JPH07165895A - New polyester - Google Patents

Abstract

PURPOSE:To obtain a polyester which gives a high-strength molding with a good moldability when used as a plasticizer for a resin material (e.g. a vinyl chloride resin) or as an internal plasticizer for a polyurethane resin. CONSTITUTION:A polyester represented by the formula (wherein Ac is a 2-10C aliph. or alicyclic hydrocarbon group; and n, the number of repeating units, is 1-250) is selected.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel polyester. Specifically, the present invention relates to resins, especially polyvinyl chloride,
The present invention relates to a novel polyester that is useful as a plasticizer such as a polyurethane resin or an internal plasticizer and that provides a resin material having good fluidity during molding and high strength.

[0002]

2. Description of the Related Art Conventionally, a polyester obtained from a polyol such as ethylene glycol or 1,4-butanediol and a fatty acid such as adipic acid or sebacic acid has been widely used as a polyurethane raw material or a plasticizer for various polymers. . For example, when an adipate compound is used as a plasticizer for a vinyl chloride resin, its properties change depending on the amount used. Generally, when the amount of the adipate compound used is increased to improve moldability, the vinyl chloride resin molded article It has the drawback of reduced strength.

Further, for example, when a general-purpose ethylene glycol or 1,4-butanediol adipate is used as the urethane elastomer, the physical properties of the elastomer change depending on the amount of adipate used, and when the strength of the urethane elastomer is increased, the adipate It is necessary to reduce the amount used, but in that case, there is a drawback that the fluidity of the polymer deteriorates and the moldability is impaired.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a new polyester which can overcome the above-mentioned drawbacks of the prior art.

[0005]

Means for Solving the Problems As a result of intensive studies on the above problems, the present inventors have found that when a new polyester having a structural unit represented by the following formula (1) is used as a plasticizer for a resin material They have found that they are good and have high strength, and have completed the present invention.

[Chemical 2] (However, Ac represents an aliphatic or alicyclic hydrocarbon group having 2 to 10 carbon atoms. N is an integer of 1 to 250 and is the number of repeating units.)

The present invention will be described in detail below. The polyester of the present invention basically has the general formula (2):

[Image Omitted]-(OCRCOOR'O) n -... (2)

In the formula (2), the OCRCO portion is abbreviated as an acid portion, and the OR'O portion is abbreviated as a diol portion, and each of them is represented by a corresponding acid or a corresponding diol. Is essential to contain 1,2-cyclohexanediol as its diol moiety. The 1,2-cyclohexanediol may be any of cis isomer, trans isomer, cis and trans mixture.

The polyester of the present invention includes not only those in which all diol moieties are 1,2-cyclohexanediol but also those in which other diols are used at the same time.
For example, the previously mentioned improvements are possible by replacing some of the diol moieties of previously known polyesters using 1,4-butanediol as the diol moiety with 1,2-cyclohexanediol.

The improvement effect tends to increase as the proportion of 1,2-cyclohexanediol in the diol portion of the polyester increases. The range of the proportion of 1,2-cyclohexanediol in the diol portion of the polyester is 2 mol% or more, preferably 10 mol% or more, more preferably 20 mol% or more.

The diol moiety that can be used simultaneously with 1,2-cyclohexanediol has 2 to 2 carbon atoms.
There may be mentioned 10 aliphatic and alicyclic diols. For example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,2-dimethyl-1,3-butanediol, 1,6-hexanediol and the like can be exemplified. , And one or more of these may be used at the same time. In addition, depending on the case, 3 as represented by trimethylol pullup and pentaerythritol.
It is also possible to use small amounts of compounds with one or more hydroxyl groups.

As the acid moiety of the polyester of the present invention, an aliphatic or alicyclic dibasic acid having 4 to 12 carbon atoms can be used. Specific examples include adipic acid, glutaric acid, succinic acid, sebacic acid and the like. For producing the polyester of the present invention, a conventionally known method for producing polyester can be adopted. That is, a method of directly dehydrating and condensing the dibasic acid or its anhydride and a diol, a method of reacting a lower alkyl ester of the dibasic acid with a diol, or an acid halide of the dibasic acid, a diol and a base. The method of reacting with and the like can be exemplified, and an appropriate catalyst or solvent may be used.

