JPS5933127B2 - Polyester compounds and manufacturing methods - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel cocondensation polymerized polyester and a method for producing the same, and more specifically to a cocondensation polymerized polyester that has improved dyeability compared to polyethylene terephthalate, or for improving dyeability thereof. It concerns the manufacturing method.

Polyethylene terephthalate-based polymers generally have 2
It has a melting point around 60°C and has excellent properties such as elasticity, heat resistance, water resistance, weather resistance, chemical resistance, and electrical properties, and is a synthetic fiber and film with names such as Tetoron, Terylene, Labusan, Mylar, and Dekron. It is widely used as

However, because polyethylene terephthalate has good crystallinity, it is generally not easy to dye it.
-C.

Special methods such as yellow dyeing, high temperature and high pressure dyeing, and thermosol dyeing are used.

Polyester fibers do not contain reactive groups that can be chemically dyed within the fibers, so they are difficult to dye with common dyes.

Furthermore, although polyester fibers have sufficient affinity for disperse dyes and azoic dyes, dyeing is still difficult because polyester fibers are dense and the speed at which dye molecules diffuse into the interior of the fibers is slow. Many studies have been conducted on improving the dyeability of polyethylene terephthalate. Polyester fibers are graft-polymerized with monomers having hydrophilic carboxylic groups, sulfonic groups, amino groups, etc., or areophthalic acid, paraoxybenzoic acid, methoxypolyethylene glycol, 3.5 di(carbomethoxy)benzenesulfonate or Copolymerization using sulfinic acid, phosphonic acid, phosphinic acid or its derivatives to synthesize easily dyeable polymers,
5 methods have been proposed, including a method in which only the outside of polyester fiber is coated with an easily dyeable polymer.

However, the graft polymerization method and coating method are not economical because they require many treatment steps during synthesis, and at present only modified polyester fibers using isophthalic acid sulfonate have been industrialized.

In this method, polyester fibers themselves or blended or woven products with cellulose fibers can be dyed as is using direct dyes, but acid dyes are used for blended or woven products with animal fibers, so the polyester fiber side In such cases, the fabrics had to be dyed separately, then blended and interwoven.

An object of the present invention is to provide a modified polyester compound with improved dyeability of a polyester compound, and the modified polyester compound is produced by reacting various reagents with epoxy groups contained in the main chain of polyethylene terephthalate. In this way, it can be further modified into a useful functional polyester compound.

That is, the present invention relates to a polyester compound having an average molecular weight of 2,000 to 15,000 and having a repeating unit of the following general formula, and a method for producing the same.

However, m/n = 0.06 to 1. In addition, the manufacturing method is to add epoxysuccinic acid diester to a product obtained by reacting ethylene glycol and terephthalic acid dimethyl ester, and to obtain it by cocondensation polymerization. I can do it.

The epoxysuccinic acid diester used in the present invention is produced by adding sulfuric acid corresponding to the amount of salt exchange and the amount of catalyst to epoxysuccinic acid disodium salt or epoxysuccinic acid monosodium salt, and reacting the mixture with alcohol in a suspension. It can be obtained by

When methanol, ethanol, etc. are used as the alcohol, dimethyl or diethyl ester of epoxysuccinic acid can be easily obtained. Further, this epoxysuccinic acid diester may be either a cis type or a trans type. Commercially available dimethyl terephthalate and ethylene glycol may contain impurities that have an adverse effect on polymerization, so the former should be recrystallized from ethanol, and the latter should be prepared by dissolving a small amount of metallic sodium in nitrogen for 1 hour. Good results can be obtained by purification by means such as refluxing and then distillation.

Polymerization is carried out by a conventional method. First, ethylene glycol and dimethyl terephthalate are placed in a hard polymerization tube with a side tube, and heated to around 180° C. in a mantle heater while passing a nitrogen stream. Methanol is distilled out within 2 hours.

