a chlorine-containing copolymerized polyester with good fluidity can be obtained by copolymerizing a specific amount of hydroxybenzoic acid, and have thus completed the present invention.

That is, the present invention consists of the following structural units (I) to (II), in which the structural unit (I) is 30 to 90 mol% of the total, and the structural unit (I)/[(II) + (III)] is 110 to 10
The present invention provides a chlorine-containing copolymerized polyester having a molecular weight of 0 mol and good fluidity.

÷o-x-co+ ・・・・・・(I)÷
o-y-o2cmz-co+...(I[I)(
However, in the formula, X represents one or more groups selected from + or -) O-, Y represents one or more groups selected from +, >, and Z represents →嘗ト, 1: ", -C]-1 or a group.

In the chlorine-containing copolymerized polyester of the present invention, the above tf4
The structural unit (billion units) indicates a structural unit of a polyester produced from p-hydroxybenzoic acid and/or 6-hydroxy-2-naphthoic acid.

The above structural unit (II) is hydroquinone, chlorohydroquinone, methylhydroquinone, t-butylhydroquinone or 4,4'-dihydroxybiphenyl, preferably hydroquinone, t-butylhydroquinone, 4,4'-dihydroxybiphenyl,
, 4'-dihydroxybiphenyl, particularly preferably hydroquinone, and 1,2-bis(2-
The structural unit of polyester produced from chlorophenoxy)ethane-4,4°-dicarboxylic acid is shown.

Further, the above structural unit (III) may be combined with one or more of the above dihydroxy compounds such as terephthalic acid, isophthalic acid, 2.6-
Structural units of polyesters derived from one or more of dicarboxynaphthalene, 1,2-bis(phenoxy>ethane-4,4'-dicarboxylic acid, preferably terephthalic acid, isophthalic acid, particularly preferably terephthalic acid) shows.

The above structural unit (I) is 30 to 90 mol% of the total,
Preferably 40-80 mol%, most preferably 50-7
It is 5 mol%. If it exceeds 90 mol % or is less than 30 mol %, the melting point of the chlorine-containing copolyester increases and fluidity decreases, making melt polymerization and melt molding sometimes difficult, making it impractical.

The chlorine-containing copolymerized polyester of the present invention can be produced according to conventional polycondensation methods for polyesters, and there are no particular restrictions on the production method, but typical production methods include the following (a).
~ (d) Laws are mentioned.

(a) Acylated products of oxycarboxylic acids such as p-acetoxybenzoic acid, diacylated products of dioxy compounds such as hydroquinone diacetate, and 1,2-bis(2-chlorophenoxy)ethane-4,4°-dicarboxylic acids, etc. A method for producing aromatic dicarboxylic acids by deacetic acid polycondensation reaction.

(b) Oxycarboxylic acids such as p-oxybenzoic acid, dioxy compounds such as hydroquinone, and 1,2-bis(2
-Chlorphenoxy)ethane-4,4'-dicarboxylic acid and other aromatic dicarboxylic acids and acetic anhydride by deacetic acid polycondensation reaction.

(c) Phenyl ester of oxycarboxylic acid such as Kanooxybenzoic acid and dioxy compound such as hydroquinone and 1,2-bis(2-chlorophenoxy)ethane-4
, 4°-dicarboxylic acid and other aromatic dicarboxylic acids by dephenolization polycondensation.

(d) Oxycarboxylic acid such as Kanooxybenzoic acid and 1,2-bis(2-chlorophenoxy)ethane-4,4
゛-A method in which an aromatic dicarboxylic acid such as a dicarboxylic acid is reacted with a predetermined amount of diphenyl carbonate to form a diphenyl ester, and then a dioxy compound such as hydroquinone is added to perform dephenol polycondensation.

Typical catalysts used in polycondensation reactions include metal compounds such as stannous acetate, tetrabutyl titanate, potassium acetate, antimony trioxide, magnesium, and sodium acetate, and are particularly effective in dephenol polycondensation. be.

Some of the chlorine-containing copolymerized polyesters of the present invention can be measured for their logarithmic viscosity in pentafluorophenol;
The value measured at °C is preferably 0.5 or more, especially 1.0
~15.0 is preferred.

Further, the melt viscosity of the chlorine-containing copolyester of the present invention is preferably 100 to 15,000 poise, particularly 200 to 15,000 poise.
5,000 voids is more preferred.

In addition, this melt viscosity is (liquid crystal starting temperature +40 to 60°C)
The molecular weight of these chlorine-containing copolymerized polyesters is preferably 1,000 to 200,000, more preferably 3,000, as measured by a Koka type flow tester at a slip rate of 2,000 to 4,000 (1/sec). ~100,000.

