WO2019203542A1 - Environmentally friendly thermoplastic polyether ester elastomer comprising anhydrous sugar alcohol derivatives and method for preparing same - Google Patents

Environmentally friendly thermoplastic polyether ester elastomer comprising anhydrous sugar alcohol derivatives and method for preparing same Download PDF

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Publication number
WO2019203542A1
WO2019203542A1 PCT/KR2019/004585 KR2019004585W WO2019203542A1 WO 2019203542 A1 WO2019203542 A1 WO 2019203542A1 KR 2019004585 W KR2019004585 W KR 2019004585W WO 2019203542 A1 WO2019203542 A1 WO 2019203542A1
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Prior art keywords
polyether ester
thermoplastic polyether
furan
compound
ester elastomer
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PCT/KR2019/004585
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French (fr)
Korean (ko)
Inventor
김미란
이민선
장윤주
권재관
이철한
권영도
유진
임용찬
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주식회사 삼양사
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Publication of WO2019203542A1 publication Critical patent/WO2019203542A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/199—Acids or hydroxy compounds containing cycloaliphatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/40—Polyesters derived from ester-forming derivatives of polycarboxylic acids or of polyhydroxy compounds, other than from esters thereof
    • C08G63/42—Cyclic ethers; Cyclic carbonates; Cyclic sulfites; Cyclic orthoesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/672—Dicarboxylic acids and dihydroxy compounds

Definitions

  • the present invention relates to a thermoplastic polyether ester elastomer (TPEE) having a hard segment and a soft segment and a method for preparing the same, more particularly, to a furan dicarboxylic compound in the hard segment and the soft segment, or It contains elastic units which are derived from a combination of a furan group dicarboxylic compound and an aromatic dicarboxyl compound, and includes an anhydrosugar alcohol derivative derived unit having improved reactivity derived from biomass in the soft segment, and is an important characteristic of the elastomer.
  • TPEE thermoplastic polyether ester elastomer
  • Elastomers are used in many applications such as packaging containers, automotive interior materials, elastic fibers, etc. due to their unique elastic properties, and especially in the case of thermoplastic polyether ester copolymers, their usage is increasing due to a wide range of elastic properties. Also, since elastomers are easy to recycle, unlike rubber materials that cannot be recycled, the demand for elastomers is greatly increased.
  • Thermoplastic elastomers are polymers that have both two different properties: the elastic properties of elastomers, which are thermoplastic and rubbery polymers that can be reformed upon heating.
  • the type of thermoplastic elastomer is a block copolymer, which is generally composed of a hard segment block that can exhibit the characteristics of thermoplastic and a soft segment block that can exhibit the elastic properties of the elastomer, simultaneously exhibiting two different properties.
  • polyether ester copolymers having a polybutylene terephthalate-based polyester as a hard segment and a polybutylene ether ester as a soft segment exhibit excellent elastic properties. Is also used as a soft segment.
  • Hard segment / soft segment copolyesters are prepared from dihydroxy compounds selected from (1) dicarboxylic acid or ester forming derivatives, (2) polyethylene glycol ethers, and (3) bisphenols and lower aliphatic glycols.
  • Polyethers used as soft segments with polyethylene glycol include polypropylene glycol, polytetramethylene glycol, polyhexamethylene glycol, and the like, and polyethers having a molecular weight of about 350 to 6,000 are used.
  • U.S. Patent No. 4,937,314 discloses thermoplastic polyether ester elastomers comprising at least 70 parts by weight of soft segments derived from poly (alkylene oxide) glycol and terephthalic acid.
  • the hard segment comprises 10 to 30 parts by weight of the elastomer, of which the poly (1,3-propylene terephthalate) is 95 to 100 parts by weight.
  • the molecular weight of the poly (alkylene oxide) glycols is from about 1,500 to about 5,000, and the carbon to oxygen ratio is shown to be 2 to 4.3.
