JPS604529A - Copolymer polyester - Google Patents

Abstract

PURPOSE:A novel copolymer polyester providing a polymer having high polymerization degree only by melt polymerization, having improved molding properties, providing a molded article having high strength and high modulus of elasticity. CONSTITUTION:A copolymer polyester consisting of 20-50mol% carboxylate unit shown by the formula I and 80-50wt% carboxylate unit shown by the formula II. To obtain the copolymer polyester, preferably a polyethylene-1,2- bis(2-chlorophenoxy)ethane-4,4'-dicarboxylate having 0.4-1.20 intrinsic viscosity is reacted with an acyloxy aromatic carboxylic acid and subjected to polycondensation. p-Acyloxybenzoic acid and/or 6-acyloxy-2-naphthoic acid is used as the acyloxy aromatic carboxylic acid.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel copolymerized polyester p which has excellent moldability and can provide molded articles with high strength and high modulus of elasticity.

In recent years, there has been an increasing demand for high performance plastics, and many polymers with various new performances have been developed. /Oki7
It is known that a copolyester obtained by reacting an aromatic carboxylic acid (Japanese Unexamined Patent Publication No. 49-72593) becomes anisotropic (liquid crystal) and provides various molded products with excellent mechanical properties. However, it has been found that the degree of polymerization of molded articles obtained from the above-mentioned copolyester does not increase sufficiently by melt polymerization alone, and both strength and elastic modulus are insufficient for industrial applications such as tire needles. It was also found that it has a drawback of having a low glass transition temperature.

On the other hand, it is known that boriesdep made from 112-bis(2-chronolephenoxy)ethane-4,4'-dicarboxylic acid and ethylene glycol provides high strength and high elastic modulus (Japanese Patent Publication No. 49/1989). No. 1795), it had the drawback of poor melt fluidity due to high melt viscosity, and it was found that the elastic modulus was not sufficient.

Therefore, the present inventors improved the drawbacks of the above polyester,
As a result of our research aimed at obtaining a copolyester that does not have a very high melting point (and can give molded products with high strength and high modulus of elasticity), we have discovered a new copolyester that meets the above objectives, and have accomplished the present invention. It happened.

That is, the present invention provides the following formula (I) of 2o to 5o) V%
It is a copolymerized polyester having 80 to 50 moles of carboxylate units represented by the following formula (I) (-ORC-)-(Iv).

Compared to the conventional copolymerized polyester made by reacting polyethylene terephthalate M with acyloxybenzoic acid, the copolymerized polyester of the present invention can be obtained by melt polymerization alone, and is superior to ordinary melt molding. Various molded products such as fibers, films, and resins with mechanical properties
It can be easily molded and has a high glass transition temperature.

Also, 1,2-bis(2-chlorphenoquine)ethane-
Even when compared with polyesters made from 4+47-dicarboxylic acid and ethylene glycol, the copolyester obtained by the present invention has excellent melt flowability and can provide molded articles with improved mechanical properties.

The copolymerized polyester of the present invention can be obtained by any method, but preferably polyethylene-1+2-hydroxy
, (2-chlorophenoxy)ethane-4,4'-dicarboxylate? This acyloxy aromatic carbonate is reacted and polycondensed to obtain 2.

Polyethylene-1,2-pinu (2
-Chlorphenoxy)ethane-4,4'-dicarboxylate is a polyester represented by the following structural unit. Intrinsic viscosity (1,4~1
- 20 is preferably used.

This polyethylene-1,2-bis(2-chlorophenoquine)ethane-4+4'-dicarboxylate polymer is 1,2-bis(2-chlorophenoxy)ethane-4+4'-dicarboxylate polymer.
It can be obtained by polycondensing 4,4'-dicarboxylic acid or its ester-forming derivative with ethylene glycol, and furthermore, 1-(2-chlorophenoquine)-2
(phenoxy)ethane-4+47-dicarvone IJ,L
2-bis(phenoquine)ethane-4,4'-dicarboxylic acid, 216-naphthalene dicarboxylic acid LY2.4+4'
J phenyl dicarboxylic acid is '5.5'-diphenyl dicarboxylic acid [@, 3.4'-diphenyl dicarboxylic acid,
2,2'-diphenyldicarvone r11, terephthal 1
Aromatic and aliphatic dicarboxylic acids such as hexahydroterephtha)V acid or ester-forming derivatives thereof and diethylenequinol, '++3--flovandiol 1.1.4-butanedio-/l/ , 116
- It is possible to contain a small amount of glycol component such as hexanediol as a copolymer component. The most preferred copolymerization component is 1-(2-chlorophenoxy)-2(phenoxy)ethane-4,4'-dicarboxylic acid component.

