JPS58174421A - Preparation of water-soluble polyester - Google Patents

Abstract

PURPOSE:To provide the titled polymer having high light resistance and useful as a paste, etc., by polymerizing a specific amount of an ester-forming sulfonic acid alkali metal salt as the dicarboxylic acid component and a specific amount of a polyoxyalkylene glycol as the glycol component. CONSTITUTION:A polyester is prepared from (A) a dicarboxylic acid component composed mainly of an aromatic dicarboxylic acid (e.g. terephthalic acid) and containing an ester-forming sulfonic acid alkali metal salt compound and (B) a glycol component composed mainly of an alkylene glycol (e.g. ethylene glycol) and containing the glycol of formula (R is 4-20C bivalent aliphatic hydrocarbon group; i and j are integer of 2-4; m and n are integer of >=0; 2<=m+n<=15). The amount of the alkali metal salt compound is 1-50mol% of the dicarboxylic acid component, and that of the glycol of formula is 10-80wt% of the polyester.

Description

DETAILED DESCRIPTION OF THE INVENTION The present Ij1 has a polymer composition that can be easily controlled during production;
The present invention also relates to a method for producing a light-resistant water-soluble polyester.

Conventionally, water-soluble polyesters have been useful for easily soluble polymers that can be dissolved and removed from starches, adhesives, and synthetic fibers composed of multiple components.
Polyesters are known in which an ester-forming sulfonic acid metal salt compound is copolymerized with low-molecular weight or high-molecular weight polyethylene glycol C (hereinafter abbreviated as FEQ). However, when using low molecular weight PEG such as diethylene glycol or triethylene glycol, PEG tends to distill out of the reaction system during the polycondensation reaction of polyester, making it difficult to control the amount of PEG in the polyester produced. Moreover, there is a problem in that the distillate is significantly contaminated. On the other hand, P.E.
As the molecular weight of G increases, this problem related to distillation decreases, but the light resistance of the PEG copolymerized polyester decreases. Fi becomes noticeable. Further, when the PEQ copolymer polyester is dissolved and removed from the fibers, some of the polyester may remain uneluted, but in such a case, the above-mentioned decrease in light resistance causes a significant decrease in product quality.

The present inventors have conducted intensive studies to obtain a water-soluble polyester that does not have these drawbacks, and as a result have completed the present invention.

That is, in the present invention, when producing a polyester from a dicarboxylic acid component mainly consisting of an aromatic dicarboxylic acid and a glycol component mainly consisting of an alkylene glycol,
As the dicarboxylic acid component, an ester-forming sulfonic acid alkali metal salt compound is used in an amount of 1 to -0 mole based on the dicarboxylic acid component.

A method for producing a water-soluble polyester characterized by using a glycol represented by the following general formula (1) as a glycol component, exceeding 10% by weight and not exceeding 80% by weight based on the resulting polyester (0 pressure) (CIH □0ru, R-
0((!, H, /J), I'I (1)C in the formula,
几 is a divalent aliphatic hydrocarbon group or aromatic hydrocarbon group having 4 to 20 carbon atoms, +ejFi is the same or different integer of 2 to 4, m, nlj is the same or different integer of 0 or more and 2≦
man≦15. ) The carvone brewing components for producing the water-soluble polyester in the process of the invention are aliphatic or aromatic acids and their ester-forming derivatives. Specific examples include oxalic acid, malonic acid, dimethylmalonic acid, moss
acid, glutaric acid, adipic acid, azelaic acid, sepacin, maleic acid, itaconic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid,
Phthalic acid, isophthalic acid, terephthalic acid, 2.5-dimethylterephthalic acid, 2.5-norbornanedicarboxylic acid, siphenic acid, 1.4-naphthalenedicarponic acid, 2
．． 5-naphthalene dicarboxylic acid, 2.6-naphthalene dicarboxylic acid % 1.2'1:: Dicarboxylic acids such as monobis(phenoxy)ethane-P, 'P'-dicarboxylic acid, or ester-forming derivatives thereof! -(2-Hydroxyethoxy)benzoic acid and its ester-forming derivatives are exemplified.

In the present invention, it is preferable to use terephthalic acid or its ester-forming derivative as the main dicarboxylic acid component from the viewpoint of heat resistance, moldability, etc. of the resulting water-soluble polyester.