  • Thermoplastic elastomers based on those exemplified in the prior art are soft segments which are mainly polytetramethylene glycol ethers, copolymers of tetrahydrofuran and 3-alkyltetrahydrofuran, polyethylene glycol ethers, polytrimethylene glycol ethers and copolymers thereof Use
  • the melting point and physical properties of these copolymers are determined by the molecular weight and composition ratio of the polyalkylene glycol ethers used as soft segments.
  • a high molecular weight polyalkylene glycol ether is used to express tough physical and elastic properties, it cannot be applied to a process requiring a low melting point manufacturing process because of its high melting point.
  • the thermal stability is drastically deteriorated when the content of the soft segment is added 20% by weight or more.
  • the present invention further improves the environmental friendliness, while maintaining excellent elastic and physical properties of the thermoplastic elastomer, it is possible to more easily control the melting point required in the molding process of the final product
  • An object of the present invention is to provide a thermoplastic polyether ester elastomer and a method for producing the same.
  • thermoplastic polyether ester elastomer comprising a hard segment and a soft segment, wherein the hard segment includes a dicarboxylic compound and an aliphatic diol component as a polymer unit, and the soft segment is a polymer unit.
  • a dicarboxylic compound and a glycol component wherein the glycol component comprises anhydrosugar alcohol-alkylene glycol, and the dicarboxyl compound is a furan dicarboxylic compound or a furan dicarboxylic compound and an aromatic dica
  • thermoplastic polyether ester elastomers which are combinations of carboxyl compounds.
  • the present invention comprises a polycondensation reaction of a dicarboxylic compound and a polyol, wherein the polyol comprises an aliphatic diol component and a glycol component, the glycol component is an anhydrosugar alcohol-alkylene glycol
  • the dicarboxylic compound is a furan dicarboxyl compound, or a combination of a furan dicarboxyl compound and an aromatic dicarboxyl compound.
  • thermoplastic polyether ester elastomer of the present invention there is provided a molded article comprising the thermoplastic polyether ester elastomer of the present invention.
  • thermoplastic polyether ester elastomer according to the present invention consists of a hard segment and a soft segment, and a furan dicarboxylic compound or a combination of a furan dicarboxylic compound and an aromatic dicarboxylic compound in the hard segment and the soft segment. And a unit derived from anhydrosugar alcohol derivative having improved reactivity derived from biomass in the soft segment, and the elastic and physical properties (e.g., hardness, pyrolysis temperature, etc.), which are important properties of the elastomer, are included in the soft segment. While maintaining excellent, it is possible to more easily control the melting point required in the molding process of the final product, to solve the problem of exhaustion of petroleum resources, which is a finite resource, and to further improve the environmental friendliness.
  • the hard segment constituting the thermoplastic polyether ester elastomer of the present invention includes a dicarboxylic compound and an aliphatic diol component as polymerized units.
  • the dicarboxylic compound may be a furan group dicarboxyl compound, or a combination of a furan group dicarboxyl compound and an aromatic dicarboxyl compound.
  • the furan dicarboxylic compound is, for example, dimethyl-2,3-furan dicarboxylate, dimethyl-2,4-furan dicarboxylate, dimethyl-3,4-furan dicarboxylate, dimethyl- 2,5-furan dicarboxylate, 2,3-furan dicarboxylic acid, 2,4-furan dicarboxylic acid, 3,4-furan dicarboxylic acid, 2,5-furan dicarboxylic acid, Diethyl-2,3-furan dicarboxylate, diethyl-2,4-furan dicarboxylate, diethyl-3,4-furan dicarboxylate, diethyl-2,5-furan dicarboxylate Late, dipropyl-2,3-furan dicarboxylate, dipropyl-2,4-furan dicarboxylate, dipropyl-3,4-furan dicarboxylate, dipropyl-2,5-furan dica Carboxylate or a mixture of two or
  • the furan group dicarboxylic compound may be a furan group dicarboxylic compound derived from biomass.
  • the aromatic dicarboxylic compound may be an aromatic dicarboxylic acid or an aromatic dicarboxylate compound, and more specifically, terephthalic acid, isophthalic acid, 1,5-dinaphthalene dicarboxylic acid, 2,6-dinaphthalene It may be selected from the group consisting of dicarboxylic acid, dimethyl terephthalate, dimethyl isophthalate or a combination thereof.
