JPS62205119A - Novel polyester polymer and production thereof - Google Patents

Abstract

PURPOSE:To obtain the titled polymer useful as industrial device material such as optical fiber reinforcing agent, magnetic tape, etc., by reacting polyethylene terephthalate with an acyloxybenzoic acid, etc. CONSTITUTION:(A) A polyethylene terephthalate having preferably 0.1-1.0dl/g reduced viscosity is blended with (B) an acyloxybenzoic acid (e.g. m- acetoxybenzoic acid, etc.), (C) terephthalic acid and (D) a 2,6-di(acyloxyaryloxy) benzonitrile [e.g. 2,6-di(4-acetoxyphenoxy)benzonitrile, etc.] and reacted in an inert gas such as argon, etc., at 200-350 deg.C for 0.5-5hr to give the aimed polymer having >=0.2dl/g reduced viscosity and repeating units shown by formulas I, II and III (Ar is aromatic residue).

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, floppy disks, etc., and a method for producing the same.

[Conventional technology]

JP-A-49-72393 proposes a polyester with improved mechanical properties obtained by reacting polyethylene terephthalate with an acyloxy aromatic carboxylic acid.

However, when this polyester is extruded, the extrusion molded product exhibits excellent strength and elastic modulus in the extrusion direction, but does not have sufficient strength in the direction perpendicular to the extrusion direction. 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.

[Means for solving problems]

The novel polymer of the present invention has a repeating unit represented by the formula % formula %) formula + oc-<feather 0+ (II) and formula - CN, and 0.2 g using p-chlorophenol as a solvent. /dl? The reduced viscosity [ηsp/c) of a 711f solution at 60°C is 0.2d 1
It is characterized by being 7g or more.

If the numbers of repeating units represented by CI), (II), and [■] are l, m, and n, respectively, n/j! is not particularly limited, but n/j! +m=0.01~0゜2, m+
n/l = 0.4 to 4.0 is preferred.

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 produced, for example, by reacting polyethylene terephthalate with acyloxybenzoic acid, terephthalic acid and 2,6-di(acyloxyaryloxy)benzonitrile according to the method of the present invention. .

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

As acyloxybenzoic acid, Those represented by the alkyl group) 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.

As the 2.6-di(acyloxyaryloxy)benzonitrile, those having the general formula CN are preferably used.

Specifically, 2,6-di(4-acetoxyphenoxy)benzonitrile, 2,6-bis(4-(4-acetoxyphenyl)phenoxybenzonitrile, 2,6-di(5-acetoxyphenoxy)benzonitrile,
-acetoxyα-naphthoxy)benzonitrile, among others, 2,6-di(4-acetoxyphenoxy)
Benzonitrile is preferably used.

Further, the terephthalic acid used in the present invention may partially contain isophthalic acid.

In the method of the present invention, the four ingredients of the raw materials are
C., preferably 250 to 300.degree. C., polyethylene terephthalate 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
0 reaction pressure carried out for ~5 hours is approximately 800 ~ 0,05 m
11 g, the pre-reaction stage is preferably carried out under approximately atmospheric pressure, and the post-reaction stage is preferably 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, plasticizers, 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 Polyethylene terephthalate 1-7.68 g (40 mmol) was placed in a reactor equipped with a stirrer and an argon gas inlet tube.
and 9-909-90 mmol of acetoxybenzoic acid),
2.02 g (5 mmol) of 6-di(4-acetoxyphenoxy)benzonitrile and 0.8 g of terephthalic acid
Add 3g (5 mmol) and heat at 280℃ under argon stream.
heated to. The reaction was carried out at 280°C for 1 hour with stirring, and after distilling off the acetic acid produced, the pressure was reduced to 1 mm/1 g, and the reaction was carried out at 280°C with stirring for 2 hours.

As a result, 16.4 g of polymer was obtained. This polymer was prepared at 0.2 g/d using p-chlorophenol as a solvent.
Reduced viscosity at 60°C of a solution with one concentration [ηsp/c]
was 0.73 dl/g. Mata, as a result of infrared absorption spectrum analysis of this polymer, 1580 and 1490
Absorption by benzene ring at cm-' position, 1650aa
Absorption due to carbonyl group at position -', 1240 cm-
Absorption by ether group at position ', 2220C11-'
Absorption due to nitrile group was observed at the position. moreover,
This polymer was confirmed to exhibit liquid crystallinity at 250° C. under a polarizing microscope.

Next, this polymer was extruded at 300° C. through a nozzle with an inner diameter of 1 inch 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 acetoxybenzoic acid used was 9.0 g (50 mmol), 2.6-di(4-acetoxyphenoxy)benzonitrile was 4.04 g (10 mmol), and terephthalic acid was 1.66 g (10 mmol). 17.8 g of a polymer was obtained in the same manner as in Example 1 except for the following. The reduced viscosity [η sp/c) of this polymer was 0.85 d 1 /g. The results of infrared absorption spectrum analysis are shown in Example °1.
It was the same. Table 1 shows the mechanical properties of fibers obtained by extrusion molding this polymer.

Example 3 The amounts used were 5.4 g (30 mmol) of acetoxybenzoic acid, 12.12 g (30 mmol) of 2,6-di(4-acetoxyphenoxy)benzonitrile, and 4 g (30 mmol) of terephthalic acid.
．． The same procedure as in Example 1 was carried out except that the amount was changed to 98 g (30 mmol) to obtain 24.2 g of a polymer. The reduced viscosity [ηsp/e) of this polymer is 0.37 dI/g
The results of infrared absorption spectrum analysis were the same as in Example 1. Table 1 shows the mechanical properties of fibers obtained by extrusion molding this polymer.

Example 4 2.78 g (5 mmol) of 2,6-bis(4-(4-acetoxyphenyl)phenoxy)benzonitrile was used instead of 2.6-di(4-acetoxyphenoxy)benzonitrile. The same operation as in Example 1 was carried out to obtain 17.1 g of a polymer.

The reduced viscosity (η31)/C) of this polymer is 0.21 dl
/g, and the results of infrared absorption spectrum analysis were the same as those on the real male side 1. The mechanical properties of fibers obtained from this polymer are shown in Table 1.

Comparative Example 1 Same as Example 1 except that 2.6-di(4-acetoxyphenoxy)benzonitrile and terephthalic acid were not used at all, and the amount of acetoxybenzoic acid used was 10.73 g (60 mmol). and 14.3 g of polymer
I got it. The reduced viscosity (ηsp/c) of this polymer is 0.4
The mechanical properties of the fibers obtained from this polymer are shown in Table 1.

Margin below Table 1 It was resistant to JIS L-1069.

〔Effect of the invention〕

According to the present invention, a new polyester polymer has been obtained which is excellent in flexibility, has a good balance of physical properties in a molded article, that is, has a small difference in strength between the extrusion direction and the direction perpendicular thereto, and has excellent knot strength.

Claims (1)

[Claims] 1. Having a repeating unit represented by the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ A novel polyester polymer characterized in that the reduced viscosity [ηsP/c] at 60° C. of a solution with a concentration of 0.2 g/dl using p-chlorophenol as a solvent is 0.2 dl/g or more. 2. A method for producing a novel polyester polymer, which comprises reacting polyethylene terephthalate with acyloxybenzoic acid, terephthalic acid, and 2,6-di(acyloxyaryloxy)benzonitrile.