JPS6067530A - Copolyester - Google Patents

Abstract

PURPOSE:To provide a polyester capable of giving, in good formability, formed article of high strength and high modulus with adequately high melting point, having both specific two sorts of carboxylate units. CONSTITUTION:The objective copolyester having (A) 50-98mol% of a carboxylate unit of formula I and (B) 50-2mol% of a second carboxylate unit of formula II (R is of formula III or IV). The manufacturing process is as follows: (1) 50-98mol%, on a recurring unit basis, of polyethylene-1,2-bis(2-chlorophenoxy) ethane-4,4'-dicarboxylate with an intrinsic viscosity 0.4-1.20 and (2) 50-2mol% of an acyloxy aromatic carboxylic acid are made to react, at 250-300 deg.C, to prepare a prepolymer while eliminating the oxy acid generated. The resulting prepolymer is heated to 290-310 deg.C under a reduced pressure <=1mm.Hg to further proceed with a polycondensation.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel copolyester that has excellent moldability and can provide molded articles with a high modulus of elasticity.

Polyethylene-1,2-bis(2-chlorophenoxy)
Ethane-4,4'-dicarboxylate is known to provide m-fibers with high elastic modulus (Japanese Patent Publication No. 49-1795
(Japanese Patent Publication No. 2003-110023), it has the drawbacks of high melt viscosity, poor spinnability, and low flexural strength. Furthermore, although a film made from this polymer also has a high modulus of elasticity, it was found that the stretching tension during stretching was large and the stretchability was not necessarily sufficient, and the film had poor impact resistance.

Therefore, the present inventors investigated with the aim of improving the drawbacks of the above polyester and obtaining a copolyester that does not have a very high melting point and can provide molded products with high strength and high modulus of elasticity. We have discovered a new copolymerized polyester, and have completed the present invention.

That is, the present invention provides for
Is the carboxylate unit represented by the following formula (I) l and less than 50 mol % or more than 2 mol % of the carboxylate unit represented by the following formula (IF)? (-ORC+ (indicating Il)) is provided.

Polyethylene-1,2-bis(2
-Chlorphenoxy)ethane-4,4'-dicarboxylate is a polyester having the structural unit shown below and having an intrinsic viscosity of 1° and 0.4 to 1.
．． 20 is preferably used.

Note that this polyethylene-1,2-bis(2-chlorophenoxy)ethane-4,4'-dicarboxylate polymer is 1,2-bis(2-chlorophenoxy)ethane-4,4'-dicarboxylate polymer.
It is obtained by polycondensing 4,4'-dicarboxylic acid or its ester-forming derivative with ethylene glycol, and further contains 1-(2-chlorophenoxy)-2(phenoxy)ethane-4,4'-dicarboxylic acid. , 1.2-
bis(phenoxy)ethane-4,4'-dicarboxylic acid,
2.6-naphthalenedicarboxylic acid, 4.4'-diphenyldicarboxylic acid, 3.3'-diphenyldicarboxylic acid,
3. Aromatic and alicyclic dicarboxylic acids such as 4'-diphenylcarboxylic acid, 2.2'-diphenyldicarboxylic acid, terephthalic acid, hexahydroterephthalic acid, or ester-forming derivatives thereof, diethylene glycol, 1.3-propane A small amount of glycol components such as diol, 1,4-butanediol, and 1,6-hexanediol can be contained as a copolymer component. The most preferred copolymerization component is 1-(2-chlorophenoxy)-2(
phenoxy)ethane-4,4'-=3-dicarboxylic acid component.

This polyethylene-1,2-bis(2-chlorophenoxy)ethane-4,4'-dicarboxylate is 50 to 98 mol%, especially 55 to 95 mol% in terms of repeat units.
/% acyloxy aromatic carboxylic acid 50-2 mol%,
In particular, the copolymerized polyester of the present invention can be produced by further reacting and polycondensing 45 to 5 mol%. The acyloxy aromatic carboxylic acids mentioned here include P-acyloxybenzoic acid and/or 6-acyloxy-
2-naphthoic acid, such as P-acetoxybenzoic acid,
6-acetoxy-2-naphthoic acid and the like. If the amount of these acyloxy aromatic carboxylic acids used exceeds 50 mol % of the total, anisotropy (liquid crystal) will be exhibited, resulting in a highly anisotropic film or resin, which is not preferable. If it is less than 2 mol %, the effects of improving spinnability, fiber bending strength, film stretchability, and impact resistance, which are the objectives of the present invention, are small and the objectives of the present invention cannot be achieved.