  • the aliphatic diol component included as a polymer unit in the hard segment may be a linear or cyclic aliphatic diol, specifically a linear aliphatic diol having 2 to 8 carbon atoms or a cyclic aliphatic diol having 3 to 8 carbon atoms, and more specifically , Ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol or combinations thereof.
  • the soft segment constituting the thermoplastic polyether ester elastomer of the present invention comprises a dicarboxylic compound and a glycol component as polymerized units, wherein the glycol component comprises anhydrosugar alcohol-alkylene glycol.
  • dicarboxyl compound contained in a soft segment as a polymerization unit the thing similar to what was demonstrated previously in the hard segment can be used.
  • the anhydrosugar alcohol-alkylene glycol is an adduct obtained by reacting an alkylene oxide with a hydroxyl group at both ends or at one end (preferably both ends) of the anhydrosugar alcohol.
  • the anhydrosugar alcohol may be selected from the group consisting of isosorbide, isomannide, isoidide, or a combination thereof, preferably isosorbide.
  • the alkylene oxide may be linear or branched alkylene oxide of 2 to 8 carbon atoms, more specifically ethylene oxide, propylene oxide or a combination thereof.
  • the anhydrosugar alcohol-alkylene glycol may be a compound represented by the following formula (1).
  • R 1 and R 2 each independently represent a linear or branched alkylene group having 2 to 8 carbon atoms or 3 to 8 carbon atoms,
  • n each independently represent an integer of 0 to 15,
  • n the integer of 1-30.
  • R 1 and R 2 each independently represent an ethylene group, a propylene group or an isopropylene group, preferably R 1 and R 2 are the same as each other,
  • n each independently represent an integer of 1 to 14,
  • n the integer of 2-15.
  • isosorbide-propylene glycol isosorbide-ethylene glycol or a mixture thereof may be used as the anhydrosugar alcohol-alkylene glycol.
  • a and b each independently represent an integer of 0 to 15
  • a + b may be an integer of 1 to 30, more preferably a and b each independently represent an integer of 1 to 14, a + b may be an integer from 2 to 15.
  • c and d each independently represent an integer of 0 to 15
  • c + d may be an integer of 1 to 30, more preferably c and d each independently represent an integer of 1 to 14, c + d may be an integer from 2 to 15.
  • the isosorbide-alkylene glycol is 1% by weight, 2% by weight, 3% by weight, 5% by weight, 8% by weight. Or more, 10 wt% or more or 15 wt% or more, and 40 wt% or less, 39 wt% or less, 35 wt% or less, 33 wt% or less, 31 wt% or less, 28 wt% or less, or 25 wt% or less. It may be included as.
  • the isosorbide-alkylene glycol content in the TPEE is lower than the above range, the eco-friendliness of the elastomer is poor, on the contrary, if the content is too high, the crystalline portion of the elastomer disappears and the melting point is lost.
  • the glycol component included as polymerized units in the soft segment may further comprise polyalkylene ether glycol.
  • the polyalkylene ether glycol may be poly (C 2 -C 8 ) alkylene ether glycol, preferably selected from the group consisting of polyethylene ether glycol, polypropylene ether glycol, polytetramethylene ether glycol or combinations thereof. More preferably polytetramethylene ether glycol.
  • the soft segment may be included, for example, from 5% by weight to 75% by weight, more preferably from 30% by weight to 70% by weight. have. It is preferable that the soft segment content in the TPEE be within the above range in view of blow molding processability, mechanical strength and flexibility. If the content of the soft segment in the TPEE is too small than the above-mentioned level, the hardness becomes high, so that it is difficult to expect flexibility, and on the contrary, too much, it is difficult to expect high heat resistance.
  • the present invention comprises a polycondensation reaction of a dicarboxylic compound and a polyol, wherein the polyol comprises an aliphatic diol component and a glycol component, the glycol component is an anhydrosugar alcohol-alkylene glycol
  • the dicarboxylic compound is a furan dicarboxyl compound, or a combination of a furan dicarboxyl compound and an aromatic dicarboxyl compound.
