JPS60217234A - Production of copolymerized polyester - Google Patents

Abstract

PURPOSE:Tetrakis(2,4-di-t-butylphenyl)-4,4-biphenylenediphosphanite is added until the medium stage of the polycondensation to facilitate the production of PEG- copolymerized polyester of good color tone and heat resistance. CONSTITUTION:In the production of a copolymer from (A) a polyester mainly composed of, preferably more than 85mol% of ethylene terephthalate units and (B) 3-50, preferably 5-35wt% of polyethylene glycol (PEG) of 500-10,000 average molecular weight, (C) 0.01-0.1wt%, preferably 0.02-0.07wt%, based on the copolyester, of tetrakis(2,4-di-t-butylphenyl)-4,4-diphenylenediphosphanite, preferably in combination with 0.05-0.2wt% of pentaerythrityl-tetrakis[3-(3,5-di-t- butyl-4-hydroxyphenyl)propionate] is added to the copolyester until the middle stage of the polycondensation.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a method for producing a polyethylene glycol (hereinafter referred to as PIEG) compound copolyester having excellent color tone and heat resistance.

(Prior art) Conventionally, P was used to impart various properties to polyester.
Copolymerizing the EG compound alone or with other auxiliary agents,
Blending methods are widely used. For example, a method of copolymerizing PEG to promote crystallization (Japanese Unexamined Patent Publication No. 55
-86835, etc.), a method of blending PEG alone or in combination with a metal salt, etc. to impart antistatic properties and hydrophilicity (Japanese Patent Application Laid-open No. 52-63292, etc.), and a method of copolymerizing a large amount of PEG. Method of manufacturing an elastic body (Japanese Patent Application Laid-Open No. 52-11195
No. 5) etc.

According to these methods, it is possible to considerably improve the above-mentioned disadvantages of polyester, such as slow crystallization rate, poor antistatic properties, and poor hydrophilic properties.

When PEG is copolymerized with polyester or when the copolymer is molded, heating often causes the color tone of the polymer to worsen or even to lower the degree of polymerization, resulting in a significant loss of polymer properties.

As a means to solve this problem, it is possible to add stabilizers such as heat-resistant and oxidation-resistant agents.
Special Publications No. 44-12591 and No. 45-3113.

5B-10428, etc.), but this has not yet reached a satisfactory stage.

(Object of the Invention) An object of the present invention is to provide a method for producing a PEG compound copolyester having excellent color tone and heat resistance.

(Structure of the Invention) As a result of intensive research to achieve the above object, the present inventors discovered that when producing a PEG compound copolymerized polyester, by the middle stage of the 9-polymer condensation reaction, tetrakis (2,4-ditertiary-butyl Phenyl)-4°4-biphenylene diphosphanite (hereinafter referred to as TFS) or rFS together with pentaerythyl-tetrakis (3-(3,5-ditertiary-butyl-4-hydroxyphenyl)propionate) (hereinafter referred to as INX). ) was found to be effective by adding a predetermined amount of 2, and the present invention was completed.

That is, 9 the present invention uses a polyester mainly composed of ethylene terephthalate units with an average molecular weight of 500 to 10,000.
When producing a copolyester obtained by copolymerizing 3 to 50% by weight of a PEG compound, at any stage up to the middle stage of the single polycondensation reaction, +11 IFS O, 01 to 0.1% by weight.
or (2) IFS O, 01-0.1% by weight and lN
It is characterized by containing X0105 to 0.2% by weight. In the present invention, PI! The polyester that serves as the base for copolymerizing the G compound is mainly composed of ethylene terephthalate units (preferably 85 mol% or more).
Polyester 9 Usually polyethylene terephthalate is used, but isophthalic acid, 5-
Contains acid components such as sodium or potassium sulfoisophthalic acid, p-oxybenzoic acid, adipic acid, sebacic acid, and dodecanedicarboxylic acid, and glycol components such as propylene glycol, butanediol, neopentyl glycol, and cyclohexane dimetatool. It's okay.

In addition, in one aspect of the present invention, PI! The G compound refers to a compound having a PEG chain with ester-forming ability, and is a PEG with a molecular weight of 500 to 10,000 that is easy to copolymerize with polyester and has a large effect of improving crystallinity, dyeability, antistatic properties, etc. is preferably used.

The PEG compound may be added to the polyester at any time before the polycondensation reaction of the polyester is completed.

For example, PE in polyester-forming monomers or oligomers.
A G compound can be added to carry out melt polycondensation.

5- Furthermore, it is preferable to add rFs to the polyester-forming monomer or low polymer, the PEG compound, or the reactant from the time of the esterification or transesterification reaction to the middle stage of the polycondensation reaction before addition of the PEG compound.