In the methods (a) and (b) above, this molecular weight can be determined by quantifying the amount of acetyl groups using the infrared absorption spectrum of the hot-pressed film, or by measuring the amount of acetic acid produced after hydrolyzing the polymer by gas chromatography. It can be determined by quantitative determination using a graph. Furthermore, since these polymers dissolve in pentafluorophenol, they can be measured by light scattering.

In addition, when polycondensing the chlorine-containing copolymerized polyester of the present invention, in addition to the components constituting the above <I>, (II) and (III), 4,4'-diphenyldicarboxylic acid, 3
, 3°-diphenyldicarboxylic acid, 3.4′-diphenyldicarboxylic acid, 2,2′-diphenyldicarboxylic acid, aromatic dicarboxylic acids such as 4.4-dicarboxydiphenyl ether, and alicyclic dicarboxylic acids such as hexahydroterephthalic acid. acids, resorcinol, aromatic dihydroxy compounds such as 2.6-hydroxynaphthalene and 2.7-hydroxynaphthalene, aromatic oxycarboxylic acids such as m-oxybenzoic acid, aminophenol, p-aminobenzoic acid, etc. Further copolymerization may be carried out within a small proportion that does not impair the purpose of the present invention.

The chlorine-containing copolymerized polyester of the present invention thus obtained has a low melting point of 400°C or less, and can be subjected to ordinary melt molding such as extrusion molding, injection molding, compression molding, and blow molding, and can be used to produce fibers, films, and three-dimensional molded products. It can be processed into containers, hoses, etc.

In addition, for the chlorine-containing copolymerized polyester of the present invention, reinforcing agents such as glass fiber, carbon fiber, and asbestos, fillers,
Additives such as nucleating agents, pigments, antioxidants, stabilizers, plasticizers, lubricants, mold release agents, and flame retardants, as well as other thermoplastics, can be added to impart desired properties.

Note that the strength of the obtained molded product can be increased by heat treatment, and the elastic modulus can also be increased in many cases.

This heat treatment can be carried out, for example, by heat treating the molded article in an inert gas atmosphere such as nitrogen, argon, helium or water vapor or in an oxygen-containing gas atmosphere such as air or under reduced pressure at a temperature below the melting point of the polymer. . This heat treatment may or may not be under tension, and can be carried out for several tens of minutes to several days.

The molded article obtained from the chlorine-containing copolyester of the present invention has good optical anisotropy and fluidity due to its parallel molecular alignment, and has extremely excellent mechanical properties and heat resistance.

<Example> The present invention will be further explained below with reference to Examples.

Example 1 60.3 p-acetoxybenzoic acid (1) in a test tube for polymerization
5g (33,5X10'mo'/shi), Hytroki/
'j Schiff'c = Tate (II) 32. '04 g
(i6.5X10-2 mol) and 1.2-bis(2-
Chlorphenoxy)ethane-4,4'-dicarbonate H(
I [[) 61.25 g (16.5 x 10-2 mol) was charged so that the ratio of (I)/[(I) + (II)] = 67 mol%, and acetic acid depolymerization was performed under the following conditions. . First, when the nitrogen atmosphere was completed, almost the stoichiometric amount of #acid was distilled out, and a brown polymer was obtained.

The theoretical structural formula of this polymer is as follows, and the elemental analysis results showed good agreement with the theoretical values as shown in Table 1. The logarithmic viscosity of this polymer is defined as pentafluorophenol (0,
1r/dρ concentration, 60℃) 3.2df
It was J/f.

m/n=67/33 Table 1 However, oxygen content (%) is (100%-0%-8%-01%
).

When this polyester was placed on a sample stage of a polarizing microscope and the temperature was raised to check the optical anisotropy, it showed good optical anisotropy at 259° C. or higher. The melt viscosity of this polymer was 2300 at 310°C and a sliding speed of 3000 (1/sec).
Voids and fluidity were extremely good.

Further, when the thermal properties were measured using a differential scanning calorimeter (Perkin-Elmer type), the glass transition temperature was 142°C, and the melting point was 281°C.

Comparative Example 1 Polymerization was carried out in the same manner as in Example 1 using terephthalic acid instead of 1,2-bis(2-chlorophenoxy)ethane-4,4'-dicarboxylic acid in Example 1, but solidification occurred during polymerization. However, only a low polymerization degree polymer with poor fluidity was obtained. Therefore, the polymerization temperature was set to 250 to 380 DEG C. and repolymerization was carried out, but only a blackish brown polymer with a low polymerization degree in the form of a powder, which solidified during polymerization and partially gelled, was obtained.

Comparative Example 2 Implemented using 1.2-bis(phenoxy)ethane-4,4'-dicarboxylic acid in place of 1.2-bis(2-chlorophenoxy)ethane-4,4-dicarboxylic acid of Example 1. When polymerization was carried out in the same manner as in Example 1, it solidified during polymerization.
Only a powdery low polymerization polymer was obtained.

Therefore, repolymerization was carried out at a polymerization temperature of 250 to 360°C, but the polymer partially gelled to become a blackish brown polymer.

Although this polymer exhibited slight optical anisotropy at 261°C, its fluidity was extremely poor, and its melt viscosity was over 10,000 poise at 310°C and a shear rate of 3000 (1/sec).

Example 2 Hydroquinone diacetate (I[) in Example 1 was replaced with 4,4゛-diacetoxybiphenyl (I[>44,
Polymerization was carried out in the same manner as in Example 1 except that 60 g (16.5 x 10 -2 mol) was used to obtain a brown polymer with good fluidity.

The logarithmic viscosity of this polymer is pentafluorophenol (0
, 1 tr /IQ concentration, 60°C), it was 3°5 dρ/g.

The theoretical structural formula of this polymer is as follows, and the elemental analysis results are shown in Table 2, showing good agreement with the theoretical values.

m/n=67/33 Table 2 However, the oxygen content (%) is (100%-0%-I-I%-C
, 0%).

This polymer showed good optical anisotropy at temperatures above 304°C. In addition, the melt viscosity is 350°C and the shear rate is 3000 (1/
The fluidity was extremely good, with a reading of 1,700 poise.

Further, when the thermal properties were measured using a differential scanning calorimetry system (Perkin-Elmer model), the glass transition temperature was 139°C and the melting point was 316°C.

Comparative Example 3 Polymerization was carried out in the same manner as in Example 2 using terephthalic acid instead of 1,2-bis(2-chlorophenoxy)ethane-4,4°-dicarboxylic acid in Example 2, but solidification occurred during polymerization. However, only a low polymerization degree polymer with poor fluidity was obtained. Therefore, the polymerization temperature was changed to 250 to 380 DEG C., and repolymerization was carried out, but it solidified during the polymerization, and only a partially gelled powdery blackish brown polymer with a low degree of polymerization was obtained.

Comparative Example 4 1.2-bis(2-chlorophenoxy)ethane-4,4°-dicarboxylic acid of Example 2 was replaced with 1.2-bis(2-chlorophenoxy)ethane-4,4°-dicarboxylic acid.
Polymerization was carried out in the same manner as in Example 2 using phenoxy)ethane-4,4'-dicarboxylic acid, but it solidified during polymerization and only a low polymerization degree polymer with poor fluidity was obtained. Therefore, repolymerization was carried out by changing the polymerization temperature to 250 to 360°C as in Comparative Example 2, but since solidification occurred during polymerization, the temperature was further raised to 370°C and polymerization occurred, but only a blackish brown polymer with some gelation was obtained. I couldn't.

Examples 3 to 11, Comparative Examples 5 to 10 In a polymerization test tube, p-acetoxybenzoic acid (I), 6-acetoxy-2-naphthoic acid (II), hydroquinone diacetate (■), and chlorohydroquinone diacetate (■
), methylhydroquinone diacetate) (V),
t-butylhydroquinone diacetate) (VT),
4.4-Diacetoxybiphenyl (■), 1.2-bis(2-chlorophenoxy)ethane-4,4-dicarboxylic acid (■), Terephthal M (■), Isophthalic acid (X),
2.6-naphthalene dicarboxylic acid (X), 1.2-
Bis(phenoxy)ethane-4,4-cicaflebonic acid (
XII) wo [(III)+ (IV)+(V)+
(Vl) ten (■)] = [(■) + (IN) thousand (X) -
(X engineering) + (XII)] were prepared in the proportions shown in Table 3 and polymerized in the same manner as in Example 1.

The polymers of Examples 3 to 11 can be uniformly melt-polymerized and have good fluidity, whereas the polymers of Comparative Examples 5 to 10 all solidified during polymerization, and although the polymerization temperature was raised to 380°C, the mold Only partially gelled and foamed polymer was obtained.

<Effects of the Invention> The chlorine-containing copolyester of the present invention has good fluidity and can be used for various thin-walled and precision molded products.

Patent application Daitoshi Co., Ltd.

Claims (1)

[Claims] Consisting of the following structural units (I) to (III), the structural unit (
I) is 30 to 90 mol% of the total, structural unit (II)/[(
II)+(III)] is 10 to 100 mol%, a chlorine-containing copolymer polyester with good fluidity. -(O-X-CO)-...(I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(II) -(O-Y-O_2C-Z-CO)-... ...(I
II) (In the formula, X represents one or more groups selected from ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, and Y represents ▲ Mathematical formulas, chemical formulas, tables, etc. There are▼、▲There are mathematical formulas, chemical formulas, tables, etc.▼、
▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas, chemical formulas,
Indicates one or more groups selected from ▼There are tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼Z indicates ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc. Indicates one or more groups selected from ▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, or ▲There are mathematical formulas, chemical formulas, tables, etc.▼.