  • dicarboxylic compound those as described above in the hard segment may be used.
  • the polycondensation reaction can be carried out under reduced pressure, optionally in the presence of a catalyst, for example under temperature conditions of 210 to 250 ° C.
  • thermoplastic polyether ester elastomer of the present invention is suitable for molding processing such as blow, extrusion, injection, and the like, while maintaining excellent elastic properties and physical properties (for example, hardness and pyrolysis temperature, etc.), which are important properties of the elastomer, and the final product. Melting point required in the molding process of the various can be easily adjusted.
  • thermoplastic polyether ester elastomer of the present invention there is provided a molded article comprising the thermoplastic polyether ester elastomer of the present invention.
  • the reactant of the composition shown in Table 2 was added to a 15 L melt condensation reactor, and 700 ppm titanium-based catalyst was added based on the acid component (FDME; or a combination of FDME and DMT), and then the temperature was increased to 210 ° C by-product. The resulting alcohol was removed, and a 300 ppm titanium catalyst was added to increase the temperature to 245 ° C. while gradually reducing the pressure of the reaction system to 1 mmHg to prepare a thermoplastic polyether ester elastomer according to Comparative Examples 1 to 3.
  • thermoplastic polyether ester elastomers of Examples 1 to 9 according to the present invention furan dicarboxylic compound or furan dicarboxylic compound as a dicarboxylic compound and TPEE) containing a combination of aromatic dicarboxyl compounds and containing anhydrosugar alcohol-alkylene glycol within a range of 1 to 40% by weight, while maintaining physical properties such as hardness and pyrolysis temperature, It is further improved, and it can be seen that the melting point of the elastomer is easily adjusted in the lower range.
  • Examples 1 to 9 while maintaining the viscosity, elasticity and physical properties (for example, hardness and pyrolysis temperature, etc.), which are important properties of the elastomer at the same level, while improving environmental friendliness,
  • the melting point required in the molding process of the final product can be easily controlled, but in the case of Comparative Example 1 (TPEE not containing a furan dicarboxylic compound and anhydrosugar alcohol-alkylene glycol) according to the present invention
  • the environmental friendliness was remarkably poor, the melting point was very high, and in Comparative Example 2 (TPEE containing no furan dicarboxylic compound), the melting point was very high, and in Comparative Example 3 (range of more than 40% by weight).
  • TPEE) containing anhydrosugar alcohol-alkylene glycol the crystalline portion disappears, it can be seen that the melting point is not measured.
  • thermoplastic elastomer prepared in Examples and Comparative Examples Measurement of physical properties of the thermoplastic elastomer prepared in Examples and Comparative Examples was carried out as follows.
  • the hardness was measured by a Showa D hardness tester manufactured by Handpi.
  • T d (° C.): The temperature at the time of 5% by weight reduction was measured using a thermogravimetric analyzer (TGA-7 from Perkin-Elmer).

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  • Health & Medical Sciences (AREA)
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Abstract

The present invention relates to a thermoplastic polyether ester elastomer (TPEE) having a hard segment and a soft segment, and a method for preparing same. More specifically, the present invention relates to a TPEE comprising, within a hard segment and a soft segment, units derived from a furandicarboxylic compound or from a combination of a furandicarboxylic compound and an aromatic dicarboxylic compound, and in the soft segment, units derived from biomass-derived anhydrous sugar alcohol derivatives having improved reactivity, and to a method for preparing the TPEE. The present invention enables more convenient control over the melting point, which is required to vary in the forming process for end products, while maintaining desirable elastic properties and physical properties (for example, hardness and thermal degradation temperature), which are important properties for an elastomer, can address the issue of the exhaustion of petroleum, which is a non-renewable resource, and can further improve environmental friendliness.