As the glycol component, an aliphatic or aromatic glycol other than the glycol represented by general formula (1) is used. Specific examples include ethylene glycol, glopylene glycol, 1.3-7'ropanediol, 2.2-dimethyl-i,a-propanediol, 1.4-butanediol, 1.6-hexanediol, 1.2 -Cyclohexane dimetatool, 1.4-cyclohexane dimetatool, 1.10-decamethylene glycol, 4.4'-methylene diphenol, 4.4'-dihydroxybisphyl
nor, 4,4'-isopropylidenediphenol, 2
．． Examples include 5-naphthalene diol and P-xylylene glycol. 2. PEGtl having a low to high molecular weight can also be used within a range that does not impede the effects of the present invention. As the glycol component, ethylene glycol, 1,4-butanediol, 1,4-cyclohexane dimetatool, etc. are particularly preferred.

Examples of ester-forming sulfonic acid alkali metal salt compounds include sulfoterephthalic acid, 5-sulfoiphthalic acid,
-Sulfo-7-thalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, 4-sulfo-7-ni-3,5-dicarboxybenzenesulfonic acid, 5-[4-sulfophenoxy]
Inphthalic acid, sulfo-P-xylylene glycol, 2
Examples include alkali metal salts of -sulfo-1,4-bisfhydroxyethoxy)benzenato and ester-forming derivatives thereof. Among these, the sodium and potassium salts of 5-sulfoinphthalic acid and sulfoterephthalic acid are particularly preferred.
If the amount is less than 1 mole, preferably 5 to 40 moles, the water solubility of the obtained polyester will decrease and the stability as a solution will also deteriorate. If the amount is more than 50 mol, the melt viscosity during polyester polymerization becomes extremely high, making it difficult to increase the degree of polymerization. Further, the chemical stability of the obtained polyester is also lowered, which is not preferable. Note that if the metal layer of the sulfonate compound is a polyvalent metal other than an alkali metal, the water solubility of the obtained polyester will be significantly reduced, which is not preferable.

In the glycol represented by the general formula (RI) used in the present invention, divalent fatty monogroups having an RFi carbon number of 4 to 20 can be mentioned. In the general formula (1), 1.1 is an integer different by the same -t number. and m and w+ are the same or different integers of 0 or more, and 2≦man≦15. K 1.j if 2 is the most preferred method for obtaining a highly water-soluble polyester.

When m + n is smaller than 2, distillation tends to occur during the polyester polycondensation reaction, and the resulting polyester has low water solubility. If man exceeds 15, the light resistance of the polyester decreases, which is not preferable. The preferred range is 3≦man
≦10.

According to the present invention, the glycol represented by the general formula (1) is copolymerized with the resulting polyester in an amount exceeding 10% by weight and not more than 80% by weight. If it is less than 10% by weight, the water solubility of the polyester will be low, and if it is more than 80% by weight, the chemical and thermal stability of the polyester will be poor and the polyester will become rusty when handled after polymerization. The preferred range is 20~
70 weight - 66., 1° The method for producing water-soluble polyester using each of the above raw materials is not particularly limited, and can be carried out according to a normal polyester production method. As a general method, (1) dicarboxylic acid or its ester-forming derivative is
Examples include a method in which a dicarboxylic acid component and a glycol component are subjected to an esterification reaction and then subjected to a polycondensation reaction, and the like. In addition, in the polymerization to obtain a polyester through an esterification reaction in the present invention, the glycol of general formula (1) is added from just before the end of the esterification reaction to the start of the polycondensation reaction to suppress the decomposition of the ether bond. Good.

Metal compounds such as sodium, magnesium, calcium, manganese, zinc, titanium, lead, tin, antimony, germanium, and tungsten are generally used as catalysts in the above transesterification reactions, esterification reactions, and polycondensation reactions. $P, the water-soluble polyester of the present invention may optionally contain additives such as a stabilizer, a flame retardant, and a lubricant.

In addition, the reduced viscosity (η, p10) of the water-soluble polyester obtained by the method of the present invention (0.25 per 100 sL of a solvent of phenol/tetrachloroethane = 6/4, measured at 25°C) has a Fio of 27 or more. In terms of moldability, a value of 90.3 or higher is desirable.

When the method of the present invention having the above configuration is used, the glycol represented by the general formula (1) does not distill out during the polycondensation reaction, so a water-soluble polyester with a stable composition can be obtained. The water-soluble polyester is water,
It is a material that can be substantially dissolved in an aqueous or alkaline aqueous solution, in some cases under heating.2 It has particularly good light resistance, so fibers, knitted fabrics, etc. to which it is attached or left,
The quality of molded products etc. will not be degraded. It is also very useful as a paste, adhesive, or polyester as a dissolving/removable component.

The present invention will be illustrated in a different manner using examples below, but the present invention is limited to these examples and is expressed as I/'i. Note that parts in the examples mean parts by weight.