The molecular weight of the polyester of the present invention varies depending on the use, but it is usually in the range of 500 to 50,000, preferably in the range of 600 to 30,000 on the number average basis. Further, although the terminal of the polyester of the present invention depends on the use, it is desirable that it is substantially a hydroxyl group when it is used for a polyurethane resin, for example. When an inactive end is required for other purposes, the end is inactivated by using a monobasic acid or monoalcohol.

The molecular weight of the polyester of the present invention can be controlled by
A method generally used in the production of polyester is used, for example, a method such as a method of adjusting the ratio of a diol and a dibasic acid, an anhydride or an ester, a method of using a monobasic acid or a monoalcohol as a terminal terminator, and a generally known method. Is adopted.

When the polyester of the present invention is used as a plasticizer, particularly when it is used as a plasticizer for vinyl chloride resin, it is 10 to 15 per 100 parts by weight of vinyl chloride resin.
0 parts, preferably 40-150 parts are mixed. If it is less than 10 parts by weight, a sufficient plasticizing effect cannot be obtained, and if it exceeds 150 parts by weight, the tackiness increases, which is not preferable.

As a method for mixing the polyester of the present invention with a resin material such as a vinyl chloride resin, a commonly used roller, Henschel mixer, Banbury mixer or the like is used. Generally, when processing a vinyl chloride resin, a lubricant and a stabilizer are required, but various commercially available compounding agents can be used.

A resin using the polyester of the present invention as an internal plasticizer, for example, a polyurethane resin, includes an aliphatic, alicyclic or aromatic polyisocyanate having two or more isocyanate groups in the molecule and a terminal. It is obtained by polymerizing the polyester of the present invention in which is substantially a hydroxyl group and a chain extender.

When the polyester of the present invention is used as an internal plasticizer, the polyester becomes one of the hydroxyl components, so that other hydroxyl components such as a chain extender or a hydroxyl component may be used depending on the intended use and performance. And the ratio is represented by the molar ratio of the hydroxyl groups contained in the polyester and the other hydroxyl component, 20/1 to 1/20, more preferably 10/1 to
It is 1/10.

The polyisocyanate constituting the polyester of the present invention includes 4,4'-diphenylmethane diisocyanate, p-phenylene diisocyanate, tolylene diisocyanate, 1,5-naphthylene diisocyanate and xylylene diisocyanate. Nato, hexamethylene diisocyanate, isophorone diisocyanate, 4,
Examples include 4'-dicyclohexylmethane diisocyanate, water adducts of the above diisocyanates, alcohol adducts, isocyanurates, and the like.

As the chain extender, a molecular weight of 400 containing at least two hydrogen atoms capable of reacting with isocyanate is used.
The following low molecular weight compounds, which are commonly used in the polyurethane industry, can be used. For example, ethylene glycol, propylene glycol, 1,4-
Butanediol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,4-cyclohexanediol and other diols;
Water; diamines such as ethylenediamine, propylenediamine, xylylenediamine, isophoronediamine, and phenylenediamine; and hydrazine can be exemplified, and these can be used alone or in combination of two or more kinds.

For the polymerization of the above reaction components, the conditions adopted in the known urethane formation reaction are applied. For example, the ratio of the total number of the polyester of the present invention having a hydroxyl group at the terminal to the number of active hydrogen atoms contained in the chain extender to the isocyanate group contained in the polyisocyanate is about 1: 1. The mixture is mixed so as to be reacted at a temperature of about 50 to 150 ° C. It is also possible to carry out the reaction in a solvent,
Examples of the solvent include hydrocarbon, ketone, ether, formamide, acetamide, sulfoxide and the like. Known urethane polymerization catalysts can be used, and various additives such as antioxidants, light stabilizers and pigments can be added during the polymerization or after the polymerization.

