KR960005796B1 - Process for the preparation of polyester - Google Patents

Abstract

(a) making soft segment(I) from estertification reaction of dimer acid, which is a mixture of monomer, dimer above 95wt% and trimer of aliphatic acid such as oleic acid, linolenic acid or linoleic acid, and glycol such as 1,4-cyclohexane dimethanol; (b) polycondensating and estertificating the soft segment(I) and the monomer of hard segment(II). It can be used for tubes, hoses and shoes material because it has good properties in stability, heat resistance, soft ability and elastic restoring force.

Description

Polyester ester block copolymer resin and its manufacturing method

The present invention relates to a polyester ester block copolymer resin with improved stabilization properties.

In general, polyester block copolymers have been replaced with vulcanized rubber in rubber materials because of their excellent flexibility and elastic recovery ability, and particularly excellent moldability. Of these polyester block copolymers, polyester ester block copolymers have excellent flexibility and elastic recovery ability, and have superior advantages in heat resistance and moldability compared to vulcanized rubbers. It has been widely used in the manufacture of parts.

Such polyester ester block copolymers have molecular structural properties that require increasing the content of the polyether component in order to improve the rubber properties of the copolymer because the rubber properties depend on the content of the copolymerized polyether component. have.

However, since the ether bond of the polyether component does not have good stability to the external air environment such as heat and humidity, there is a problem that the physical properties such as heat resistance and weather resistance of the polyether ether terpolymer containing the same are deteriorated.

Accordingly, polyether ester block copolymers have been limited in their use.

Many improvements have been studied to reduce the ether linkage of polyether ester block copolymers having the above problems.

As a result, a method of using an aliphatic ester of polycaprolactone using a segment of a polyether ester block copolymer has been proposed. However, polycarrolactone has a low physical stability of its own, which is the final product of the polyether ester block copolymer. There is a problem that the technical limitation that the stability improvement can be made within a low range.

Recently, US Pat. No. 3,954,689 discloses a polyether ester block copolymer constituting a soft segment with dimer acid and an aliphatic glycol component instead of polycaprolactone, but the polyether ester block copolymer produced by this method is industrially There is a problem that the crystallinity and melting point is so low that it is almost impossible to use.

In addition, US Patent No. 4,254,001 discloses a composition using a mixture of poly (alkylene oxide) glycol and dimer acid as a soft segment of a block copolymer. However, the polyether ester block copolymer of this method still has a large number of ether bonds in the molecule, so that the effect of improving stability is insignificant. In addition to the methods described above, another method is to prepare a dimer acid and a glycol component by esterification to protect the crystallinity of the hard segment of the polyether ester block copolymer disclosed in US Pat. No. 4,562,232, and then There is a method of reacting with a polyalkylene oxide glycol component and other acid components, but this method also has the same problem as described in US Pat. No. 4,254,001.

In order to solve the problems caused by the structural characteristics of the polyether ester block copolymer as described above, polyester ester block copolymers which completely exclude the ether bonds in the polyester block copolymer have recently been introduced. Since the polyester ester block copolymer has no ether bond in the molecule, the polyester ester block copolymer has better moldability, elastic modulus, flexibility, and stability than the conventional polyether ester block copolymer, and thus can be used in a wider use than the polyester ester block copolymer.

However, this polyester ester block copolymer has a problem that the soft segment of the block copolymer is composed of ester bonds, so that the stability is better than that of the polyether ester block copolymer, but the hydrolysis resistance is poor.

In addition, the use of dimer acid to improve the hydrolysis resistance of the polyester ester block copolymer decreases the amount of ester bond, thereby improving the hydrolysis resistance of the polyester ester block copolymer, but the segment of the block copolymer is sensitive to heat. There is a problem that the heat resistance and strength is reduced by increasing.

The present invention has been made to solve the above problems of the prior art, the polyester ester block copolymer which can improve the hydrolysis resistance without compromising the inherent heat resistance and mechanical properties of the polyether ester block copolymer The purpose is to provide a method for the preparation of.

It is another object of the present invention to provide a novel polyester ester block copolymer composition suitable for the use of a dustproof agent, a tube, a hose and a shoe material by the above method.

In order to achieve the above object, the present invention provides a method for producing a thermoplastic polyester block copolymer, in which the polycondensation step is carried out by a) the general formula (I) wherein esterification reaction of dimer acid and alicyclic glycol is carried out. Process for producing the soft segment to be displayed, b) The thermoplastic polyester characterized by including the step of ester-reacting and polycondensation-reacting the said soft segment with the monomer component of the hard segment represented by following General formula (II). Provided is a method for preparing a block copolymer.

(In Formula (I), R ¹ is a moiety forming a dimer acid or a lower esterified product thereof, D ¹ is a moiety forming an alicyclic glycol, and in Formula (II), R ² is terephthalic acid, isophthalic acid, old phthalic acid. , Adipic acid, sebacic acid, dimer acid or cyclo nucleic acid dicarboxylic acid, and D ² is an aliphatic glycol having 2 to 8 carbon atoms.)

In addition, the present invention provides a method for producing a thermoplastic polyester block copolymer, in which the polycondensation step produces a soft segment represented by general formula (I) wherein a) esterification of dimer acid and alicyclic glycol is carried out. Step, b) producing a thermoplastic polyester block copolymer comprising a step of subjecting the soft segment to a polycondensation reaction with an esterification reactant of a constituent of a hard segment represented by the following general formula (II). Provide a method.

(In Formula (I), R ¹ is a moiety forming a dimer acid or a lower esterified product thereof, D ¹ is a moiety forming an alicyclic glycol, and in Formula (II), R ² is terephthalic acid, isophthalic acid, old phthalic acid. , Adipic acid, sebacic acid, dimer acid or cyclo nucleic acid dicarboxylic acid, and D ² is an aliphatic glycol having 2 to 8 carbon atoms.)

According to the present invention, the polyester ester block copolymer production method will be described in more detail as follows.

(1) Manufacturing method of soft segment

After dimer acid and alicyclic glycol constituting the soft segment represented by the structural formula (I) were put into a conventional polyester polymerization reaction tube and the reaction tube was sealed, the pressure of the polymerization reaction tube was 1.5 to 3.0 kg / cm 2, The reaction is carried out at a temperature of 150 to 250 ° C. for 1 to 3 hours, and the esterification by-products are removed except the pressure gradually.

(2) polycondensation process

Dicarboxylic acid and glycol constituting the hard segment represented by the structural formula (II) and an additive such as a polymerization catalyst, a stabilizer and, if necessary, a pigment, a heat-resistant agent and a plasticizer are administered, and the temperature of the ester polymerization tube is 150-220 ° C. After reacting with the soft segment prepared in step (1) for 2 hours, the esterification reaction was removed, and the pressure of the polymerization tube was gradually reduced to 1.0 mmHg or less and the temperature of the reaction tube was gradually reduced for 0.5 to 1.0 hour. It is made to polycondensate for 0.5 to 2.0 hours, it raises to 250-270 degreeC, and nitrogen is charged to a polymerization tube, the reaction is complete | finished, and the resin melt is granulated and the polyester ester block copolymer of this invention is manufactured.

This is because, in the above method, first producing the soft segment represented by Structural Formula (I) has the effect of lengthening a considerable length of the soft segment.

In this way, if the considerable length of the soft segment represented by the structural formula (I) is lengthened, the crystal melting point is increased, thereby improving the stability and flexibility of the soft segment.

In the present invention, in addition to the above-described method, the soft segment represented by the formula (I) and the hard segment represented by the formula (II) are produced by an esterification reaction, respectively, and the soft segment represented by the formula (I). And block copolymerization with a hard segment represented by the above formula (II) to produce a polyester ester block copolymer.

In this case, a polyester ester block polymer can be produced in which the number of steps in manufacturing is increased as compared with the method of esterifying the soft segment with the constituent equivalent of the hard segment and then performing the polycondensation reaction.

This method increases the blockability of the hard segments in the block polymer, so that the soft segments of the block copolymer not only improve the stability but also improve the crystallinity and formability of the block copolymer.

This method can increase the blockability in the block polymer as described above, especially when producing a low hardness polyester ester block copolymer having a high content of soft segments, which is a useful method.

The present invention also provides a polyester ester block copolymer composed of a soft segment represented by formula (I) and a hard segment represented by formula (II).

Dimer acid according to the present invention, monomers as well as dimers prepared by the dimerization reaction of US Pat. No. 2,347,562, which is a known method, of 18 linear fatty acids having unsaturated double bonds, such as oleic acid, linoleic acid, niolenic acid. As a compound mixed with trimers, the content of the dimer is preferably 95% by weight or more. In addition, as the alicyclic glycol of the soft segment of the formula (I) according to the present invention, it is possible to use petanediol, cyclohexanediol, cycloheptadiol, but in the present invention, it is particularly preferable to use 1,4-cyclohexanedimethanol. Do.

The content of the soft segment represented by the soft segment represented by Formula (I) and the hard segment represented by Formula (II) is preferably 3 to 80% by weight based on the total resin composition. If the content of the soft segment is less than 3% by weight, there is no bullet transport property of the resin, and if it is 80% by weight or more, there is a problem in that the crystal melting point of the resin is lowered, resulting in poor moldability and limited use.

However, in the case of a special use, the content of the soft segment represented by the above formula (I) may be 80% or more.

The polyester ester block copolymer may exhibit the effect even if a stabilizer, pigment, antistatic agent or the like, such as ordinary heat resistance, weathering material, etc., is added depending on the use in the production.

The polyester ester block copolymer according to the present invention is expected to be usefully used in dustproof materials, tubes, hoses, shoes materials, etc., which require flexibility and rubber properties because of excellent stability, heat resistance, hydrolysis resistance, flexibility, and elastic recovery ability. do.

Next, a preferred embodiment according to the present invention is presented.

However, the following examples are merely provided to more easily understand the present invention, and the present invention is not limited to these examples.

Example 1

32.0 parts by weight of 1,4-cyclohexane dimethanol and dimer acid (trade name: Empoul 1010, manufacturer: Emmery Co., Ltd.-68.0 parts by weight), the reaction tube is sealed, and the pressure of the ester reaction tube 2.0 kg / cm 2, the temperature was raised to 200 ° C., and the esterification reaction was carried out for 2 hours, and while the pressure in the ester reaction tube was gradually reduced to normal pressure over 1 hour, water as a byproduct of the esterification reaction was removed to obtain 1,4. An esterified product consisting of -cyclohexane dimethanol and dimer acid was obtained, and this esterified product was designated as Soft Segment-1.

26.0 parts by weight of the above-mentioned soft segment-1, 41.8 parts by weight of dimethyl terephthalate, 32.0 parts by weight of 1,4-butanediol, 0.1 part by weight of terra-butyl titanate as a catalyst, and a stabilizer (trade name: Iganox 1010, manufacturer: Switch Shivagai 0.10 parts by weight of the domestic product was added to an ester polymerization tube and subjected to transesterification at 200 ° C for 2 hours.

At this time, methanol, which is a byproduct of the reaction, was simultaneously removed from the polymerization tube.

When the methanol distillation is completed, the end point of the transesterification reaction is completed. When the methanol distillation is completed, the pressure of the ester polymerization tube is decompressed to a final pressure of 0.1 mmHg over 1 hour, and the temperature of the reaction tube is raised to 255 ° C. Induction of the sum to remove the over-administered 1,4-butadiol to the outside of the reaction tube, the polycondensation reaction is carried out for 1 hour, and then nitrogen is added to stop the reaction, and further 2kg / The polyester ester block copolymer was granulated as cm 2.

Example 2

A soft segment-1 was prepared in the same manner as in Example 1, 41.8 parts by weight of dimethyl terephthalate, 32.0 parts by weight of 1,4-butanediol, 0.1 part by weight of tetrabutyl titanate, and a stabilizer (trade name: Iganox 1010, manufacturer: Swiss Ciba-Geigy Co., Ltd.) 0.1 part by weight of an ester reaction tube was subjected to a transesterification reaction at 200 ° C. for 2 hours, and then 26.8 parts by weight of the soft segment-1 was added to the ester reaction tube, and condensed in the same manner as in Example 1. The synthesis reaction proceeded and the polyester ester block copolymer granulated.

Example 3

In Example 1, the amount of soft segment-1 was 43.9 parts by weight, the amount of dimentyl terephthalate was 31.7 parts, the amount of 1,4-butanediol was 24.2 parts by weight, the amount of tetrabutyl titanate was 0.1 part by weight, and a stabilizer. The same procedure as in Example 1 was carried out except that the amount of (Product Name: Iganox 1010, Manufacturer: Ciba, Ltd., Switzerland) was 0.1 parts by weight.

Example 4

After preparing Soft Segment-1 in the same manner as in Example 1, 0.1 parts by weight of tetrabutyl titanate was added to 0.1 parts by weight based on 100 parts by weight of the total reactants, and the ester reaction tube was added for 1 hour. The polycondensation reaction was performed for 30 minutes, heating up the temperature to 250 degreeC, reducing pressure of 1.0mmHg, and the soft segment-2 with higher polymerization degree than the soft segment-1 was manufactured.

The same procedure as in Example 1 was repeated except that Soft Segment-2 was used instead of Soft Segment-1 in Example 1.

Example 5

The same procedure as in Example 2 was conducted except that Soft Segment-2 was used instead of Soft Segment-1 in Example 2.

Example 6

In Example 3, it was substantially the same as Example 3 except having used Soft Segment-2 instead of Soft Segment-1.