Example 1 1000 parts of dimethyl terephthalate, 810 parts of dimethyl ester of 5-sodium sulfoine heptatalate, 1080 parts of ethylene glycol, and 1016 parts of the glycol represented by the following formula (1) were placed in a transesterification reactor, and anhydrous sodium acetate was added thereto. 11.2 parts, zinc acetate/2 water beds 0.5
The temperature was raised over 150 minutes to m + n = 5 (average value) 150 to 230'O, and the by-product methanol was distilled off through the tube to carry out the transesterification reaction. .5 parts, diethyl-2
After adding 1.1 parts of -carboethoxyethylphosphonate and stirring for 10 minutes, one reactant was transferred to a 230-Q polycondensation vessel.

Temperature VI - While increasing the temperature to 275°C for 30 minutes, the system was gradually reduced to 0.111 HjF'', then 275°C,
Perform the polycondensation reaction at 0-1 wHP for 45 minutes to obtain 2 co□y
HIJr-X7A't! picture. M”::1::・f IJ
Z X. .

This polyester, whose original viscosity was 0.40, was
From the gas chromatogram of the solution portion when thermally decomposed with 5N-Xl)H ethanol solution, it was found that the yield rate relative to the amount of glycol charged as shown by the formula (1) was 97°-.

A 2.1 s aqueous solution of this polyester 'i 6 G-Q was prepared by dissolving it in warm water, and after drying it on a 25μ polyethylene terephthalate film, it was pressure-bonded with another 25μ polyethylene terephthalate film at 140°C, and strong adhesion was observed. I was scolded.

Comparative Example 1 Example 1 except that 1016 parts of diethylene glycol (DEG) was used instead of glycol (It) in Example 1.
A copolymerized polyester having a reduced viscosity of 0.42 was obtained in the same manner as above. DIG yield characteristic Fi6 in this polyester
It was 3-.

Example 2 10 parts of the polyester obtained in Example 1 had an intrinsic viscosity of 0.6.
3. Polyethylene terephthalate chips 11.1 90 parts Kt and put into Zukuri complete set extrusion spinning machine.
The yarn was spun at a spinning temperature of 290°C and a take-up speed of 900 m/min, and then stretched by a conventional method to obtain a 75 denier 36
After obtaining the drawn filament, the basis weight is 2.
00f/m I made nine interlocks for the goose. This knitted fabric was treated with a 20 f/l aqueous solution of caustic soda under boiling conditions to obtain a knitted fabric with a weight loss rate of 10-. It was confirmed that this knitted fabric absorbs water easily and exhibits high water retention. This knitted fabric was dyed with Diamond Fux Blue-BQ, PR (manufactured by Mitsubishi Kasei Co., Ltd., a dispersible dye) at 130°C, subjected to reduction washing at room temperature, and dyed at 63 on a fade-o-meter. '0
After irradiation for 140 hours, the film showed excellent light fastness, with a sunlight fastness of grade Fi5 based on the blue scale standard.

Comparative Example 2 Glycol (1) K of Example 1 was replaced with molecule t2000
A water-soluble copolymerized IJ ester having a reduced viscosity of 0.39 was obtained in the same manner as in Example 1, except that 1016 parts of PEG was used. This polyester was subjected to polyethylene terephthalate Ktbubbling, spinning, stretching, knitting, and weight loss treatment in the same manner as in Example 2 to obtain a knitted fabric with a weight loss rate of 11-. This was dyed in the same manner as in Example 2, and the sunlight fastness t was examined, and it was found to be grade 4. Shown.

Patent applicant: Toyobo Co., Ltd.

Claims (1)

[Scope of Claims] When manufacturing polyester pipes from a dicarboxylic acid component mainly consisting of an aromatic dicarboxylic acid and a glycol component mainly consisting of an alkylene glycol, an ester-forming sulfone alkali metal salt compound is used as the dicarboxylic acid component as the dicarboxylic acid component. The glycol represented by the following general formula (1) was added as a glycol component to 1 to 1 mole of IsO to the polyester obtained.
1. A method for producing water-soluble polyester, characterized in that it uses more than 80% by weight and less than 80% by weight. EL) ←C 凰瓜五〇 )-1-0 ゆう c、Ill、o輻R
(1) In formula C, R has 4 to 2 carbon atoms, QC) divalent aliphatic hydrocarbon group or aromatic hydrocarbon group, j is the same or different integer of 2 to 4, m, +ali is the same Nine is a different integer greater than or equal to 0, and I≦man≦15. )