[0021]

The present invention is illustrated in more detail by the following examples, which do not limit the scope of the invention. In addition,
The viscosity of the polymer in the examples using Shimadzu flow tester CFC-100, experimental load 40 Kg / cm ^2,
Plunger diameter 1 cm ² , die size 1 mm x 2 mm
Was carried out under the conditions of The tensile strength of the obtained molded product, for example, the film, was measured according to JIS-K7113.

(Synthesis Example 1) 0.15 g of metallic sodium was dissolved in 54.2 g of cyclohexanediol of a mixture of cis and trans in a flask equipped with a stirrer and a condenser, and 87.1 g of dimethyl adipate was added. 150 ° C,
From atmospheric pressure to 220 ° C. and finally to 5 mmHg, the temperature was gradually raised over 12 hours, and methanol was flowed out while the pressure was reduced. Thereafter, the temperature was lowered to room temperature, 150 cc of dichloromethane was added to dissolve it, and the mixture was further washed with diluted hydrochloric acid and further washed with water until it became neutral. Solvents such as dichloromethylene in the oil layer were removed under reduced pressure, and then almost completely removed with a vacuum dryer. From the measurement by GPC, the polystyrene-reduced number average molecular weight and weight average molecular weight were 2,070 and 2,400, respectively.

(Synthesis Example 2) In a flask equipped with a stirrer,
250 cc of 1,4-dioxane, 100.0 g of adipoyl chloride and trans-cyclohexanediol 7
1.0 g was added and dissolved. At 50 ° C., 108.0 g of pyridine was added dropwise to this solution over about 1 hour, and heating and stirring were continued for another 1 hour. The resulting pyridine hydrochloride crystals were filtered and most of the 1,4-dioxane in the filtrate was removed under reduced pressure. 150 cc of dichloromethane was added to the obtained solution to dissolve it, and the solution was washed with dilute hydrochloric acid and further washed with water until it became neutral. Solvents such as dichloromethane in the oil layer were removed under reduced pressure, and then almost completely removed with a vacuum dryer.

The acid value of the obtained polyester is 0.25 m.
The g / g and OH value were 55.1 mg / g. The polystyrene-reduced number average molecular weight and weight average molecular weight obtained from GPC were 2,270 and 2,620, respectively.
Met.

(Synthesis Example 3) In a flask equipped with a stirrer,
250 cc of 1,4-dioxane, 100.0 g of adipoyl chloride and trans-cyclohexanediol 2
1.3 g and 1,4-butanediol 38.6 g were added and dissolved. At 50 ° C., 108.0 g of pyridine was added dropwise to this solution over about 1 hour, and heating and stirring were continued for another 1 hour. The resulting pyridine hydrochloride crystals were filtered and most of the 1,4-dioxane in the filtrate was removed under reduced pressure. 150 cc of dichloromethane was added to the obtained solution to dissolve it, and the solution was washed with dilute hydrochloric acid and further washed with water until it became neutral. Solvents such as dichloromethylene in the oil layer were removed under reduced pressure, and then almost completely removed with a vacuum dryer.

The acid value of the obtained polyester is 0.25 m.
The g / g and OH value were 52.2 mg / g. The polystyrene-reduced number average molecular weight and weight average molecular weight obtained from GPC were 2,120 and 2,460, respectively.
Met.

Example 1 40 g of the cyclohexanediol-adipic acid polyester obtained in Synthesis Example 1 and 60 g of polyvinyl chloride for softening having a polymerization degree of 1,300 were used as 100 parts.
Kneading at ℃, about 100μ film was made by a compression molding machine, and the tensile strength was measured to be 4.97 Kg / cm ^2.
Met. Also, the viscosity by flow tester is 200 ℃
Was 1.17 × 10 ⁴ poise.

Comparative Example 1 Commercially available polyester of 1,4-butanediol and adipic acid (polystyrene-equivalent number average molecular weight and weight average molecular weight of 1, respectively
820,2,110) 40 g and polyvinyl chloride 60 g for softness having a degree of polymerization of 1,300 are kneaded at 100 ° C., a film of about 100 μ is formed by a compression molding machine, and the tensile strength is measured to be 2.68 Kg / cm ^2. Met. The viscosity measured by a flow tester is 1.69 × 1 at 200 ° C.
0 was ⁴ poise.