This polyethylene-1,2-bis(2-chlorphenoquine)ethane-4,4'-dicarboxylate (20 to 50 mole and (25 to 45 mo#% in terms of repeat unit t) f-Acylleoxy aromatic carboxylic acid 80~
50 mol, and (75 to 55 mol)
The copolyester of the present invention can be produced by further reaction and polycondensation. The acyloxy aromatic carboxylate mentioned here includes P-acyloxybenzoic acid and/or 6-acyloxy-2-naphthoic acid, such as P-acetoxybenzoic acid and 6-acetoxy-2-naphthoic acid. be. If the amount of these acyloxy aromatic carboxylic acids used is less than 50 MoJv% of the total, anisotropy (liquid crystal) will not be exhibited and melt fluidity will be poor (
If it exceeds 8°/I/%, the melting point is high and decomposition occurs during melt molding, resulting in insufficient toughness and elastic modulus of the final copolyester obtained, which is undesirable.

The copolymerized polyester of the present invention is most preferably produced in the following two-stage PubX process. First, in the first step, polyethylene-1,2-bis(2-chlorophenoxy)ethane-4,4'-dicarboxylate polymer is reacted with acyloxy aromatic carboxylic acid to form a deacyloxy acid as an initial polymer. In the second step, the polycondensation of this initial polymer is accelerated to increase the intrinsic viscosity and obtain the desired copolymerized polyester.

The reaction conditions for the first stage were under an inert gas atmosphere at normal pressure. : <E2
Conditions are employed in which the acyloxy acid to be desorbed is actively removed by heating at 50 to 500 tEK. If the reaction temperature in the first stage is 240°C or less, the reaction rate is slow, and if it is 520'C or more, thermal decomposition of the reactants may occur, which is not preferable.

The reaction conditions of the second stage are 1 target Hg of the initial polymer in the molten state.
Add 290 to 310'C1 under the following reduced pressure? ＾Do it. A catalyst can be used to increase the intrinsic viscosity to a desired value in a short period of time. Typical catalysts used in this method include acetate, strontium acetate, cobalt acetate, antimony trioxide, and tetrabutyl titanate. Most preferred is sodium acetate. The amount of catalyst used is generally from 0.0001 to 0.1% by weight per acyloxyaromatic carboxylic acid, preferably 0.00% by weight.
It is 1 to 0.05% by weight.

Thus, it has 20 to 50 mo) v% of carboquine sort units of the formula (I) and 80 to 50 moles of carboquine V- units of the formula (carboquine V-). The copolymerized polyester of the present invention has an intrinsic viscosity range of 0.4 to 1.2 when measured in orthochlorophenol (25°C).

The copolymerized polyester of the present invention has a low melting point of 300"C or less (and has excellent melt fluidity), so it can be used in ordinary melt molding methods such as extrusion molding, injection molding, compression molding, and blow molding.
It is possible to process fiber films, resins, containers, hoses, etc.

In addition, during molding, reinforcing agents such as glass fiber, carbon fiber, asbestos, etc.
Additives such as fillers, nucleating agents, pigments, antioxidants, stabilizers, plasticizers, lubricants, mold release agents, and other thermoplastic resins are added to impart the desired properties to the molded product. I can do something.

The molded article obtained from the copolyester of the present invention has optical anisotropy and has extremely excellent mechanical properties such as strength and elastic modulus.

The present invention will be further explained below with reference to three examples.

Note that the characteristics evaluation in the examples was performed according to the following regulations.

Intrinsic viscosity: Measured using orthochlorophenol (25').

Melting point, glass transition temperature...Differential scanning calorimeter (D
Strength of fiber measured by SC-] Type I) ... ASTM D1708 Elongation of fiber ... ASTM D1708 Elastic modulus of fiber ... Tensile strength of AEITM D790 molded product ... ASTM D1708 molded product Flexural modulus of elasticity ... ASTM D790 melt viscosity ...
Ripping speed 1000 sec-' with Koka type flow tester
Liquid crystal start temperature measured by... Measured by microscopic observation on a hot stage.

Example 1 Polyethylene-1,2-bis(2-
Chlorphenoquine) ethane 4,4'-dicarboxy V-
Polymer 3818Q (8 molv), 2.16 kg (12 mol) of P-7 Setquin benzoic acid, and 10.8 g of sodium vinegar were charged into a reactor equipped with a stirrer, a distillation column, and a nitrogen gas inlet. Gas calculation atmosphere 260-280
Stir at ℃. After about 1 hour, most of the acetic acid was distilled off, and a copolymerized Boriendel initial polymer with a low melt viscosity was obtained.