Description

무수당 알코올 유도체를 포함하는 친환경 열가소성 폴리에테르 에스테르 엘라스토머 및 이의 제조 방법Environmentally Friendly Thermoplastic Polyether Ester Elastomers Containing Anhydrosugar Alcohol Derivatives and Methods for Producing the Same
본 발명은 하드 세그먼트 및 소프트 세그먼트를 갖는 열가소성 폴리에테르 에스테르 엘라스토머(Thermoplastic polyether ester elastomer, TPEE) 및 이의 제조 방법에 관한 것으로, 더욱 상세하게는, 하드 세그먼트 및 소프트 세그먼트 내에 퓨란족 디카르복실 화합물, 또는 퓨란족 디카르복실 화합물과 방향족 디카르복실 화합물의 조합의 유래 단위를 포함하며, 상기 소프트 세그먼트 내에 바이오 매스 유래의 반응성이 향상된 무수당 알코올 유도체 유래 단위를 포함하고 있어, 엘라스토머의 중요한 특성인 탄성 특성 및 물리적 특성(예를 들어, 경도, 열분해온도 등)을 우수하게 유지하면서도 최종 제품의 성형 공정에서 다양하게 요구되는 융점을 보다 용이하게 조절할 수 있고, 유한 자원인 석유 자원 고갈의 문제를 해결할 수 있으며, 친환경성을 더욱 향상시킬 수 있는 열가소성 폴리에테르 에스테르 엘라스토머 및 이의 제조 방법에 관한 것이다.The present invention relates to a thermoplastic polyether ester elastomer (TPEE) having a hard segment and a soft segment and a method for preparing the same, more particularly, to a furan dicarboxylic compound in the hard segment and the soft segment, or It contains elastic units which are derived from a combination of a furan group dicarboxylic compound and an aromatic dicarboxyl compound, and includes an anhydrosugar alcohol derivative derived unit having improved reactivity derived from biomass in the soft segment, and is an important characteristic of the elastomer. And while maintaining excellent physical properties (eg hardness, pyrolysis temperature, etc.), it is possible to more easily control the melting point required in the molding process of the final product, and solve the problem of exhaustion of finite resources , To further improve the eco-friendliness Thermoplastic polyether ester elastomer with and to a production method thereof.
엘라스토머는 특유의 탄성 특성으로 포장 용기, 자동차 내장재, 탄성 섬유 등 많은 용도에 사용되고 있으며, 특히 열가소성 폴리에테르 에스테르 공중합체의 경우 넓은 범위의 탄성 특성으로 인하여 그 사용량이 증가하고 있다. 또한 엘라스토머는, 재활용이 불가능한 고무 소재와는 달리, 재활용이 용이하기 때문에 그 수요가 크게 늘어나고 있다.Elastomers are used in many applications such as packaging containers, automotive interior materials, elastic fibers, etc. due to their unique elastic properties, and especially in the case of thermoplastic polyether ester copolymers, their usage is increasing due to a wide range of elastic properties. Also, since elastomers are easy to recycle, unlike rubber materials that cannot be recycled, the demand for elastomers is greatly increased.
열가소성 엘라스토머는 두 가지 다른 성질, 즉, 가열하면 재형성될 수 있는 열가소성과 고무상 중합체인 엘라스토머의 탄성 특성을 둘 다 가지는 중합체이다. 열가소성 엘라스토머의 형태는 일종의 블록 공중합체로서, 일반적으로 열가소성의 특징을 나타낼 수 있는 하드 세그먼트 블록과 엘라스토머의 탄성 특성을 나타낼 수 있는 소프트 세그먼트 블록으로 구성되어 상이한 두 가지 특성을 동시에 나타낸다.Thermoplastic elastomers are polymers that have both two different properties: the elastic properties of elastomers, which are thermoplastic and rubbery polymers that can be reformed upon heating. The type of thermoplastic elastomer is a block copolymer, which is generally composed of a hard segment block that can exhibit the characteristics of thermoplastic and a soft segment block that can exhibit the elastic properties of the elastomer, simultaneously exhibiting two different properties.
