WO2009123287A1

WO2009123287A1 - Process for producing thermoplastic polyester elastomer and polycarbonate oligomer composition as starting material for the thermoplastic polyester elastomer

Info

Publication number: WO2009123287A1
Application number: PCT/JP2009/056896
Authority: WO
Inventors: 哲祥矢野; 朝光吉原
Original assignee: 日本ポリウレタン工業株式会社
Priority date: 2008-04-03
Filing date: 2009-04-02
Publication date: 2009-10-08
Also published as: JP2009249465A

Abstract

Disclosed is a production process that can cost effectively produce a thermoplastic polyester elastomer which can simultaneously realize excellent heat resistance, thermal aging resistance, water resistance, light stability, low-temperature properties and other properties, has excellent block property retention in molding, has excellent extrudability, and is less likely to cause drawdown during blow molding, i.e., has excellent moldability. Also disclosed is a polycarbonate oligomer composition as a starting material for the thermoplastic polyester elastomer. The production process is a process for producing a thermoplastic polyester elastomer comprising a hard segment and a soft segment bonded to each other, the hard segment being formed of a polyester comprising an aromatic dicarboxylic acid and an aliphatic or alicyclic diol, the soft segment being composed mainly of an aliphatic polycarbonate. In the production process, a polycarbonate oligomer having a terminal alkyl carbonate group or terminal aryl carbonate group in which the proportion of the terminal group is not less than 10% is provided as a starting material, and the polycarbonate oligomer and the polyester hard segment are subjected to a transesterification reaction to obtain the thermoplastic polyester elastomer.

Description

Method for producing thermoplastic polyester elastomer and raw material polycarbonate oligomer composition

The present invention relates to a method for producing a thermoplastic polyester elastomer and a raw material polycarbonate oligomer composition suitable for use in the production. Specifically, it is used for thermoplastic polyester elastomers with excellent heat resistance, light resistance, heat aging resistance, water resistance (also called water aging resistance), low temperature characteristics, etc., especially for various molding materials including fibers, films, and sheets. The present invention relates to a process for producing a thermoplastic polyester elastomer that can be used and a raw material polycarbonate oligomer composition. More specifically, it is suitable for molding materials such as elastic yarns and boots, gears, tubes, packings, etc., for example, applications requiring heat aging resistance, water resistance, low temperature characteristics, heat resistance, etc. for automobiles, home appliance parts, etc. The present invention relates to a method for producing a thermoplastic polyester elastomer useful for joint boots, wire covering materials, and the like, and a raw material polycarbonate oligomer composition thereof.

As thermoplastic polyester elastomers, crystalline polyesters such as polybutylene terephthalate (PBT) and polybutylene naphthalate (PBN) are used as hard segments, and polyoxyalkylene glycols such as polytetramethylene glycol (PTMG) and A polyester having a soft segment such as polycaprolactone (PCL) and polybutylene adipate (PBA) is known and put into practical use (for example, Patent Documents 1 and 2).

Japanese Patent Laid-Open No. 10-17657 Japanese Patent Laid-Open No. 2003-192778

However, polyester polyether type elastomers that use polyoxyalkylene glycols in the soft segment are superior in water resistance and low temperature properties but are inferior in heat aging resistance. Also, polyester polyester type elastomers that use polyester in the soft segment Is known to be inferior in water resistance and low-temperature properties, although it is excellent in heat aging resistance.

In order to solve the above drawbacks, polyester polycarbonate type elastomers using polycarbonate as a soft segment have been proposed (see, for example, Patent Documents 3 to 8).
Japanese Patent Publication No.7-39480 Japanese Patent Laid-Open No. 5-295049 JP-A-6-306202 Japanese Patent Laid-Open No. 10-182782 Japanese Patent Laid-Open No. 2001-206939 Japanese Patent Laid-Open No. 2001-240663

Although the above-mentioned problems are solved, the polyester polycarbonate type elastomer disclosed in these patent documents has a block property that is obtained because the polycarbonate diol elastomer used as a raw material has a low molecular weight. Inferior property (hereinafter, sometimes simply referred to as blockability retention) leads to a problem that the melting point of the polyester polycarbonate type elastomer is lowered. For example, in the case of the joint boot or the wire covering material described above, an automobile engine In applications used in a high temperature environment such as around, lack of heat resistance may be a problem. Patent Documents 4, 7 and 8 disclose that the melting point can be increased by introducing a naphthalate skeleton as a polyester component. However, since introduction of the naphthalate skeleton is expensive, polyester having an inexpensive terephthalate skeleton is disclosed. It is desired to increase the melting point of the components.

On the other hand, in Patent Documents 7 and 8, a production method in which a polyester component that forms a hard segment and a polycarbonate diol component that forms a soft segment are reacted in a molten state to form a block polymer, and then the molecular weight is increased with a chain extender Is disclosed. The production method is an effective method for increasing the molecular weight of the block polymer. However, the block property and block property retention are largely influenced by the reaction in the process of forming the block polymer. It is difficult to improve the block property and the block property retention by the method of increasing the molecular weight with a chain extender after forming the block polymer.

In order to solve this problem, it has been proposed that a polyester composed of an aromatic dicarboxylic acid and an aliphatic or alicyclic diol is reacted with an aliphatic polycarbonate diol having a molecular weight of 5000 to 80000 in a molten state. Yes.
International Publication No. 2007/072748 Pamphlet Japanese Patent Laid-Open No. 2001-240663 International Publication No. 95/27749 Pamphlet

Although the above problems can be solved, polyester polycarbonate type elastomers disclosed in these patent documents are difficult to find in the market for polycarbonates having a molecular weight of 5000 or more, which are used as raw materials. Since the temperature is high and the viscosity is high, the workability at the time of preparation as a raw material is extremely bad, and it is not practically used.
In addition, when transesterification is performed with a high molecular weight polycarbonate diol and a polyester constituting a hard segment, the carbonate bond of the polycarbonate diol is also involved in the transesterification reaction in parallel, and the transesterification rate of each carbonate group is increased. Because they are identical, transesterification occurs randomly. As a result, it is difficult to control the regularity of the molecular weight of the formed soft segment and the block property due to permutation with the hard segment, and a high-performance thermoplastic ester. Elastomers are always difficult to obtain stably, and it is difficult to commercialize them.

In view of the problems of the conventional thermoplastic polyester elastomer, the present invention has excellent heat resistance, heat aging resistance, water resistance (also referred to as water aging resistance), light resistance, low temperature characteristics, etc., and at the time of molding. An object of the present invention is to provide an economical method for producing a thermoplastic polyester elastomer having excellent blockability, extrudability and difficulty in drawing down during extrusion molding and blow molding, and a polycarbonate oligomer composition as a raw material thereof. To do.