The copolymerization ratio of the PEG compound is preferably 3 to 50% by weight, preferably 5 to 35% by weight based on the copolymerized polyester. P
If the proportion of the EG compound is too low, the crystallinity, dyeability, and antistatic properties of the polyester cannot be sufficiently improved.
On the other hand, if the amount is too large, the properties of the molded product made from the copolymerized polyester will be significantly inferior, which is not preferable.

In addition, the amount of IFS added is 0% to the copolymerized polyester.
．． 01~0.10)! Amount%, preferably 0.02-0.
07% by weight is good. If the amount of IFS added is too small, the polymer color tone will deteriorate and the degree of polymerization will decrease due to thermal decomposition during copolymerization reaction, molding, etc. On the other hand, if the amount is too large, the polycondensation reaction will be inhibited, making it impossible to obtain a polymer with a high degree of polymerization.

In addition, when INX is included together with IFS, the heat resistance is 6-1. can be further encouraged.

The amount of TNX added is 0.05 based on the copolymerized polyester.
The content is preferably 0.2% by weight. If the amount added is less than this range, the effect of promoting heat resistance will be poor, and if it is added in an amount exceeding this range, the effect will reach a plateau, undesirably increasing the product cost.

Note that INX alone is insufficient to achieve the object of the present invention.

Also, suitable light stabilizers, heat stabilizers, matting agents, and pigments during or after the production of the copolyester.

It is also possible to contain dyes, various inorganic and organic electrolyte surface modifiers, N fuel, and the like.

There are no particular restrictions on the method for producing the copolyester, and a wide range of conventional production methods can be employed.

The copolyester obtained by the method of the present invention is widely used as fibers, films, other molded products, etc.

(Example) The present invention will be specifically explained below using Examples.

In the examples, "parts" indicate parts by weight.

Each characteristic value was determined according to the following method.

(1) Intrinsic viscosity of polyester Measured at 30°C in a phenol/tetrachloroethane-674 weight ratio mixed solvent.

(2) Polyester color tone (b value) Colorimetric color difference meter (Nippon Denshoku Co., Ltd. ND-1010 model)
Measured at

Example 1 49.8 parts of terephthalic acid and 29.8 parts of ethylene glycol
1 part and heat-stirred under pressure to proceed with esterification.

When the distilled water reached 97% of the theoretical amount, it was transferred to a polycondensation reaction tank under nitrogen pressure, and 0.058 parts of antimony trioxide, 2.6 parts of PEG with a molecular weight of 2000 or 5000, and 1.
Add the amount of IFS shown in the table, temperature 280°C, pressure 0.
The polycondensation reaction was carried out at lnunHg for 4 hours.

Intrinsic viscosity and color tone (b value) of the obtained copolymerized polyester
are shown in Table 1. (Symbols D-F are comparative examples.) Put the copolymerized polyesters with symbols A-E in Table 1 into a hot air dryer,
Heat treatment was performed at 180°C and 210°C for 5 hours.

Table 2 shows the results of measuring the color tone (b value) and intrinsic viscosity of the copolymerized polyester after heat treatment. (Intrinsic viscosity retention is the percentage of the value after heat treatment to the value before heat treatment.) 91 Example 2 The same operation as in Example 1 was performed using 1FSh INX. The results are shown in Table 3 and It is shown in Table 4. (In the symbol, L
is a comparative example. ) Table 3 ((1) Symbol L7-44 The degree of integration did not increase and it was a blackish brown polymer.

Table 4 10- (Effects of the Invention) According to the present invention, a PEG compound copolyester that has a good color tone and has little decrease in degree of polymerization due to heating in the polymer manufacturing process or heating during molded product manufacturing is produced. without causing any trouble.

It can be easily manufactured.

Patent applicant Nippon Ester Co., Ltd. Surrogate child Yuzo Tama 11-

Claims (1)

[Scope of Claims] (When producing a copolyester in which 3' to 50% by weight of a polyethylene glycol compound having an average molecular weight of 500 to 10,000 is copolymerized to a polyester mainly containing 11-ethylene terephthalate units, the middle stage of a single polycondensation reaction at any stage up to.tetrakis(2,4-ditertiary-butylphenyl)
-4,4-biphenylene diphosphanite 0.01
A method for producing a copolyester characterized by containing ~0.1% by weight. (2) At any stage up to the middle of the double condensation reaction when producing a copolymerized polyester in which 3 to 50% by weight of a polyethylene glycol compound having an average molecular weight of 500 to 10,000 is copolymerized to a polyester mainly containing ethylene terephthalate units. Tetrakis (2,4-ditertiary-butylphenyl)
-4,4-biphenylene diphosphanite 0.01~
0.1% by weight and pentaerythrityl tetrakis(
3-3,5-ditert-butyl-4-hydroxyphenyl)probionate) 0.05-0.2% by weight
A method for producing a copolyester comprising: