JPH07298891A - Method for producing polyester and catalyst for producing polyester - Google Patents

Abstract

PURPOSE:To obtain a polyester by using a catalyst excellent in catalyst effects without causing side reactions, reducing insulating properties and deteriorating performances even when remaining in a product by polymerizing a divinyl dicarboxylate with a glycol in the presence of a hydrolase. CONSTITUTION:This method for producing a polyester is to polymerize a divinyl dicarboxylate such as a divinyl ester of an aliphatic dicarboxylic acid or a carbocyclic dicarboxylic acid (e.g. divinyl adipate) with a glycol (e.g. 1,4- butanediol) in the presence of a hydrolase such as a lipase, a protease or a cellulase in isopropyl ether at 45 deg.C temperature for 8hr, then add chloroform to the polymerization solution, carry out the ultrasonic treatment, disperse the enzyme therein, filter the resultant solution, separate the enzyme, distill away the organic phase under reduced pressure, pour the residual substance into methanol, deposit a polymer, separate the deposited polymer by filtration and dry the separated polymer. The polyester is useful for synthetic fibers, films, engineering plastics, etc.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a polyester using a hydrolase catalyst.

[0002]

2. Description of the Related Art Polyester is a polycondensation product of polyhydric carboxylic acid and polyhydric alcohol, and has been widely used for a long time as a synthetic fiber or film. Furthermore, recently, engineering plastics having high strength and high elasticity have been developed, and they are industrially extremely important polymers.

Polyesters are produced by polycondensation of polyhydric carboxylic acids, their acid chlorides or their ester derivatives with polyhydric alcohols, or ring-opening polymerization of cyclic esters such as lactones and lactides. For its production, p-toluenesulfonic acid or a metal acetate such as zinc acetate, lead acetate or cadmium acid acid, or a catalyst such as sodium alcoholate or lead oxide is required.

[0004]

However, in the case of these conventional catalysts, 1) the catalytic effect is small, 2) side reactions other than polymerization occur, and 3) when they are incorporated as impurities in the produced polymer. It has been pointed out that such problems as impairing the electrical insulating property of the polymer and causing deterioration of the performance of the polymer are caused.

Therefore, the object of the present invention is to provide a catalyst which has an excellent catalytic effect, does not cause a side reaction, and does not cause deterioration of its insulating property or performance deterioration even when contained in the produced polymer. It is to provide a method for producing polyester using the same.

As a result of intensive studies, the present inventors have found that the above problems can be solved by using a hydrolase as a catalyst in the method for producing polyester, and have conceived the present invention.

That is, in order to achieve the above object, claim 1
The invention of 1. is a method for producing a polyester, which is characterized by polymerizing a dicarboxylic acid divinyl ester and a glycol in the presence of a hydrolase.

The invention of claim 2 is characterized in that in the method for producing the polyester of claim 1, the hydrolase is at least one hydrolase selected from the group consisting of lipase, protease and cellulase. .

The invention of claim 3 is characterized in that in the method for producing a polyester of claim 1 or 2, the dicarboxylic acid divinyl ester is a vinyl ester of an aliphatic dicarboxylic acid or a carbocyclic dicarboxylic acid.

The invention of claim 4 is a catalyst for producing polyester, which is characterized by comprising a hydrolase.

The reaction that proceeds in the method for producing a polyester according to the present invention follows the following chemical formula (I).

[0012]

[Chemical 1]

The hydrolase which can be used in the present invention includes lipase, protease, cellulase and the like. Examples of the lipase include Pseudomonas fluorescens, Pseu
domonas species, Candida cylindracea, Porcine pancre
Those derived from us, Rhizopus delemer can be mentioned. Examples of proteases include chymotrypsin, papain, pepsin and the like. As cellulase, for example, Trichoderma, Fusarium, Pse
Those derived from domonas can be mentioned. It is necessary to use at least one of the above hydrolases, but it is also possible to use a combination of two or more depending on the case.

Examples of the carboxylic acid vinyl ester that can be used in the present invention include divinyl oxalate,
Divinyl adipate, divinyl succinate, divinyl glutarate, divinyl piperate, divinyl suberate, divinyl sebacate, etc. Divinyl esters of aliphatic dicarboxylic acids, divinyl phthalate, divinyl terephthalate,
Examples thereof include divinyl esters of carbocyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid divinyl.

Examples of glycols that can be used in the present invention are ethylene glycol, propylene glycol, trimethylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1, Examples thereof include 10-decanediol, pinacol, hydrobenzoin, benzpinacol, cyclohexane 1,4-diol and the like.

In the method for producing a polyester according to the present invention, dicarboxylic acid divinyl ester and glycol as monomers and a hydrolase as a catalyst are contained in the reaction system as essential components, but if necessary, as a reaction diluent. Various solvents such as isopropyl ether and isooctane may be added.

The amounts of the dicarboxylic acid divinyl ester, which is a monomer, and the glycol are not particularly limited, but it is preferable to use them in the same molar amount.

The amount of hydrolase added is not particularly limited, but it is preferable to add 1 g or more of hydrolase to 1 mol of dicarboxylic acid divinyl ester as a monomer. This is because a good yield can be expected in this range.

The reaction temperature and reaction time are not particularly limited, but the reaction temperature is preferably 20 ° C. to 100 ° C., and the reaction time is preferably 5 hours or more. A good yield can be expected in this range. Also,
At a temperature outside the above range, the enzyme may be deactivated and denatured.

[0020]

EXAMPLES Examples and comparative examples of the present invention will be given below, but the present invention is not limited to these examples and the like.

Example 1 A test tube was charged with 0.40 g (2.0 mmo) of vinyl adipate.
l), 0.18 g of 1,4-butanediol (2.0 mm
ol), 0.20 g of Pseudomonas Fluorecens-derived lipase (lipase P), and 10 ml of isopropyl ether were added and the tube was sealed. This test tube was placed in a constant temperature bath at 45 ° C. and shaken at 150 times per minute. After 8 hours, open the test tube and
ml of chloroform was added to the polymerization solution. After ultrasonically dispersing the enzyme, the enzyme was allowed to settle by leaving it for about 1 hour, the enzyme was filtered off with a filter paper, and the organic phase was distilled off under reduced pressure. The residue was dissolved in a small amount of chloroform, poured into a large amount of methanol to precipitate a polymer, which was isolated by filtration and dried to obtain a corresponding polyester. Table 1 shows the yield, Mn (number average molecular weight) and Mw / Mn of the produced polymer.

Example 2 A corresponding polyester was obtained in the same manner as in Example 1 except that the reaction time was 48 hours. Table 1 shows the yield, Mn (number average molecular weight) and Mw / Mn of the produced polymer.

Example 3 A corresponding polyester was obtained in the same manner as in Example 2 except that isooctane was used instead of isopropyl ether. Table 1 shows the yield, Mn (number average molecular weight) and Mw / Mn of the produced polymer.

Example 4 A corresponding polyester was obtained in the same manner as in Example 2 except that 1,6-hexanediol was used instead of 1,4-butanediol. Table 1 shows the yield, Mn (number average molecular weight) and Mw / Mn of the produced polymer.

Example 5 The same procedure as in Example 2 was repeated except that 1,10-decanediol was used instead of 1,4-butanediol.
A corresponding polyester was obtained. Table 1 shows the yield, Mn (number average molecular weight) and Mw / Mn of the produced polymer.

Comparative Example Diethyl adipate was replaced by diethyl adipate.
A treatment was carried out in the same manner as in Example 2 except that 405 g (2 mmol) was used, but no precipitated polymer was obtained.

[0027]

[Table 1]

As can be understood from the above examples, the hydrolase showed good catalytic ability. Furthermore, since the enzymatic reaction works specifically, side reactions are unlikely to occur. In addition, the hydrolase is a protein-based polymer, has a higher insulating property than conventional catalysts, and does not cause a decrease in insulating property even when it is contained in the produced polymer. Furthermore, in the state where the hydrolase is contained in the produced polymer,
It has low activity and does not show the catalytic action that causes the decomposition and deterioration of the polymer like conventional catalysts.

[0029]

As is apparent from the above, according to the present invention, the catalytic effect is excellent, side reactions do not occur,
Further, a catalyst and a method for producing polyester using the catalyst, which does not cause deterioration of the insulating property or performance deterioration even when contained in the produced polymer, are provided.

Claims (4)

[Claims] 1. A method for producing a polyester, which comprises polymerizing a dicarboxylic acid divinyl ester and a glycol in the presence of a hydrolase. 2. The method for producing a polyester according to claim 1, wherein the hydrolase is at least one hydrolase selected from the group consisting of lipase, protease and cellulase. 3. The method for producing a polyester according to claim 1, wherein the dicarboxylic acid divinyl ester is a vinyl ester of an aliphatic dicarboxylic acid or a carbocyclic dicarboxylic acid. 4. A catalyst for producing polyester, which comprises a hydrolase.