That is, the method for producing a thermoplastic polyester elastomer according to the present invention comprises a hard segment comprising a polyester composed of an aromatic dicarboxylic acid and an aliphatic or alicyclic diol, and an aliphatic polycarbonate as claimed in claim 1. A method for producing a thermoplastic polyester elastomer comprising a soft segment comprising a polycarbonate oligomer having a terminal alkyl carbonate group or a terminal aryl carbonate group having a terminal group ratio of 10% or more, and the polycarbonate oligomer and A transesterification reaction with a polyester hard segment is performed.
The method for producing a thermoplastic polyester elastomer according to claim 2 is the polycarbonate according to claim 1, wherein the polycarbonate oligomer has a terminal alkyl carbonate group or a terminal aryl carbonate group having a terminal group ratio of 15% or more. It is characterized by using an oligomer.
The method for producing a thermoplastic polyester elastomer according to claim 3 is characterized in that, in the production method according to claim 1, the number average molecular weight of the polycarbonate oligomer is 1000 to 5000.
The method for producing a thermoplastic polyester elastomer according to claim 4 is characterized in that in the production method according to claim 2, the number average molecular weight of the polycarbonate oligomer is 1000 to 5000.
The method for producing a thermoplastic polyester elastomer according to claim 5 is the method according to any one of claims 1 to 4, wherein the number average molecular weight of the polyester constituting the hard segment is 10,000 to 40,000. Features.
The raw material polycarbonate oligomer composition of the present invention comprises a hard segment composed of a polyester composed of an aromatic dicarboxylic acid and an aliphatic or alicyclic diol, and mainly an aliphatic polycarbonate. A raw material polycarbonate oligomer composition used for producing a thermoplastic polyester elastomer having a soft segment bonded, comprising a polycarbonate oligomer having a terminal alkyl carbonate group or a terminal aryl carbonate group having a terminal group ratio of 10% or more. Features.
The raw material polycarbonate oligomer composition according to claim 7 is the composition according to claim 6, wherein the polycarbonate oligomer is a polycarbonate oligomer having a terminal alkyl carbonate group or a terminal aryl carbonate group having a terminal group ratio of 15% or more. It is characterized by including.
The raw material polycarbonate oligomer composition according to claim 8 is characterized in that, in the composition according to claim 6 or 7, the number average molecular weight of the polycarbonate oligomer is 1000 to 5000.

The present invention makes it possible to stably produce a thermoplastic polyester elastomer having a polycarbonate segment as a soft segment in a short time and at a low cost.
The thermoplastic polyester elastomer obtained by the present invention and the composition thereof are used after maintaining the characteristics of the polyester polycarbonate type elastomer having good heat resistance and excellent heat aging resistance, water resistance, low temperature characteristics and the like. The difference in the reaction rate between the terminal carbonate group and the intramolecular carbonate group of the polycarbonate oligomer makes it possible to introduce a high-molecular-weight polycarbonate soft segment in a short time and greatly improves the block properties of the thermoplastic polyester elastomer. . High melting point provides a high melting point, improves heat resistance, and improves mechanical properties such as hardness, tensile strength, and elastic modulus. In addition, the improvement of the block property holding property suppresses the fluctuation of the block property during the molding process, so that the uniformity of the quality of the molded product can be enhanced. In addition, recyclability is enhanced by the characteristics, which can lead to environmental load and cost reduction. The thermoplastic polyester elastomer obtained in the present invention has the above-described excellent properties and advantages, and can be used for various molding materials including fibers, films and sheets. It is also suitable for molding materials such as elastic yarns and boots, gears, tubes, packings, etc., for example, applications such as automobiles and home appliance parts that require heat aging resistance, water resistance, low temperature characteristics, specifically, It is useful for applications such as joint boots and wire coating materials. In particular, it can be suitably used as a material for parts that require high heat resistance, such as joint boots used around automobile engines and wire coating materials.
Further, the method of the thermoplastic polyester elastomer of the present invention does not require a complicated process, and is advantageous in that a high-quality thermoplastic polyester elastomer having the above characteristics can be produced economically and stably under easy conditions. Have
Furthermore, the polycarbonate oligomer composition as a raw material for a polyester elastomer of the present invention is characterized by low viscosity and low melting temperature in addition to the selective reactivity of the end groups. For this reason, conventional high molecular weight polycarbonate diols were impossible due to their high viscosity and high melting point. After production, they were once filled into product tanks, containers, drum cans / petroleum cans, etc., and then heated during polyester elastomer synthesis. And can be melted and used separately and has good workability. Therefore, it is possible to produce the polyester elastomer by transporting the polycarbonate oligomer composition of the raw material for the polyester elastomer to another place. It was also possible to sell it as a segment-forming polycarbonate oligomer. This can contribute to industrial development.

Hereafter, the manufacturing method of the thermoplastic polyester elastomer of this invention and its raw material polycarbonate oligomer composition are demonstrated in detail.
In the production of the thermoplastic polyester elastomer of the present invention, the aromatic dicarboxylic acid constituting the hard segment polyester is not particularly limited, and the main aromatic dicarboxylic acid is terephthalic acid or naphthalene. A dicarboxylic acid is desirable.

Further, in the production of the thermoplastic polyester elastomer of the present invention, the aliphatic or alicyclic diol constituting the hard segment polyester is widely used as a general aliphatic or alicyclic diol, and is not particularly limited. An alkylene glycol having a number of 2 to 8 is desirable. Specific examples include ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, and the like. Most preferred are 1,4-butanediol and 1,4-cyclohexanedimethanol.

As the component constituting the hard segment polyester, those comprising a butylene terephthalate unit or a butylene naphthalate unit are preferable from the viewpoint of physical properties, moldability and cost performance. In the case of naphthalate units, 2,6 are preferred.

Moreover, the aromatic polyester suitable as polyester which comprises the hard segment in the thermoplastic polyester elastomer of this invention can be easily obtained according to the manufacturing method of a normal polyester. Such polyester preferably has a number average molecular weight of 10,000 to 40,000.
When a polyester having a number average molecular weight of less than 10,000 is used as the polyester constituting the hard segment, since the polyester elastomer cannot be constituted with a sufficient hard segment chain length, the resulting polyester elastomer has a low melting point and sufficient tensile strength and Unable to obtain flexural modulus.
When a polyester with a number average molecular weight exceeding 40,000 is used as the polyester constituting the hard segment, the polyester elastomer is poorly compatible with the polycarbonate oligomer that is a soft segment component during the production of the polyester elastomer, and the resulting polyester elastomer has sufficient tensile strength. I can't get it.

