JPS62161832A - Novel polymer and production thereof - Google Patents

Abstract

PURPOSE:To obtain a polymer having excellent flexibility and giving a molded article having balanced physical properties, small strength difference between the extrusion direction and the crossing direction and having excellent knot tenacity, by reacting a polyethylene terephthalate with an acyloxybenzoic acid and a specific carboxylic acid. CONSTITUTION:The objective polymer contains the recurring units of formula I-III and has a reduced viscosity [etasp/c] of >=0.2dl/g measured in p- chlorophenol at a concentration of 0.2g/dl at 60 deg.C. The polymer can be produced by reacting a polyethylene terephthalate with an acyloxybenzoic acid and N-(3- acyloxyphenyl)-phthalimide-4-carboxylic acid and/or N-(4-acyloxyphenyl)- phthalimide-4-carboxylic acid at 200-350 deg.C, preferably 250-300 deg.C in an inert gas for 0.5-5hr under 800-0.05mmHg pressure.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel polyester polymer used as an optical fiber reinforcing agent, a material for industrial equipment such as magnetic tapes and floppy disks, and a method for producing the same.

[Conventional technology]

As a polyester with improved mechanical properties,
Polyesters modified with acyloxy aromatic carboxylic acids as shown in Japanese Patent No. 9-72393 are well known. However, when this polyester is extruded,
Although the extruded product exhibits excellent strength and elastic modulus in the extrusion direction, the strength in the direction perpendicular to the extrusion direction is insufficient.

For this reason, for example, filaments have a drawback in that their knot strength is insufficient.

[Problem that the invention seeks to solve]

The present invention aims to overcome these conventional drawbacks and provide a novel polyester polymer in which a new structural unit is introduced into the above polymer to improve the balance of mechanical properties, and a method for producing the same. It is something to do.

[Means for solving problems]

The novel polymer of the present invention has a repeating unit represented by the formula % formula 1+-OC@0-)-(If ) and 0.2 g/ It is characterized in that the reduced viscosity [ηs1)/c) of a solution with di concentration at 60°C is 0.2d17g or more.

Assuming that the numbers of repeating units represented by (1), (II) and (III) are i, m and n, respectively, (m+n)/l=Q, 5 to 4.0, although not particularly limited. ,n/
(f+n)=0.01-0.3 is preferable.

If the former value is small, the strength will not be improved sufficiently, and if the latter value exceeds 0.3, the moldability will deteriorate.

Moreover, if the reduced viscosity is less than 0.2 dl/g, the mechanical strength will not be sufficient.

The novel polymer of the present invention can be prepared, for example, by adding acyloxybenzoic acid and N-(3-acyloxyphenyl)-phthalimide to polyethylene terephthalate according to the method of the present invention.
It can be produced by reacting 4-carboxylic acid and/or N-(4-acyloxyphenyl)-phthalimido-4-carboxylic acid.

There are no particular restrictions on polyethylene terephthalate, but it is usually 0.2 g/ml using parachlorophenol as a solvent.
Reduced viscosity (ηsp/c) at 60°C of a solution with a concentration of dl
) is 0.1 to 1.0 dl/H, and those in which the dicarboxylic acid component and diol component have been modified with other components can also be used within the range that does not impair the purpose of the present invention.

As acyloxybenzoic acid, the general formula is R'-Co-0@C0OH (R' has 1 to 1 carbon atoms.
Those represented by the alkyl group (3) are preferably used.

Examples of acyloxybenzoic acids include m-acetoxybenzoic acid, p-acetoxybenzoic acid, 4-acetoxy-3-
Methoxybenzoic acid, 4-acetoxy-3-chlorobenzoic acid and 4-acetoxy-3,5-dichlorobenzoic acid are used, preferably p-acetoxybenzoic acid is used.

N-(3-acyloxyphenyl)-phthalimide-4-
As the carboxylic acid and/or N-(4-acyloxyphenyl)-phthalimide-4-carboxylic acid, those represented by the following formula (R'' is an alkyl group having 1 to 3 carbon atoms) are preferably used.