일반적으로 폴리부틸렌 테레프탈레이트계 폴리에스테르를 하드 세그먼트로 하고 폴리부틸렌 에테르 에스테르를 소프트 세그먼트로 하는 폴리에테르 에스테르 공중합체가 우수한 탄성 특성을 나타내는 것은 이미 알려진 사실이며, 제조 단가를 낮추기 위하여 폴리에틸렌 에테르 에스테르도 소프트 세그먼트로 사용된다.In general, it is known that polyether ester copolymers having a polybutylene terephthalate-based polyester as a hard segment and a polybutylene ether ester as a soft segment exhibit excellent elastic properties. Is also used as a soft segment.
미국특허 제3,023,192호에는 하드 세그먼트/소프트 세그먼트 공중합 폴리에스테르 및 그로부터 제조된 엘라스토머가 제시되어 있다. 하드 세그먼트/소프트 세그먼트 공중합 폴리에스테르는 (1) 디카르복실 산 또는 에스테르 형성 유도체, (2) 폴리에틸렌 글리콜 에테르, 및 (3) 비스페놀 및 저급 지방족 글리콜 중에서 선택된 디하이드록시 화합물로부터 제조된다. 폴리에틸렌 글리콜과 함께 소프트 세그먼트로 사용되는 폴리에테르로는 폴리프로필렌 글리콜, 폴리테트라메틸렌 글리콜, 폴리헥사메틸렌 글리콜 등이 있고, 분자량은 약 350 내지 6,000의 폴리에테르가 사용된다.US 3,023,192 discloses hard segment / soft segment copolyesters and elastomers prepared therefrom. Hard segment / soft segment copolyesters are prepared from dihydroxy compounds selected from (1) dicarboxylic acid or ester forming derivatives, (2) polyethylene glycol ethers, and (3) bisphenols and lower aliphatic glycols. Polyethers used as soft segments with polyethylene glycol include polypropylene glycol, polytetramethylene glycol, polyhexamethylene glycol, and the like, and polyethers having a molecular weight of about 350 to 6,000 are used.
미국특허 제4,937,314호에는 폴리(알킬렌 옥사이드)글리콜 및 테레프탈산으로부터 유도된 소프트 세그먼트 70 중량부 이상을 포함하는 열가소성 폴리에테르 에스테르 엘라스토머가 제시되어 있다. 하드 세그먼트는 엘라스토머의 10 내지 30 중량부를 구성하고, 이 하드 세그먼트 중에서 폴리(1,3-프로필렌 테레프탈레이트)는 95 내지 100 중량부이다. 폴리(알킬렌 옥사이드) 글리콜의 분자량은 약 1,500 내지 약 5,000이고, 탄소 대 산소 비가 2 내지 4.3이라고 제시되어 있다.U.S. Patent No. 4,937,314 discloses thermoplastic polyether ester elastomers comprising at least 70 parts by weight of soft segments derived from poly (alkylene oxide) glycol and terephthalic acid. The hard segment comprises 10 to 30 parts by weight of the elastomer, of which the poly (1,3-propylene terephthalate) is 95 to 100 parts by weight. The molecular weight of the poly (alkylene oxide) glycols is from about 1,500 to about 5,000, and the carbon to oxygen ratio is shown to be 2 to 4.3.
종래 기술에서 예시된 것을 기본으로 하는 열가소성 엘라스토머는 소프트 세그먼트로서 주로 폴리테트라메틸렌 글리콜 에테르, 테트라하이드로푸란과 3-알킬테트라하이드로푸란의 공중합체, 폴리에틸렌 글리콜 에테르, 폴리트리메틸렌 글리콜 에테르 및 이들의 공중합체를 사용한다. 이들 공중합체의 융점과 물리적 특성은 소프트 세그먼트로 사용되는 폴리알킬렌 글리콜 에테르의 분자량과 조성비에 따라 정해진다. 강인한 물리적 특성과 탄성 특성을 발현하기 위하여 분자량이 높은 폴리알킬렌 글리콜 에테르를 사용하는 경우에는, 융점이 높아지기 때문에 낮은 융점의 제조 공정이 필요한 공정에는 적용할 수 없다. 또한 폴리에틸렌 글리콜 에테르를 소프트 세그먼트로 형성하는 경우에는, 소프트 세그먼트의 함량을 20 중량% 이상 첨가하면 열 안정성이 급격히 떨어진다. Thermoplastic elastomers based on those exemplified in the prior art are soft segments which are mainly polytetramethylene glycol ethers, copolymers of tetrahydrofuran and 3-alkyltetrahydrofuran, polyethylene glycol ethers, polytrimethylene glycol ethers and copolymers thereof Use The melting point and physical properties of these copolymers are determined by the molecular weight and composition ratio of the polyalkylene glycol ethers used as soft segments. When a high molecular weight polyalkylene glycol ether is used to express tough physical and elastic properties, it cannot be applied to a process requiring a low melting point manufacturing process because of its high melting point. In addition, in the case of forming the polyethylene glycol ether into the soft segment, the thermal stability is drastically deteriorated when the content of the soft segment is added 20% by weight or more.
또한 최근 지구 온난화의 주요 원인인 이산화탄소의 배출을 감소시키고, 한정된 고가의 석유 자원을 대체하기 위한 노력의 일환으로 친환경적인 바이오 매스(biomass)에 관한 활발한 연구들이 주목 받고 있다. 종래의 석유 원료 유래의 플라스틱에서 환경 부하가 적은 식물 원료 유래의 플라스틱으로의 전환이 적극적으로 요구되고 있다.In recent years, active research on eco-friendly biomass has been attracting attention as part of efforts to reduce carbon dioxide emission, which is a major cause of global warming, and to replace limited expensive oil resources. There is a strong demand for conversion from conventional petroleum-derived plastics to plastics derived from plant raw materials with less environmental load.
상기와 같은 문제점을 해결하기 위하여 본 발명은, 친환경성을 더욱 향상시키고, 열가소성 엘라스토머의 탄성 특성 및 물리적 특성은 우수하게 유지하면서도, 최종 제품의 성형 공정에서 다양하게 요구되는 융점을 보다 용이하게 조절할 수 있는 열가소성 폴리에테르 에스테르 엘라스토머 및 이의 제조 방법을 제공하는 것을 목적으로 한다.In order to solve the above problems, the present invention further improves the environmental friendliness, while maintaining excellent elastic and physical properties of the thermoplastic elastomer, it is possible to more easily control the melting point required in the molding process of the final product An object of the present invention is to provide a thermoplastic polyether ester elastomer and a method for producing the same.
상기한 기술적 과제를 해결하고자 본 발명은, 하드 세그먼트 및 소프트 세그먼트로 이루어지는 열가소성 폴리에테르 에스테르 엘라스토머로서, 상기 하드 세그먼트는 중합 단위로서 디카르복실 화합물 및 지방족 디올 성분을 포함하고, 상기 소프트 세그먼트는 중합 단위로서 디카르복실 화합물 및 글리콜 성분을 포함하며, 상기 글리콜 성분이 무수당 알코올-알킬렌 글리콜을 포함하고, 상기 디카르복실 화합물이 퓨란족 디카르복실 화합물, 또는 퓨란족 디카르복실 화합물과 방향족 디카르복실 화합물의 조합인, 열가소성 폴리에테르 에스테르 엘라스토머를 제공한다.In order to solve the above technical problem, the present invention provides a thermoplastic polyether ester elastomer comprising a hard segment and a soft segment, wherein the hard segment includes a dicarboxylic compound and an aliphatic diol component as a polymer unit, and the soft segment is a polymer unit. And a dicarboxylic compound and a glycol component, wherein the glycol component comprises anhydrosugar alcohol-alkylene glycol, and the dicarboxyl compound is a furan dicarboxylic compound or a furan dicarboxylic compound and an aromatic dica Provided are thermoplastic polyether ester elastomers, which are combinations of carboxyl compounds.