The copolyester of the present invention is most preferably produced in the following two steps. In the first step, polyethylene-1
,2-bis(2-chlorophenoxy)ethane-4,4'
- The dicarboxylate polymer is reacted with an acyloxyaromatic carboxylic acid to form a deacyloxy acid as an initial polymer, and in the second step, the initial polymer is further polycondensed to increase its intrinsic viscosity and produce the desired copolymer. Polymerized polyester is obtained.

The reaction conditions for the first stage were 24°C under an inert gas atmosphere at normal pressure.
Conditions are employed in which the acyloxy acid to be desorbed is actively removed by heating to 0 to 320°C, particularly 250 to 300°C. If the reaction temperature in the first stage is 240° C. or lower, the reaction rate is slow, and if it is 320° C. or higher, thermal decomposition of the reactants may occur, which is not preferable.

The reaction conditions for the second stage were to convert the initial polymer in the molten state into IMHg
Heat to 290-310° C. under reduced pressure. A catalyst can be used to increase the intrinsic viscosity to a desired value in a short period of time. In particular, typical catalysts used in this method include acetates such as sodium acetate, magnesium acetate, strontium acetate, and cobalt acetate, antimony trioxide, and tetrabutyl titanate, but sodium acetate is most preferred. The amount of catalyst used is generally from 0.0001 to 0 based on the acyloxyaromatic carboxylic acid.
．． 1% by weight, preferably 0.001-0.05% by weight.

Thus, the copolyester polymerized polyester of the present invention having 50 to 98 mol% of the carboxylate units represented by the formula (I) and 50 to 2 mol% of the carboxylate units represented by the formula (I) has orthochlorophenol. The intrinsic viscosity measured at medium temperature (25°C) is 0.4 to 12.

The copolymerized polyester of the present invention has a low melting point of 300°C or less and excellent melt fluidity, so it can be used for ordinary melt molding such as extrusion molding, injection molding, compression molding, and blow molding, and can be used to produce fibers and films. It can be processed into resins, containers, hoses, etc., and is particularly useful as a film.

During molding, reinforcing agents such as glass fibers, carbon fibers, and asbestos, fillers, nucleating agents, pigments, antioxidants, stabilizers, plasticizers, lubricants, mold release agents, etc. may be added to the copolymerized polyester of the present invention. Agents and other thermoplastic resins can be added to impart desired properties to the molded article.

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

The present invention will be further explained below with reference to Examples. Note that the characteristics evaluation in the examples was performed according to the following regulations.

Intrinsic viscosity: Measured using orthochlorophenol (25°C).

7- Young's modulus of mtm---ASTM D790 bending strength of fiber 11・30 single fibers with moisture balance were reciprocated from side to side at an angle of 60 rpm with a load of 200 capes per 1 tenier, and the single fibers were bent at the frictional part. Read the number of times of cutting, and calculate the bending strength (times) by dividing the sum of the number of times of cutting 30 times by the number of times of measurement.

Young's modulus of film: ASTM D882 Charpy impact strength of film: ASTM D256 Stretching speed was 2.00 (1/min).

Melt viscosity: Measured using a Koka type flow tester at a shear rate of 1000 SeC.

Example 1 Polyethylene-1,2-bis(2-chlorophenoxy)ethane-4,4'-dicarboxylate polymer with an intrinsic viscosity of 0.57, 2.78 diagonals (7 mol), P-acetoxybenzoic acid 0.54 kg (3 mol) of acid and 5.4 f of sodium acetate were charged into a reactor equipped with a stirrer, a distillation column, and a nitrogen gas inlet, and the mixture was heated under a nitrogen gas atmosphere at 260 to 28 kg.
Stirred at 0°C. After about 1 hour, most of the acetic acid was distilled off, and a copolyester initial polymer with a low melt viscosity was obtained.

Next, the temperature of the reaction system was raised to 300°C, and at the same time 0.5 nH
The pressure was reduced to 1.5 g, and stirring was continued for an additional 4 hours. As a result, a beige, opaque polymer with an intrinsic viscosity of 0.56 was obtained.

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) - 30/70 Table 1 However, the oxygen content (e) is (100% - 6% - H% - 01
%). Furthermore, this copolymerized polyester was placed on a sample stage of a polarizing microscope and the temperature was raised to confirm the optical anisotropy, and it was found that it was an isotropic polymer. Further, the melting point was measured at a heating rate of 10°C/min using a PerkinElmer DSC-I model and found to be 243°C.

This polymer was dried at 180°C for 3 hours under reduced pressure and then heated to 300°C.
An unstretched film was obtained by melt extrusion into a sheet. This unstretched film was simultaneously biaxially stretched at 120° C. to 3 times the length in the machine direction and in the transverse direction, and heat treated at 200° C. for 1 minute to obtain a biaxially stretched film.

The maximum stretching stress during stretching was 0.47 kq/- and 0.7 ky/- for polyethylene-1,2-bis(2-chlorophenoxy)ethane-4,4'-hycarboxylate.
It was found that the stretchability was considerably lower than that of the above. In addition, the Young's modulus is quite high at 650 kq,/d in both the vertical and horizontal directions, and the Charpy impact strength is 45 tg*n/-, which is higher than that of PoIJ ethylene-1,2-bis(2-chlorophenoxy)ethane-4,4' 25 ky of dicarboxylate
- It was found to be considerably higher than tM/-.

Example 2 Polyethylene-1,2-bis(2
-chlorophenoxy)ethane-4,4'-dicarboxylate and P-acetoxybenzoic acid as shown in Table 2 (intrinsic viscosity 0.5 to 0.6) was melted in the same manner as in Example 1. An extruded unstretched film was obtained. This unstretched film was simultaneously biaxially stretched at 120°C, and then immediately heat-treated at 150 to 240°C for 1 minute to obtain a biaxially stretched film.

From Table 2, it can be seen that the copolymerized polyester of the present invention has a low melt viscosity, low stretching stress during stretching, and high Young's modulus and Charpy impact strength.

On the other hand, the melt viscosity was higher (Experiment I6) and the stretching stress was higher (
Experiment 46), Young's modulus force was low (Experiment x5), and Schaffleby impact strength was low (Experiment A6).

12- Example 3 Polyethylene-1,2-bis(2-
3.58 kg (9 mol) of chlorophenoxy)ethane-4,4'-dicarboxylate polymer, 0.23 kg (1 mol) of 6-acetoxy-2-naphthoic acid, and 6.91 kg of sodium acetate were added to a stirrer and a distillation column. and charged into a reactor equipped with a nitrogen gas inlet under a nitrogen gas atmosphere at 250~2
The mixture was stirred at 70°C. 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, the temperature of the reaction system was raised to 290°C, and at the same time 0.5 jl
The pressure was reduced to 1Hg and stirring was continued for an additional 4 hours, resulting in a beige, opaque polymer with an intrinsic viscosity of 0.71.

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 3.

14- rn / n (molar ratio) = 10/90 Table 3 However, oxygen content (4) +, 1 (100% - 0% - H% -
CI96).

This polymer was spun at a spinning temperature of 300°C and a take-up speed of 150 m/min, and at a bottle temperature of 100°C and a hot plate temperature of 150°C.
When stretched 9 times, the elastic modulus was as high as 251 f/d, and the bending strength was 460 times, which is higher than that of polyethylene-1,2-bis(
It was found to be significantly better than 160 times for 2-chlorophenoxy)ethane-4,4'-dicarboxylate.

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Claims (1)

[Scope of Claims] More than 50 mol% and 98 mol% of carboxylate units represented by the following formula (I) 1 and less than 50 mol% and 2 mol% or more of carboxylate units represented by the following formula (I) A copolymerized polyester having -OR (indicating j (I)).