The mixture is further heated at VC of 225° C. for 1 hour to completely remove methanol to obtain bis(β-hydroxyethyl) terephthalate or its low polymer. Next, this was dissolved in an aprotic solvent and heated to 60°C to 80°C to carry out cocondensation polymerization. Since the epoxide group is easily ring-opened,
The solvent used for solution polymerization is not a polar solvent but an aprotic solvent. This cocondensation polymerization reaction proceeds slowly without a catalyst, but Ca. Zn. Mg. Addition of transition metal compounds such as Sn promoted polymerization. The amount of this polymerization catalyst added is 0.01 to 0.05% (W/W). The molar fraction of copolymerization components of bis(β-hydroxyethyl) terephthalate and epoxysuccinic acid dimethyl ester is arbitrary, but in order to improve dyeability, the epoxysuccinic acid component in the polyester should be 2 to 15%.
The degree is effective. The cocondensation polymerized polyester compound obtained in the present invention contains an epoxysuccinic acid component in the main chain, and can be used in common polyester solvents such as m-cresol, concentrated sulfuric acid, chlorophenol, hot phenol, hot nitrobenzene, and tetrachloroethane. Lifuenol (weight ratio 50:
50), etc., and it is possible to form fibers or films from these solutions. In addition, this cocondensation polyester compound is characterized by better hydrophilicity than conventional polyethylene terephthalate-based compounds, and because it has a highly reactive epoxide group in the main chain of the polyester, it reacts with various reagents. This has the effect of increasing the amount and rate of adsorption of dye molecules, and in particular, amino groups can be introduced into polyester by reaction with ammonia and amines, which makes it possible to dye with acid dyes and improve polyester fibers. It is possible to improve dyeability, which has been cited as a drawback.

In addition, by introducing hydroxyl groups and anion groups,
It is possible to impart ion exchange properties and permeability to fibers and membranes. Thus, the present invention can be applied over a very wide range of applications. Next, the present invention will be explained by examples.
Example 1 Ethylene glycol 13.67 and terephthalic acid dimethyl ester 21.37 and calcium acetate, 0.025
Put 7 into a hard polymer tube with a side tube, and add 18 while passing nitrogen.
Heat to 0°C to 250°C and start stirring.

Completely remove methanol within 3 hours and add 25 quarts of bis(
β-hydroxyethyl) terephthalate as well as products containing its oligomers are obtained.

Next, 22.27 grams of this product, 2 grams of dimethyl epoxysuccinate, and 0.025 grams of lead acetate were put into a polymerization tube, dissolved in 100 ml of dioxane, heated to 60-80°C, and stirring started and polymerization was carried out for 24 hours. Summer. After the polymerization, the reaction solution was poured into a large amount of acetone to precipitate it, yielding about 17 g of a white solid. From the IR spectrum of the obtained polyester, absorption peculiar to epoxide groups was observed in the vicinity of 1260 to 1200 (1-J mo V1-1).The results of elemental analysis showed that C-
47.1%, H-5.3%, which is the theoretical value of the repeating structure corresponding to the formula below (C = 47.1%, H = 4.8%)
corresponds to

This cocondensation polymerized polyester compound is soluble in concentrated sulfuric acid, m-cresol, chlorophenol, hot phenol, hot nitrobenzene, tetrachloroethanelifephenol, etc.
) The reduced viscosity measured at 30'C in a mixed solvent is 0.55, the softening point is 210-225°C, and the number average molecular weight Mn is V
The result of measurement using the PO method was 11,600. Pressure melt molding of this copolymer yielded a film, and extrusion molding of the melt yielded fibers.

Claims (1)

[Claims] 1. An average molecular weight of 200 having repeating units of the following general formula:
0-15000 polyester compound. ▲There are mathematical formulas, chemical formulas, tables, etc.▼However, m/n=0.
06-1 2 Epoxysuccinic acid diester is added to the product obtained by reacting ethylene glycol and terephthalic acid dimethyl ester, and cocondensation polymerization is performed to produce a product having an average molecular weight of 2,000 to 15,000 and having a repeating unit of the following general formula. Method for producing polyester compounds. ▲There are mathematical formulas, chemical formulas, tables, etc.▼However, m/n=0.
06-1