Example 7

In Example 4, the content of the soft segment 26.0 parts by weight, the content of dimethyl terephthalate 37.0 parts by weight, the content of dimethyl isophthalate 4.8 parts by weight, the content of 1,4-butanediol 27.0 parts by weight, the content of ethylene glycol 5.0 parts by weight, the content of tetrabutyl titanate was 0.1 parts by weight, and the content of the stabilizer (trade name: Iganox 1010, manufacturer: Ciba gauge company Switzerland) was the same as in Example 4 above except that. .

Comparative Example 1

In Example 1, 1.0 parts by weight of the soft segment-1, 53.2 parts by weight of dimethyl terephthalate, 46.6 parts by weight of 1,4-butanediol, 0.1% by weight of tetrabutyl titanate, stabilizer ( A brand name: Iganox 1010, a manufacturer: Sibagai Co., Ltd.) It carried out similarly to Example 1 except having set to 0.1 weight part.

Comparative Example 2

In Example 1, the content of the soft segment-1 is 87.3 parts by weight, the content of dimethyl terephthalate 7.8 parts by weight, the content of 1,4-butanediol 4.6 parts by weight, the content of tetrabutyl titanate 0.1 parts by weight, stabilizer It carried out similarly to Example 1 except having set the content of (Product name: Iganox 1010, a manufacturer: Sivagai Co., Ltd.) to 0.1 weight part.

Comparative Example 3

In Example 1, 35.4% by weight of dimethyl terephthalate, 29.3% by weight of 1,4-butanediol, 35.1% by weight of poly (tetramethylene oxide) glycol having an average molecular weight of 1,000, 0.1% by weight of tetrabutyl titanate, without using soft segments, 0.1 wt% of a stabilizer (product name: Iganox 1010, manufacturer: Ciba-Geigy Co., Ltd.) was added thereto, followed by transesterification and polycondensation.

Comparative Example 4

In Example 4, except that 32.0 parts by weight of 1,4-cyclohexane dimethanol and 68.0 parts by weight of dimer acid (product name: Empoul 1010, manufacturer: Elimer Co., Ltd.) were used instead of Soft Segment-2. The same was done.

The polyester ester block copolymers obtained in Examples 1 to 7 and Comparative Examples 1 to 4 were vacuum dried at 100 ° C. for 6 hours, and then evaluated for various physical properties by the following methods.

[Assessment Methods]

1. Hardness: measured according to ASTM D-2240.

2. Tensile steel, elongation: measured according to ASTM D-638.

3. Flexural modulus: measured according to ASTM D-790.

4. Impact strength: measured according to the Azod Notch method of ASTM D-256.

5. Water resistance: Thick 1/32 inch specimens were treated with boiling water for 500 hours and expressed as retention of tensile strength.

6. Heat resistance: After 1/8 inch thick specimens were treated for 200 hours at 140 ℃ oven temperature, the tensile strength retention was shown.

7. Weather resistance: The specimen with thickness of 1/32 inch was treated at 83 ° C for 100 hours in a wet furnace meta with a xenon arc lamp.

8. Molding: It was judged by cooling time and mold release in mold.

9. Crystal melting point: Measured under the condition of a temperature increase rate of 20 ° C./min with a differential calorimeter.

(Table) Physical properties of polyester ester block copolymer

* NB means non-broken.

Claims (5)

In the method for producing a thermoplastic polyester block copolymer, the polycondensation step is a) a step of esterifying a dimer acid and an alicyclic glycol to produce a soft segment represented by the following general formula (I), b) described above. A method for producing a thermoplastic polyester block copolymer, comprising the step of performing an ester reaction and a polycondensation reaction with a monomer component of a hard segment represented by the general formula (II) described below. (In Formula (I), R ¹ is a moiety forming a dimer acid or a lower esterified product thereof, D ¹ is a moiety forming an alicyclic glycol, and in Formula (II), R ² is terephthalic acid, isophthalic acid, old phthalic acid. , Adipanic acid, sebacic acid, dimer acid or cyclohexanedicarboxylic acid, and D ² is an aliphatic glycol having 2 to 8 carbon atoms. The polyester ester of claim 1, wherein the dimer acid is a mixture of monomers, dimers, and trimers of 18 linear aliphatic acids having unsaturated double bonds, and the content of the double dimer is 95% by weight or more. Process for the preparation of block copolymers. The method of claim 2, wherein the aliphatic acid is selected from the group consisting of oleic acid, linoleic acid and linolenic acid. The method for producing a polyester ester block copolymer according to claim 1, wherein the alicyclic glycol is 1,4-cyclohexanedimethanol. The method of claim 1, wherein the content of the soft segment is 3 to 80% by weight based on the total resin composition.