Moreover, the aliphatic polycarbonate oligomer which forms the soft segment in the thermoplastic polyester elastomer of the present invention is obtained by reacting an aliphatic polyol with a carbonate monomer selected from the group consisting of dialkyl carbonate, diaryl carbonate and alkylene carbonate. A polycarbonate oligomer is formed while removing by-product alcohols from the reaction mixture containing the aliphatic polyol and the carbonate monomer.
The carbonate monomer used in the present invention is selected from the group consisting of dialkyl carbonate, diaryl carbonate, and alkylene carbonate. Examples of the dialkyl carbonate include those having an alkyl group having 1 to 12 carbon atoms, such as dimethyl carbonate, diethyl carbonate, and dibutyl carbonate. Examples of the diaryl carbonate include those having an aryl group having 6 to 20 carbon atoms, such as diphenyl carbonate and dinaphthyl carbonate. The alkylene carbonate has a 5- to 7-membered ring, and specific examples include ethylene carbonate and propylene carbonate. These carbonate monomers are used alone or in combination of two or more.

The aliphatic polyol used in the present invention is preferably an aliphatic diol mainly having 2 to 12 carbon atoms. Examples of these aliphatic diols include ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 2, 2-dimethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, etc. Can be mentioned. In particular, aliphatic diols having 5 to 12 carbon atoms are preferred from the viewpoint of flexibility and low temperature characteristics of the obtained thermoplastic polyester elastomer. These components may be used alone or in combination of two or more as necessary, based on the case described below.

The above-mentioned aliphatic polycarbonate oligomer is not necessarily composed only of a polycarbonate component, and may be obtained by copolymerizing a small amount of other glycol, dicarboxylic acid, ester compound, ether compound and the like.
The copolymer component can be used to such an extent that the effect of the aliphatic polycarbonate segment is not substantially lost.

As long as the thermoplastic polyester elastomer produced in the present invention does not lose the effect of the invention, as a soft segment, for example, polyalkylene glycol such as polyethylene glycol and polyoxytetramethylene glycol, polyester such as polycaprolactone and polybutylene adipate Copolymerization components such as may be introduced.

In the thermoplastic polyester elastomer produced in the present invention, the mass part ratio of the polyester constituting the hard segment and the aliphatic polycarbonate oligomer and copolymer component constituting the soft segment is generally hard segment: soft segment = 30: 70. 95: 5, preferably 40:60 to 90:10, more preferably 45:55 to 87:13, and most preferably 50:50 to 85:15.

The thermoplastic polyester elastomer produced in the present invention has a hard segment composed of a polyester composed of an aromatic dicarboxylic acid and an aliphatic or alicyclic diol as described above and a soft segment composed mainly of an aliphatic polycarbonate segment. Is a thermoplastic polyester elastomer. Here, the term “bonded” means that the hard segment and the soft segment are not bonded by a chain extender such as an isocyanate compound, but the units constituting the hard segment and the soft segment are directly bonded by an ester bond or a carbonate bond. The state is preferable.
For example, it is preferable to obtain the polyester constituting the hard segment, the polycarbonate oligomer constituting the soft segment, and if necessary, various copolymerization components while melting and repeating the transesterification / condensation and depolymerization reactions for a certain period of time ( Hereinafter, it may be referred to as a blocking reaction).

The above-mentioned blocking reaction is preferably carried out at a temperature within the range of the melting point of the polyester constituting the hard segment to the melting point + 30 ° C. In this reaction, the concentration of the active catalyst in the system is arbitrarily set according to the temperature at which the reaction is carried out.

The catalyst may be a normal catalyst, for example, titanium compounds such as titanium tetrabutoxide and potassium oxalate titanate, or one or more tin compounds such as dibutyltin oxide and monohydroxybutyltin oxide. The catalyst may be pre-existing in the polyester or polycarbonate, in which case it need not be added anew. Furthermore, the catalyst in the polyester or polycarbonate may be partially or substantially completely deactivated in advance by any method. For example, when titanium tetrabutoxide is used as a catalyst, for example, phosphorous compounds such as phosphorous acid, phosphoric acid, triphenyl phosphate, tristriethylene glycol phosphate, orthophosphoric acid, triphenyl phosphite, trimethyl phosphate, trimethyl phosphite, etc. Although deactivation is performed by adding, it is not necessarily restricted to this.

The above reaction can be carried out by arbitrarily determining the combination of reaction temperature, catalyst concentration and reaction time. That is, the appropriate values of the reaction conditions vary depending on various factors such as the type and amount ratio of the hard segment and the soft segment to be used, the shape of the apparatus to be used, and the stirring condition.

The thermoplastic polyester elastomer of the present invention may contain a tri- or higher functional polycarboxylic acid or polyol only in a small amount. For example, trimellitic anhydride, benzophenone tetracarboxylic acid, trimethylolpropane, glycerin and the like can be used.

In the present invention, it is preferred that the hard segment is composed of polybutylene terephthalate units, and the thermoplastic polyester elastomer obtained has a melting point of 200 to 225 ° C. 205 to 225 ° C is more preferable.
In the present invention, the hard segment is preferably composed of polybutylene naphthalate units, and the thermoplastic polyester elastomer obtained preferably has a melting point of 215 to 240 ° C. 220 to 240 ° C. is more preferable.

When the hard segment is a polybutylene terephthalate unit or a polybutylene naphthalate unit, a commercially available polyester such as polybutylene terephthalate or polybutylene naphthalate can be used, which is advantageous in terms of economy.

Further, the thermoplastic polyester elastomer of the present invention has 50% elongation retention at break after the heat aging test and after the water aging test of the thermoplastic polyester elastomer composition evaluated by the method described in the measurement method section. It is preferable that it is above and 80% or more.

In the present invention, it is preferable to optimize the molecular weight and the terminal group ratio of the polycarbonate oligomer as a raw material. That is, a polyester constituting a hard segment in the above-described thermoplastic polyester elastomer of the present invention and an aliphatic polycarbonate oligomer having a molecular weight of 1000 to 5000 having a terminal alkyl carbonate group or a terminal aryl carbonate group having a terminal group ratio of 15% or more. It is preferable to produce by reacting in a molten state.

The ratio of the alkyl carbonate group or aryl carbonate group in the terminal group of the polycarbonate oligomer needs to be 10% or more, and preferably 15% or more.
When the proportion of alkyl carbonate group or aryl carbonate group in the terminal group is less than 10%, the effect of improving transesterification efficiency due to the difference in reaction rate with the terminal OH group of the polycarbonate oligomer is difficult to be obtained, and sufficient blocking property is maintained. As a result, a polyester elastomer having good physical properties cannot be obtained. To explain further, when the content is less than 10%, the reaction system becomes too uniform, making it difficult for the polycarbonate oligomer part and the polyester hard segment part to form a sea-island structure, resulting in low elasticity. Since the elongation is reduced and the molecular weight of the polyester hard segment portion is reduced, the cohesive force required as the hard segment is lowered, and the durability of the elastomer is lowered. When the proportion of the alkyl carbonate group or aryl carbonate group in the terminal group exceeds 85%, the transesterification is difficult to proceed, and the physical properties deteriorate. Therefore, it is preferably 85% or less.

The larger the molecular weight of the aliphatic polycarbonate oligomer, the higher the block property retention and block property. When the number average molecular weight of the polycarbonate oligomer is less than 1000, the sea-island structure of the polycarbonate oligomer portion and the polyester hard segment portion is unclear, resulting in low elasticity, and the polycarbonate chain introduced as a soft segment. A polyester elastomer having a sufficient physical property with insufficient length cannot be obtained. The molecular weight of the polycarbonate oligomer is more preferably 2000 or more in terms of number average molecular weight for the same reason as above. The upper limit of the molecular weight of the polycarbonate oligomer is preferably a number average molecular weight of 5000 or less in view of the viscosity during handling and the production efficiency of the oligomer. The higher the molecular weight of the aliphatic polycarbonate oligomer, the more advantageous in terms of obtaining a polyester elastomer having a higher block property. However, the higher the molecular weight, the higher the melting point of the polycarbonate oligomer, and the higher the molecular weight, the higher the viscosity at the time of melting. Thus, when the number average molecular weight exceeds 5,000, handling such as taking out, filling and charging becomes difficult. Also, the strength tends to decrease. Even if a polyester elastomer having a number average molecular weight of 10,000 to higher is used, the physical properties of the resulting polyester elastomer are hardly significant.

It is possible to contain a free alkyl carbonate monomer or aryl carbonate monomer regardless of the ratio of the end group of the alkyl carbonate group or aryl carbonate group to the end group of the polycarbonate oligomer. The content of the free alkyl carbonate monomer or aryl carbonate monomer is preferably 5% or less, more preferably 1% or less, based on the polycarbonate oligomer.
When the content of free alkyl carbonate monomer or aryl carbonate monomer exceeds 10%, it becomes difficult to control the chain length of the carbonate chain introduced as a soft segment, and at the same time, the monomer is scattered outside the reactor during the production process of the polyester elastomer. However, it may not be effective.

The method for synthesizing the polycarbonate oligomer is not limited.
For example, as a method for producing the above high molecular weight aliphatic polycarbonate oligomer, the above aliphatic diol and the above carbonate, that is, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, diisopropyl carbonate, dibutyl carbonate, dimethyl carbonate, diphenyl carbonate, etc. It can obtain by making it react.

As another method for producing an aliphatic polycarbonate oligomer, it is possible to react an aliphatic polycarbonate diol with dimethyl carbonate, diethyl carbonate, dipropyl carbonate, diisopropyl carbonate, dibutyl carbonate, dimethyl carbonate, diphenyl carbonate, etc. It is.

For example, a commercially available polycarbonate diol composed of 1,6-hexanediol (molecular weight 2000) and diethyl carbonate are charged under normal pressure to pressure and heated to remove ethanol generated by the reaction, while reacting in a molten state. It can be obtained by making it progress. The method for removing ethanol is not limited. Most ethanol is removed at reaction temperatures above 150 ° C. Further examples include a method of reducing the pressure with a vacuum pump or an ejector, a method of circulating an inert gas, and the like.
The charge molar ratio of polycarbonate diol to diethyl carbonate in the above reaction [polycarbonate diol composed of diethyl carbonate / 1,6-hexanediol (molecular weight 2000)] is preferably in the range of 1/100 to 50/100. More preferably, it is in the range of / 100 to 20/100. Outside this range, it is difficult to ensure the desired molecular weight. The temperature in the reaction vessel when the above raw materials are charged is preferably 100 to 130 ° C. After charging the raw materials, the temperature is raised to 180-220 ° C and the reaction is allowed to proceed for 30-120 minutes. It is preferable to gradually reduce the pressure in the reaction can from normal pressure to 530 Pa or less to remove ethanol desorbed by the reaction.

The above-described method using a commercially available polycarbonate diol can easily produce an aliphatic polycarbonate oligomer having an arbitrary desired end group ratio, and the production is an apparatus for producing the thermoplastic polyester elastomer of the present invention. Can also be performed on the implant prior to the production of the thermoplastic polyester elastomer.

In the method for producing a thermoplastic polyester elastomer of the present invention, a composition can be obtained by blending various additives depending on the purpose. Additives include known hindered phenol-based, sulfur-based, phosphorus-based, amine-based antioxidants, hindered amine-based, triazole-based, benzophenone-based, benzoate-based, nickel-based, salicyl-based light stabilizers, antistatic agents, etc. Agents, lubricants, molecular modifiers such as peroxides, epoxy compounds, isocyanate compounds, compounds having reactive groups such as carbodiimide compounds, metal deactivators, organic and inorganic nucleating agents, neutralizing agents, control agents Acid agents, antibacterial agents, fluorescent brighteners, fillers, flame retardants, flame retardant aids, organic and inorganic pigments, and the like can be added.

The thermoplastic polyester elastomer composition of the present invention is formed from a melt by ordinary molding techniques such as injection molding, flat film extrusion, extrusion blow molding, and coextrusion.

In the present invention, it is preferable to produce by reacting a polyester composed of an aromatic dicarboxylic acid and an aliphatic or alicyclic diol and the aliphatic polycarbonate oligomer in a molten state. The reaction may be carried out in a plurality of stages. If the requirements are satisfied, the production conditions and the like are not limited, but for example, the following method is preferable.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but is not limited thereto. In this specification, each measurement was performed according to the following method.
(1) Melting point: Measured by increasing the temperature from room temperature to 20 ° C./min using DSC.
(2) Tensile strength at break: measured in accordance with JIS K6251.
(3) Flexural modulus: measured based on ASTM D790.
(4) Heat aging resistance: Treated at 150 ° C. for 125 days using a gear type hot air dryer, and measured elongation retention at break based on ASTM D638.
(5) Water resistance: The elongation retention at break after treatment at 100 ° C. for 2 weeks was measured based on ASTM D638.
(6) Terminal OH group and terminal ethyl group of aliphatic polycarbonate oligomer The hydroxyl value (mg-KOH / g) was analyzed by the acetyl value method. The molecular end ethyl group and allyl group (unit: mg-KOH / g) are the amounts of ethyl group and allyl group (unit: mmol / g) analyzed by ¹ H-NMR converted to KOH mass. . (See JP 2007-154070)
(7) Number average molecular weight of aliphatic polycarbonate oligomer It measured on the following conditions using the GPC measuring apparatus (HLC8820 by Tosoh Corp.).
Column: TSKgel G4000HXL, 1 unit G3000HXL, 1 unit G2000HXL, 2 Eluent: THF
Flow rate: 1 ml / min Measurement temperature: 40 ° C
Detector: RI

Example 1
[Production of aliphatic polycarbonate oligomer]
Production method of aliphatic polycarbonate oligomer (polycarbonate oligomer 1):
A reactor equipped with a stirrer, thermometer, and rectifying column was charged with 824 parts by weight of 1,6-hexanediol, 800 parts by weight of diethyl carbonate and 0.3 parts by weight of lead acetate, and the temperature was raised to 130 ° C. The temperature was raised to 190 ° C. for 24 hours. During this time, by-product ethanol was removed while maintaining the temperature of the rectification column at 80 to 90 ° C. Thereafter, while maintaining the temperature at 190 ° C., the pressure in the reactor was gradually reduced to 1300 Pa in 4 hours. The contents were cooled to obtain polycarbonate oligomer 1.
The obtained polycarbonate oligomer 1 has a terminal ethyl group of 10.9 mg-KOH / g, a terminal OH group of 24.9 mg-KOH / g (the ratio of the terminal ethyl carbonate group to the terminal group is 30%), and the number average molecular weight is 3100. The kinematic viscosity at 75 ° C. was 8400 mm ² / s.
[Production of thermoplastic polyester elastomer]
100 parts by weight of polybutylene terephthalate (PBT) having a number average molecular weight of 30000 and 45 parts by weight of (polycarbonate oligomer 1) having a number average molecular weight of 3100 prepared by the above method were stirred at 230 to 245 ° C. and 130 Pa for 1 hour, After confirming that the resin became transparent, the contents were taken out and cooled to obtain polymer 1 (thermoplastic polyester elastomer).
The physical properties of the obtained polymer 1 were measured, and the results are shown in Table 1. The polymer 1 obtained in this example had good properties and high quality.

Example 2
[Production of aliphatic polycarbonate oligomer]
Method for producing aliphatic polycarbonate oligomer (polycarbonate oligomer 2):
100 parts by mass of 1,6-hexanediol and 4.0 parts by mass of diethyl carbonate were charged, respectively, and reacted at a temperature of 190 ° C. and 1300 Pa. After 4 hours, the contents were cooled to obtain polycarbonate oligomer 2.
The obtained polycarbonate oligomer 2 has a terminal ethyl group of 10 mg-KOH / g, a terminal OH group of 39 mg-KOH / g (the ratio of the terminal ethyl carbonate group to the terminal group is 20%), and the number average molecular weight is 2300. The kinematic viscosity at 75 ° C. was 2700 mm ² / s.
[Production of thermoplastic polyester elastomer]
100 parts by weight of polybutylene terephthalate (PBT) having a number average molecular weight of 30000 and 45 parts by weight of (polycarbonate oligomer 2) having a number average molecular weight of 2300 prepared by the above method were stirred at 230 to 245 ° C. under 130 Pa for 1 hour, After confirming that the resin became transparent, the contents were taken out and cooled to obtain polymer 2 (thermoplastic polyester elastomer).
The physical properties of the obtained polymer 2 were measured, and the results are shown in Table 1. The polymer 2 obtained in this example had good properties and high quality.

Example 3
[Production of aliphatic polycarbonate oligomer]
Method for producing aliphatic polycarbonate oligomer (polycarbonate oligomer 3):
100 parts by mass of a copolymer (non-crystalline) of 1,6-hexanediol and 3-methyl-1,5-pentanediol and 8.0 parts by mass of diethyl carbonate were charged and reacted at a temperature of 205 ° C. and 1300 Pa. . After 2 hours, the contents were cooled to obtain polycarbonate oligomer 3.
The obtained polycarbonate oligomer 3 has a terminal ethyl group of 38 mg-KOH / g, a terminal OH group of 15 mg-KOH / g (the ratio of the terminal ethyl carbonate group to the terminal group is 72%), and the number average molecular weight is 2100. The kinematic viscosity at 75 ° C. was 2900 mm ² / s.
[Production of thermoplastic polyester elastomer]
100 parts by weight of polybutylene terephthalate (PBT) having a number average molecular weight of 30000 and 45 parts by weight of (polycarbonate oligomer 3) having a number average molecular weight of 2100 prepared by the above method were stirred at 230 to 245 ° C. and 130 Pa for 1 hour, After confirming that the resin became transparent, the contents were taken out and cooled to obtain polymer 3 (thermoplastic polyester elastomer).
The physical properties of the obtained polymer 3 were measured, and the results are shown in Table 1. The polymer 3 obtained in this example had good properties and high quality.

Example 4
[Production of aliphatic polycarbonate oligomer]
100 parts by mass of a copolymer (non-crystalline) of 1,6-hexanediol and 1,5-pentanediol and 8.0 parts by mass of diethyl carbonate were respectively charged and reacted at a temperature of 205 ° C. and 1300 Pa. After 2 hours, the contents were cooled to obtain polycarbonate oligomer 4.
The obtained polycarbonate oligomer 4 has a terminal ethyl group of 35 mg-KOH / g, a terminal OH group of 16 mg-KOH / g (the ratio of the terminal ethyl carbonate group to the terminal group is 69%), and the number average molecular weight is 2200. The kinematic viscosity at 75 ° C. was 3500 mm ² / s.
[Production of thermoplastic polyester elastomer]
230 parts by mass of polybutylene terephthalate (PBT) having a number average molecular weight of 30000 was added to 100 parts by mass of the polycarbonate oligomer inherent in the reactor (mass ratio of PBT / polycarbonate oligomer = 100/43), 230 to 245 ° C., The mixture was stirred for 1 hour under 130 Pa, and it was confirmed that the resin became transparent. The contents were taken out and cooled to obtain polymer 4 (thermoplastic polyester elastomer).
The physical properties of the obtained polymer 4 were measured, and the results are shown in Table 1. The polymer 4 obtained in this example had good properties and high quality.