Next, the temperature of the reaction system was raised by 300t3r, and at the same time 0.5m
The pressure was reduced to mHg and stirring was continued for an additional 4 hours, resulting in a beige, opaque polymer with a solid melt viscosity of 0.78.

The theoretical structural formula of this polymer is as follows, and the elemental analysis results of this polyester showed good agreement with the theoretical values as shown in Table 1.

m / n (molar ratio) = 60/40 Table 1 However, oxygen content ((6) is (I D 0%-C%-H%
-C1cII). Further, when this copolymerized polyester was placed on a sample stage of a polarizing microscope and its optical anisotropy was confirmed by raising the temperature, it showed good optical anisotropy from 156°C. In addition, the melting point was determined using a Perkin Elma Model 14Dec-2 at a heating rate of 10°C/min.
The temperature was 85°C.

This polymer was subjected to a high-speed flow tester at a spinning temperature of 270.
C. and a spinneret hole diameter of 0.39 φ to obtain a spun yarn (undrawn yarn) of 0.15 Mφ. As a result of measuring the fiber properties of this spun yarn, as shown in Table 2, the strength was 7.5 (g
/a), Young's modulus was 258 (g/(1)), which showed high strength and high elastic modulus.This polymer was also manufactured by Toshiba 1.→ Seiko S5.
- Used in a 50A injection molding machine, cylinder temperature 250~2
A dumbbell test piece was molded under the conditions of 90℃ and mold temperature of 80℃, and the mechanical properties were measured.As shown in Table 2, the tensile strength was 2380 CL (41/ca), and the flexural modulus was 13X.
It had high strength and elastic modulus of 10' (kg/cJ).

Example 2 Polyethylene-1,2-bis(2
-Chlorphenoxy)ethane 414'-dicarpoquinate polymer, P-acetoxybenzoic acid, polyethylene terephthalate and sodium acetate were charged in the proportions shown in Table 2, and polycondensation reaction was carried out under the same conditions as in Example 1. I did this.

As is clear from the results in Table 2, polyethylene-1+2
-His, (2-chlorphenoquine)ethane-4+4'-
Dicarboxylate polymer and P-acetoxybenzoic acid copolymerized polyester has a higher intrinsic viscosity pre-transfer temperature and It can be seen that fibers and molded products with high mechanical properties, high strength, and high modulus of elasticity can be obtained.

Mataforiethylene-1,2-bis(2-chloro)v phenoxy)ethane-4,4'-dicarboxylate copolymer and P-acetoxybenzoic acid copolymer polyester/L/3
In this case, when P-7 setoxybenzoic acid is less than 50%, it does not show optical anisotropy (liquid crystal) because it is an isotropic polyester, and has poor melt flowability, resulting in high strength, high modulus fibers and molding. If the molar ratio exceeds 80, the melting point becomes high and decomposition occurs during melt molding, making spinning and molding impossible.

Example 3 Polyethylene-1,2-bis(2-
Chlorphenoxy)ethane 414'-dicarpoquinlate compound 3.18 kg (8 mo/I/), 6-acetoxy-2-naphtho: acid 2.74# (12 mo/l/) and 1-lium acetate 15 .7 g was charged into a reactor equipped with a stirrer, a distillation column, and a nitrogen gas inlet, and stirred at 250 to 270° C. under a nitrogen gas atmosphere. After about 1 hour, the acetic acid in the heated portion was distilled off, yielding a copolyester initial polymer with a low melt viscosity.

Next 1 = Simultaneously raise the temperature of the reaction system to 285°C for 0.5 seconds
The pressure was reduced to 100 m Hgf, and stirring was continued for 4 hours to obtain a beige, opaque polymer with a solid melt viscosity of #0.75.

The theoretical structural formula of this polymer is as follows, and the elemental analysis results of this polyester showed good agreement with the theoretical values as shown in Table 6.

Table 6 However, the oxygen content @) is (100%-C%-H%-01%
). In addition, this copolymerized polyester was placed on a sample stand using a polarized light microscope and the temperature was raised to confirm the optical anisotropy. As a result, good optical anisotropy was exhibited from 145°C. Further, the melting point was measured using DSG and was found to be 178°C.

Claims (1)

[Claims] 20 to 50 moles of carboxylate units represented by the following formula (1) 1 and 80 to 50 mo/L/% of the following formula (power represented by 1 levoxylate unit + oRc) - (IL) Copolymerized polyester A/.