COMPARATIVE EXAMPLE 2 Commercially available polyester of 1,4-butanediol and adipic acid (polystyrene-equivalent number average molecular weight by GPC, weight average molecular weight of 1, respectively)
820,2,110) 20 g and polyvinyl chloride for softening having a degree of polymerization of 1,300 80 g are kneaded at 100 ° C., a film of about 100 μ is formed by a compression molding machine, and the tensile strength is measured to be 4.46 Kg / cm ^2. Met. Moreover, the viscosity by a flow tester is 1.88 × 1 at 200 ° C.
It was 0 ⁵ poise.

Example 2 40 g of the polyester of cyclohexanediol and adipic acid obtained in Synthesis Example 3 and 60 g of polyvinyl chloride for softening having a polymerization degree of 1,300 were used as 100 parts.
Kneading at ℃, about 100μ film was made by the compression molding machine, and the tensile strength was measured to be 3.88 Kg / cm ^2.
Met. Also, the viscosity by flow tester is 200 ℃
Was 1.27 × 10 ⁴ poise.

(Example 3) Polyester 4 of cyclohexanediol and adipic acid synthesized according to Synthesis Example 2 in 500 g of toluene and 500 g of methyl isobutyl ketone.
52.7 g, 4,4′-diphenylmethane diisocyanate 83.4 g, and 1,4-butanediol 10.0 g as a chain extender were dissolved, dibutyltin dilaurate 50 mg was added as a catalyst, and the mixture was stirred at 80 ° C. for 5 Reacted for hours. The solvent of the obtained polyurethane solution was almost completely removed under reduced pressure.

The resulting polyurethane had a number average molecular weight in terms of styrene of 71,500. This polyurethane was molded into a film of about 100 μm by a compression molding machine and the tensile strength was measured and found to be 4.28 Kg / cm ² .

Comparative Example 3 Polyester of commercially available 1,4-butanediol and adipic acid in 500 g of toluene and 500 g of methyl isobutyl ketone (OH value: 54.3 mg /
g) 469.1 g, 4,4′-diphenylmethane diisocyanate 83.4 g, 1,4-butanediol 10.0 g as a chain extender are dissolved, dibutyltin dilaurate 50 mg is added as a catalyst, and the mixture is stirred at 80 ° C. Was reacted for 5 hours.

The solvent of the obtained polyurethane solution was almost completely removed under reduced pressure. The resulting polyurethane had a styrene-equivalent number average molecular weight of 75,000. This urethane was molded into a film of about 100μ with a compression molding machine, and the tensile strength was measured to be 3.23 Kg / cm.
^{Was 2} .

(Comparative Example 4) A commercially available polyester of ethylene glycol and adipic acid in 500 g of toluene and 500 g of methyl isobutyl ketone (OH value: 56.8 mg / g)
438.9 g, 4,4′-diphenylmethane diisocyanate 83.4 g, and 1,4-butanediol 10.0 g as a chain extender are dissolved, dibutyltin dilaurate 50 mg is added as a catalyst, and the mixture is stirred at 80 ° C. for 5 Reacted for hours.

The solvent of the obtained polyurethane solution was almost completely removed under reduced pressure. The resulting polyurethane had a styrene-equivalent number average molecular weight of 72,000. This polyurethane was molded into a 100 μ film by a compression molding machine and the tensile strength was measured to be 2.08 Kg / cm ²
Met.

[0037]

EFFECT OF THE INVENTION The polyester represented by the formula (1) of the present invention has high moldability and high strength when used as a plasticizer for resin materials such as vinyl chloride resin plasticizer and polyurethane internal plasticizer. A plasticized vinyl chloride resin or an internally plasticized polyurethane can be obtained.

Claims (1)

[Claims] 1. A polyester containing a structural unit represented by the following formula (1). [Chemical 1] (However, Ac represents an aliphatic or alicyclic hydrocarbon group having 2 to 10 carbon atoms. N is an integer of 1 to 250 and is the number of repeating units.)