Example 5
[Production of aliphatic polycarbonate oligomer]
Method for producing aliphatic polycarbonate oligomer (polycarbonate oligomer 5):
(1,6-hexanediol type) 100 parts by mass and 4 parts by mass of diethyl carbonate were charged, respectively, and reacted at a temperature of 205 ° C. and 130 Pa for 2 hours. The contents were 5 mg-KOH / g terminal ethyl, 22 mg-KOH / g terminal OH group, and the number average molecular weight was 4050. Furthermore, 2 parts by mass of diethyl carbonate was charged and reacted at a temperature of 205 ° C. and 1300 Pa. After 2 hours, the contents were cooled to obtain polycarbonate oligomer 5.
The obtained polycarbonate oligomer 6 has a terminal ethyl group of 5 mg-KOH / g, a terminal OH group of 22 mg-KOH / g (the ratio of the terminal ethyl carbonate group to the terminal group is 19%), and the number average molecular weight is 4200. The kinematic viscosity at 75 ° C. was 18000 mm ² / s.
[Production of thermoplastic polyester elastomer]
100 parts by weight of polybutylene terephthalate (PBT) having a number average molecular weight of 30000 and 45 parts by weight of (polycarbonate oligomer 5) having a number average molecular weight of 4200 prepared by the above method were stirred at 230 to 245 ° C. and 130 Pa for 1 hour, After confirming that the resin became transparent, the contents were taken out and cooled to obtain polymer 5 (thermoplastic polyester elastomer).
The physical properties of the obtained polymer 5 were measured, and the results are shown in Table 1. The polymer 5 obtained in this example had good properties and high quality.

Example 6
[Production of aliphatic polycarbonate oligomer]
Method for producing aliphatic polycarbonate oligomer (polycarbonate oligomer 6):
100 parts by mass of 1,6-hexanediol and 2.6 parts by mass of diethyl carbonate were charged, respectively, and reacted at a temperature of 190 ° C. and 1300 Pa. After 2 hours, the contents were cooled to obtain polycarbonate oligomer 6.
The obtained polycarbonate oligomer 6 has a terminal ethyl group of 7 mg-KOH / g, a terminal OH group of 29 mg-KOH / g (the ratio of the terminal ethyl carbonate group to the terminal group is 19%), and the number average molecular weight is 3100. The kinematic viscosity at 75 ° C. was 7500 mm ² / s.
[Production of thermoplastic polyester elastomer]
100 parts by mass of polybutylene terephthalate (PBT) having a number average molecular weight of 30000 and 45 parts by mass of (polycarbonate oligomer 6) having a number average molecular weight of 3100 prepared by the above method were stirred at 230 to 245 ° C. under 130 Pa for 1 hour, After confirming that the resin became transparent, the contents were taken out and cooled to obtain polymer 6 (thermoplastic polyester elastomer).
The physical properties of the obtained polymer were measured, and the results are shown in Table 1. The polymer 1 obtained in this example had good properties and high quality.

Example 7
[Production of thermoplastic polyester elastomer]
(Polycarbonate oligomer 6) 43 having 100 parts by mass of polybutylene naphthalate (PBN) having a number average molecular weight of 30000 and a number average molecular weight of 3100 prepared by the above method (the ratio of terminal ethyl carbonate groups to terminal groups is 19%) The mixture was stirred at 245 to 260 ° C. and 130 Pa for 1 hour to confirm that the resin became transparent, and the contents were taken out and cooled to obtain polymer 7 (thermoplastic polyester elastomer). The physical properties of the obtained polymer 7 were measured, and the results are shown in Table 1. The polymer 7 obtained in this example has the same block properties and block properties as the thermoplastic polyester elastomer obtained in example 6. It had retention and had a higher melting point and higher quality than the thermoplastic polyester elastomer obtained in Example 6.

Example 8
[Production of aliphatic polycarbonate oligomer]
Method for producing aliphatic polycarbonate oligomer (polycarbonate oligomer 8):
100 parts by mass of 1,6-hexanediol and 5 parts by mass of diethyl carbonate were charged, respectively, and reacted at a temperature of 190 ° C. and 1300 Pa. After 2 hours, the contents were cooled to obtain polycarbonate oligomer 8.
The obtained polycarbonate oligomer 8 has a terminal ethyl group of 7 mg-KOH / g, a terminal OH group of 12 mg-KOH / g (the ratio of the terminal ethyl carbonate group to the terminal group is 37%), and the number average molecular weight is 5900, The kinematic viscosity at 75 ° C. was 52000 mm ² / s.
[Production of thermoplastic polyester elastomer]
100 parts by mass of polybutylene terephthalate (PBT) having a number average molecular weight of 30000 and 45 parts by mass of (polycarbonate oligomer 8) having a number average molecular weight of 5900 prepared by the above method were stirred at 230 to 245 ° C. and 130 Pa for 1 hour, After confirming that the resin became transparent, the contents were taken out and cooled to obtain polymer 8 (thermoplastic polyester elastomer).
The physical properties of the obtained polymer were measured, and the results are shown in Table 1. The polymer 8 obtained in this example had good properties and high quality. However, in the synthesis work of this example, the melting temperature of the polycarbonate diol having a number average molecular weight of more than 5000 and the number average molecular weight of 5900 is high and the viscosity is high, so the melting and charging work into the reactor is very difficult. It was.

Example 9
[Production of aliphatic polycarbonate oligomer]
Production method of aliphatic polycarbonate oligomer (polycarbonate oligomer 9):
100 parts by mass of 1,6-hexanediol and 6 parts by mass of diethyl carbonate were charged, respectively, and reacted at a temperature of 190 ° C. and 1300 Pa. After 2 hours, the contents were cooled to obtain polycarbonate oligomer 9.
The obtained polycarbonate oligomer 9 has a terminal ethyl group of 4 mg-KOH / g, a terminal OH group of 32 mg-KOH / g (the ratio of the terminal ethyl carbonate group to the terminal group is 11%), and the number average molecular weight is 3100. The kinematic viscosity at 75 ° C. was 7000 mm ² / s.
[Production of thermoplastic polyester elastomer]
100 parts by weight of polybutylene terephthalate (PBT) having a number average molecular weight of 30000 and 45 parts by weight of (polycarbonate oligomer 9) having a number average molecular weight of 3100 prepared by the above method were stirred at 230 to 245 ° C. and 130 Pa for 1 hour, After confirming that the resin became transparent, the contents were taken out and cooled to obtain polymer 9 (thermoplastic polyester elastomer).
The physical properties of the obtained polymer 9 were measured, and the results are shown in Table 1. The polymer 9 obtained in this example had good properties and high quality. However, since the terminal group ratio of the polycarbonate oligomer 9 was 11%, the physical properties were slightly inferior compared with the case where the polycarbonate oligomer having a terminal group ratio of 15% or more was used.

Example 10
[Production of aliphatic polycarbonate oligomer]
Method for producing aliphatic polycarbonate oligomer (polycarbonate oligomer 10):
100 parts by mass of 1,6-hexanediol and 25 parts by mass of diethyl carbonate were charged, respectively, and reacted at a temperature of 190 ° C. and 1300 Pa. After 4 hours, the contents were cooled to obtain polycarbonate oligomer 10.
The obtained polycarbonate oligomer 10 has a terminal ethyl group of 40 mg-KOH / g, a terminal OH group of 160 mg-KOH / g (the ratio of the terminal ethyl carbonate group to the terminal group is 20%), and the number average molecular weight is 600. The kinematic viscosity at 75 ° C. was 10 mm ² / s or less.
[Production of thermoplastic polyester elastomer]
100 parts by weight of polybutylene terephthalate (PBT) having a number average molecular weight of 30000 and 45 parts by weight of (polycarbonate oligomer 10) having a number average molecular weight of 600 prepared by the above method were stirred at 230 to 245 ° C. and 130 Pa for 1 hour, After confirming that the resin became transparent, the contents were taken out and cooled to obtain polymer 10 (thermoplastic polyester elastomer).
Each physical property of the obtained polymer 10 was measured, and the result is shown in Table 1. The polymer 10 obtained in this example had good properties and high quality. However, since the number average molecular weight of the polymer 10 was as small as less than 1000, the sea-island structure was unclear, the elasticity was small, and there was almost no elongation.

Example 11
[Production of aliphatic polycarbonate oligomer]
Method for producing aliphatic polycarbonate oligomer (polycarbonate oligomer 11):
100 parts by mass of 1,6-hexanediol and 12 parts by mass of diethyl carbonate were charged, respectively, and reacted at a temperature of 190 ° C. and 1300 Pa. After 4 hours, the contents were cooled to obtain polycarbonate oligomer 11.
The obtained polycarbonate oligomer 11 has a terminal ethyl group of 48 mg-KOH / g, a terminal OH group of 5 mg-KOH / g (the ratio of the terminal ethyl carbonate group to the terminal group is 91%), and the number average molecular weight is 2100. The kinematic viscosity at 75 ° C. was 2900 mm ² / s.
[Production of thermoplastic polyester elastomer]
100 parts by weight of polybutylene terephthalate (PBT) having a number average molecular weight of 30000 and 45 parts by weight of (polycarbonate oligomer 11) having a number average molecular weight of 2100 prepared by the above method were stirred at 230 to 245 ° C. and 130 Pa for 1 hour, After confirming that the resin became transparent, the contents were taken out and cooled to obtain polymer 11 (thermoplastic polyester elastomer).
The physical properties of the obtained polymer 11 were measured, and the results are shown in Table 1. The polymer 1 obtained in this example had good properties and high quality. However, since the terminal group ratio of the polycarbonate oligomer 11 was 92%, the physical properties were slightly inferior to those of the polycarbonate oligomer having a terminal group ratio of 85% or less.

Comparative Example 1
[Production of thermoplastic polyester elastomer]
230 parts by mass of 100 parts by mass of polybutylene terephthalate (PBT) having a number average molecular weight of 30000 and 43 parts by mass of 1,6-hexanediol having a number average molecular weight of 2000 (the ratio of terminal ethyl carbonate groups to terminal groups is 0%) The mixture was stirred at 245 ° C. and 130 Pa for 10 minutes to confirm that the resin became transparent. The contents were taken out and cooled to obtain polymer 21 (thermoplastic polyester elastomer). The physical properties of the obtained polymer were measured, and the results are shown in Table 2. The polymer 21 obtained in this comparative example was poor in heat aging resistance and low quality. Moreover, since the number average molecular weight was low, the bending elastic modulus could not be measured.

Comparative Example 2
[Production of thermoplastic polyester elastomer]
230 parts by weight of 100 parts by weight of polybutylene terephthalate (PBT) having a number average molecular weight of 30000 and 43 parts by weight of 1,6-hexanediol having a number average molecular weight of 30000 (the ratio of terminal ethyl carbonate groups in the terminal groups is 0%) The mixture was stirred at ˜245 ° C. and 130 Pa for 10 minutes to confirm that the resin became transparent, and the contents were taken out and cooled to obtain polymer 22 (thermoplastic polyester elastomer). The physical properties of the obtained polymer were measured, and the results are shown in Table 1. The polymer 22 obtained in this comparative example was poor in heat aging resistance and low quality. Moreover, since the molecular weight was low, the flexural modulus could not be measured.

Comparative Example 3
[Production of thermoplastic polyester elastomer]
230 parts by mass of 100 parts by mass of polybutylene terephthalate (PBT) having a number average molecular weight of 30000 and 1,6 hexanediol having a number average molecular weight of 5000 (the ratio of terminal ethyl carbonate groups to terminal groups is 0%) The mixture was stirred at ˜245 ° C. and 130 Pa for 10 minutes to confirm that the resin became transparent, and the contents were taken out and cooled to obtain polymer 23 (thermoplastic polyester elastomer). Each physical property of the obtained polymer 23 was measured, and the result is shown in Table 2. The polymer 23 obtained in this comparative example was inferior in heat aging resistance and low in quality. In addition, in the synthesis work of this comparative example, the melting temperature of the polycarbonate diol having a number average molecular weight of over 5000 and the number average molecular weight of 5099 is high and the viscosity is high. It was.

Comparative Example 4
[Production of aliphatic polycarbonate oligomer]
Production method of aliphatic polycarbonate oligomer (polycarbonate oligomer 24):
100 parts by mass of 1,6-hexanediol and 0.6 part by mass of diethyl carbonate were charged, respectively, and reacted at 190 ° C. and 1300 Pa. After 2 hours, the contents were cooled to obtain polycarbonate oligomer 24.
The obtained polycarbonate oligomer had a terminal ethyl group of 3 mg-KOH / g, a terminal OH group of 53 mg-KOH / g (the ratio of the terminal ethyl carbonate group to the terminal group was 5%), and the number average molecular weight was 2004. The kinematic viscosity at 20 ° C. was 2050 mm ² / s.
[Production of thermoplastic polyester elastomer]
When 100 parts by mass of polybutylene terephthalate (PBT) having a fractional average molecular weight of 30000 and 45 parts by mass of polycarbonate diol 24 (number average molecular weight is 2004) are stirred at 230 to 245 ° C. and 130 Pa for 10 minutes, the resin becomes transparent. It was confirmed that the contents were taken out and cooled to obtain polymer 24 (thermoplastic polyester elastomer). The physical properties of the obtained polymer 24 were measured, and the results are shown in Table 1. The polymer 24 obtained in this comparative example was poor in heat aging resistance and low quality. Moreover, since the molecular weight was low, the flexural modulus could not be measured.

Comparative Example 5
Regarding the polyether diol having a number average molecular weight of 2000 obtained by ring-opening addition of tetrahydrofuran to 1,4-butanediol, the physical properties were measured and the results are shown in Table 2. It is clear that the heat aging resistance is inferior. is there.

Comparative Example 6
Various properties of the polyester diol having a number average molecular weight of 2000 obtained by ring-opening addition of ε-caprolactone to ethylene glycol were measured and the results are shown in Table 2. It is clear that the water aging resistance is poor. Further, a slight odor was felt when remelted.

Comparative Example 7
[Production of aliphatic polycarbonate oligomer]
Method for producing aliphatic polycarbonate oligomer (polycarbonate oligomer 27):
100 parts by mass of 1,6-hexanediol having a number average molecular weight of 2000 and 4.7 parts by mass of diethyl carbonate were charged and reacted at a temperature of 190 ° C. and 1300 Pa. After 2 hours, the contents were cooled to obtain polycarbonate oligomer 27.
The obtained polycarbonate oligomer 27 has a terminal ethyl group 0 mg-KOH / g, a terminal OH group 11 mg-KOH / g (the ratio of the terminal ethyl carbonate group to the terminal group is 0%), and the number average molecular weight is 10,000. The kinematic viscosity at 75 ° C. was 95000 mm ² / s.
[Production of thermoplastic polyester elastomer]
100 parts by weight of polybutylene terephthalate (PBT) having a number average molecular weight of 30000 and 43 parts by weight of polycarbonate diol 27 (number average molecular weight is 10,000) were stirred at 230 to 245 ° C. and 130 Pa for 10 minutes, and the resin became transparent. After confirming this, the contents were taken out and cooled to obtain polymer 27 (thermoplastic polyester elastomer). Each physical property of the obtained polymer 27 was measured, and the result is shown in Table 1. The polymer 27 obtained in this comparative example was inferior in heat aging resistance and low in quality. In addition, in the synthesis work of this comparative example, the melting temperature of the polycarbonate diol having a number average molecular weight exceeding 5000 and the number average molecular weight 10000 is high and the viscosity is high, and therefore the melting and charging work into the reactor is extremely difficult. It was.

As mentioned above, although the manufacturing method of the thermoplastic polyester elastomer of this invention and its raw material polycarbonate oligomer composition were demonstrated based on the several Example, this invention is not limited to the structure described in the said Example, The configuration can be changed as appropriate without departing from the spirit of the invention, for example, by appropriately combining the configurations described in the embodiments.

The thermoplastic polyester elastomer obtained by the production method of the present invention and the composition thereof have good heat resistance, and have maintained the characteristics of the polyester polycarbonate type elastomer that are excellent in heat aging resistance, water resistance, low temperature characteristics, etc. Above, the block property and the block property retention are improved. Due to the high block property, a decrease in heat resistance due to a decrease in melting point is suppressed, and mechanical properties such as hardness, tensile strength and elastic modulus are improved. In addition, the improvement of the block property holding property suppresses the fluctuation of the block property during the molding process, so that the uniformity of the quality of the molded product can be enhanced. In addition, by containing 0.01 to 20 parts by mass of a compound having at least one reactive group, an effect of improving heat aging resistance, water resistance and residual strain and a melt flow rate suitable for blow molding and extrusion molding are obtained. I can do things. In addition, recyclability is enhanced by the characteristics, which can lead to environmental load and cost reduction. Therefore, since the thermoplastic polyester elastomer obtained by the production method of the present invention has the above-described excellent characteristics and advantages, it can be used for various molding materials including fibers, films and sheets. It is also suitable for molding materials such as elastic yarns and boots, gears, tubes, packings, etc., for example, applications such as automobiles and home appliance parts that require heat aging resistance, water resistance, low temperature characteristics, specifically, It is useful for applications such as joint boots and wire coating materials. In particular, it can be suitably used as a material for parts that require high heat resistance such as joint boots used around automobile engines and wire coating materials, which greatly contributes to the industry.

Claims

A method for producing a thermoplastic polyester elastomer comprising a hard segment composed of a polyester composed of an aromatic dicarboxylic acid and an aliphatic or alicyclic diol, and a soft segment composed mainly of an aliphatic polycarbonate. Production of a thermoplastic polyester elastomer, wherein a polycarbonate oligomer having a terminal alkyl carbonate group or a terminal aryl carbonate group having a group ratio of 10% or more is used, and a transesterification reaction between the polycarbonate oligomer and the polyester hard segment is performed. Method.
The production method according to claim 1, wherein a polycarbonate oligomer having a terminal alkyl carbonate group or a terminal aryl carbonate group having a terminal group ratio of 15% or more is used as the polycarbonate oligomer.
The method according to claim 1, wherein the number average molecular weight of the polycarbonate oligomer is 1000 to 5000.
The production method according to claim 2, wherein the number average molecular weight of the polycarbonate oligomer is 1000 to 5000.
The production method according to any one of claims 1 to 4, wherein the number average molecular weight of the polyester constituting the hard segment is 10,000 to 40,000.
Raw material polycarbonate oligomer composition used in the production of a thermoplastic segment elastomer comprising a hard segment composed of a polyester composed of an aromatic dicarboxylic acid and an aliphatic or alicyclic diol, and a soft segment composed mainly of an aliphatic polycarbonate A raw material polycarbonate oligomer composition comprising a polycarbonate oligomer having a terminal alkyl carbonate group or a terminal aryl carbonate group having a terminal group ratio of 10% or more.
7. The raw material polycarbonate oligomer composition according to claim 6, comprising a polycarbonate oligomer having a terminal alkyl carbonate group or a terminal aryl carbonate group having a terminal group ratio of 15% or more as the polycarbonate oligomer.
The raw material polycarbonate oligomer composition according to claim 6 or 7, wherein the polycarbonate oligomer has a number average molecular weight of 1,000 to 5,000.