Specific examples include N-(4-acetoxyphenyl)-phthalimido-4-carboxylic acid and N-(3-acetoxyphenyl)-phthalimide-4-carboxylic acid.

In the method of the present invention, the three ingredients of raw materials are
C., preferably 250 to 300.degree. C., the polyester is first decomposed by an acidolysis reaction, and then a comonomer is bonded to the decomposition product to polymerize it again to obtain a polymer.

The reaction is preferably carried out in an inert gas such as argon at a temperature of 0.5
It will last for ~5 hours. The reaction pressure is about 800-0.05 n
It is preferable to carry out the reaction at +8 g, with the pre-reaction stage being carried out under approximately atmospheric pressure and the post-reaction stage being carried out under reduced pressure.

The reaction can be carried out without the use of a catalyst, but
Catalysts such as cobalt can be used to accelerate the polymerization reaction.

The novel polymer obtained by the present invention is useful for producing molded articles and has sufficient knot strength in filaments.

The novel polymers of this invention can be made into useful products using conventional conventional methods and conventional equipment. For example, fibers can be formed by conventional melt spinning techniques and injection molded using conventional conventional equipment and techniques.

The novel polymers of the present invention may also contain fillers, pigments, glass fibers, asbestos fibers, antioxidants, stabilizers, desensitizers, lubricants and other additives.

〔Example〕

EXAMPLES The present invention will be explained below with reference to Examples, but the scope of the present invention is not limited by these Examples.

Example 1 9.60 g (50 mmol) of polyethylene terephthalate was placed in a reactor equipped with a stirrer and an argon gas inlet tube.
Acetoxybenzoic acid 5.40 g (30 mmol), N-
(3-acetoxyphenyl)-phthalimido-4-carboxylic acid 3.25 g (10 mmol) and N-(4-acetoxyphenyl)-phthalimido-4-carboxylic acid 3
．． 25 g (10 mmol) was charged and heated to 280° C. under an argon stream. 1 at 280°C under stirring.
After carrying out the reaction for an hour and distilling off the acetic acid produced, 1■■H
The reaction was carried out under stirring for 2 hours under reduced pressure.

As a result, 18.1 g of polymer was obtained. This polymer was prepared at 0.2 g/d using p-chlorophenol as a solvent.
Reduced viscosity (77 sp/
c) was 0.54 dl/g. In addition, as a result of infrared absorption spectrum analysis of this polymer, 1580aa- and 1
Absorption by benzene ring at 490 cm- position, 1650
Absorption due to carbonyl group at aa- position, 1780-1
Absorption due to imide groups was observed at the 680 cm- and 720 cffi- positions, and absorption due to an ether bond was observed at the 1240 cIm- position. 'Furthermore, it was confirmed from observation using a polarizing microscope that this polymer exhibits liquid crystallinity at temperatures of 250°C or higher.

Next, this polymer was extruded at 220° C. through a nozzle with an inner diameter of 1 mm to obtain fibers with a thread diameter of 30 μm. The mechanical properties of the obtained fibers are shown in Table 1.

Example 2 The amount of polyethylene terephthalate used was 7.68g (4
0 mmol) and the amount of acetoxybenzoic acid used was 7.20 g (40 mmol), but the same procedure as in Example 1 was carried out to obtain 17.6 g of a polymer. The reduced viscosity [η sp/c) of this polymer was 0.83 dl/g, and the results of IR analysis were the same as in Example 1. Table 1 shows the mechanical properties of fibers having a diameter of 30 μm obtained by spinning this polymer at 350°C.

Example 3 The amount of polyethylene terephthalate used was 9.60g (5
4.0 mmol), 3.60 g (20 mmol) of acetoxybenzoic acid, and both N-(3-acetoxyphenyl)-phthalimido-4-carboxylic acid and N-(4-acetoxyphenyl)-phthalimido-4-carboxylic acid. 87
19.5 g of a polymer was obtained by carrying out the same operation as in Example 1, except that the amount was changed to 5 g (15 mmol). The reduced viscosity (7751)/C) of this polymer was 0.63 dl/g, and the results of IR analysis were the same as in Example 1. Table 1 shows the mechanical properties of fibers having a diameter of 30 μm obtained by spinning this polymer at 270°C.

Example 4 The amount of polyethylene terephthalate used was 7.68g (4
0 mmol), 9.00 g (50 mmol) of acetoxybenzoic acid, and both N-(3-acetoxyphenyl)-phthalimido-4-carboxylic acid and N-(4-acetoxyphenyl)-phthalimido-4-carboxylic acid 1. 625
g (5 mmol), the same operation as in Example 1 was carried out to obtain 16.2 g of a polymer. The reduced viscosity [η sp/c) of this polymer was 0.55 dl/g, and the results of TR analysis were the same as in Example 1. 30% of this polymer
Table 1 shows the mechanical properties of fibers with a yarn diameter of -30 μm obtained by spinning at 0°C.

Example 5 The amount of polyethylene terephthalate used was 7.68g (4
0 mmol), 7.20 g (40 mmol) of acetoxybenzoic acid, 4.875 g (15 mmol) of N-(3-acetoxyphenyl)-phthalimide-4-carboxylic acid, N-(4-acetoxyphenyl)-phthalimide-
The same procedure as in Example 1 was carried out except that 1.625 g (5 mmol) of 4-carboxylic acid was used to obtain a polymer of 17.3 g (5 mmol).
I got g. The reduced viscosity (yy sp/c) of this polymer was 0.47 dl/g, and the results of TR analysis were the same as in Example 1. Table 1 shows the mechanical properties of fibers with a diameter of 30 μm obtained by spinning this polymer at 300° C.

Example 6 The amount of polyethylene terephthalate used was 7.68 g (4
0 mmol), acetoxybenzoic acid 9.00 g (50 mmol), N-(3-acetoxyphenyl)-phthalimido-4-carboxylic acid 3.25 g (10 mmol)
Polymer 1 was obtained by performing the same operation as in Example 1 except that
6.1 g was obtained. Reduced viscosity of this polymer (ηsp/c
) was 0.43 dl/g, and the results of the TR analysis were the same as in Example 1. Table 1 shows the mechanical properties of fibers having a diameter of 30 μm obtained by spinning this polymer at 250° C.

Example 7 The amount of polyethylene terephthalate used was 5.76g (3
0 mmol), 10.8 g (60 mmol) of acetoxybenzoic acid, 3.25 g (10 mmol) of N-(3-acetoxyphenyl)-phthalimido-4-carboxylic acid.
Polymer 1 was obtained by performing the same operation as in Example 1 except that
5.3 g was obtained. Reduced viscosity of this polymer [ηsp/c
) was 0.40 dl/g, and the results of the TR analysis were the same as in Example 1. Table 1 shows the mechanical properties of fibers with a diameter of 30 μI obtained by spinning this polymer at 300°C.

Comparative Example 1 7.68 g (40 mmol) of polyethylene terephthalate was reacted in the same manner as in Example 1 using 10.8 g (60 mmol) of acetoxybenzoic acid. The reduced viscosity [ηsp/c) of the obtained polymer was 0.40 dl/g
Met. Table 1 shows the mechanical properties of fibers having a diameter of 30 μm obtained by spinning this polymer at 250° C.

The test method in Table 1 is based on JTS L 1069. [Effects of the Invention] The present invention has excellent flexibility and a good balance of physical properties of the molded product, that is, the difference in strength between the extrusion direction and the orthogonal direction is small, and there are no knots. A new polymer with excellent strength was obtained.

Claims (1)

[Claims] 1. A repeating unit represented by the following formulas: 1. A novel polymer having a reduced viscosity [ηsp/c] of 0.2 dl/g or more at 60°C in a solution with a concentration of 0.2 g/dl using p-chlorophenol as a solvent. 2. Reacting acyloxybenzoic acid with N-(3-acyloxyphenyl)-phthalimido-4-carboxylic acid and/or N-(4-acyloxyphenyl)-phthalimide-4-carboxylic acid with respect to polyethylene terephthalate. A method for producing a novel polymer characterized by the following.