본 발명의 다른 측면에 따르면, 디카르복실 화합물과 폴리올을 축중합 반응시키는 것을 포함하며, 여기서, 상기 폴리올이 지방족 디올 성분과 글리콜 성분을 포함하고, 상기 글리콜 성분이 무수당 알코올-알킬렌 글리콜을 포함하며, 상기 디카르복실 화합물이 퓨란족 디카르복실 화합물, 또는 퓨란족 디카르복실 화합물과 방향족 디카르복실 화합물의 조합인, 열가소성 폴리에테르 에스테르 엘라스토머의 제조 방법이 제공된다.According to another aspect of the present invention, it comprises a polycondensation reaction of a dicarboxylic compound and a polyol, wherein the polyol comprises an aliphatic diol component and a glycol component, the glycol component is an anhydrosugar alcohol-alkylene glycol A method for producing a thermoplastic polyether ester elastomer is provided, wherein the dicarboxylic compound is a furan dicarboxyl compound, or a combination of a furan dicarboxyl compound and an aromatic dicarboxyl compound.
본 발명의 또 다른 측면에 따르면, 상기 본 발명의 열가소성 폴리에테르 에스테르 엘라스토머를 포함하는 성형품이 제공된다.According to another aspect of the present invention, there is provided a molded article comprising the thermoplastic polyether ester elastomer of the present invention.
본 발명에 따른 열가소성 폴리에테르 에스테르 엘라스토머(TPEE)는 하드 세그먼트 및 소프트 세그먼트로 이루어지며, 하드 세그먼트 및 소프트 세그먼트 내에 퓨란족 디카르복실 화합물, 또는 퓨란족 디카르복실 화합물과 방향족 디카르복실 화합물의 조합의 유래 단위를 포함하며, 상기 소프트 세그먼트 내에 바이오 매스 유래의 반응성이 향상된 무수당 알코올 유도체 유래 단위를 포함하고 있어, 엘라스토머의 중요한 특성인 탄성 특성 및 물리적 특성(예를 들어, 경도, 열분해온도 등)을 우수하게 유지하면서도 최종 제품의 성형 공정에서 다양하게 요구되는 융점을 보다 용이하게 조절할 수 있고, 유한 자원인 석유 자원 고갈의 문제를 해결할 수 있으며, 친환경성을 더욱 향상시킬 수 있다.The thermoplastic polyether ester elastomer (TPEE) according to the present invention consists of a hard segment and a soft segment, and a furan dicarboxylic compound or a combination of a furan dicarboxylic compound and an aromatic dicarboxylic compound in the hard segment and the soft segment. And a unit derived from anhydrosugar alcohol derivative having improved reactivity derived from biomass in the soft segment, and the elastic and physical properties (e.g., hardness, pyrolysis temperature, etc.), which are important properties of the elastomer, are included in the soft segment. While maintaining excellent, it is possible to more easily control the melting point required in the molding process of the final product, to solve the problem of exhaustion of petroleum resources, which is a finite resource, and to further improve the environmental friendliness.
이하에서 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
본 발명의 열가소성 폴리에테르 에스테르 엘라스토머를 구성하는 하드 세그먼트는 중합 단위로서 디카르복실 화합물 및 지방족 디올 성분을 포함한다.The hard segment constituting the thermoplastic polyether ester elastomer of the present invention includes a dicarboxylic compound and an aliphatic diol component as polymerized units.
상기 디카르복실 화합물은 퓨란족 디카르복실 화합물, 또는 퓨란족 디카르복실 화합물과 방향족 디카르복실 화합물의 조합일 수 있다.The dicarboxylic compound may be a furan group dicarboxyl compound, or a combination of a furan group dicarboxyl compound and an aromatic dicarboxyl compound.
상기 퓨란족 디카르복실 화합물은 예를 들면, 디메틸-2,3-퓨란 디카르복실레이트, 디메틸-2,4-퓨란 디카르복실레이트, 디메틸-3,4-퓨란 디카르복실레이트, 디메틸-2,5-퓨란 디카르복실레이트, 2,3-퓨란 디카르복실산, 2,4-퓨란 디카르복실산, 3,4-퓨란 디카르복실산, 2,5-퓨란 디카르복실산, 디에틸-2,3-퓨란 디카르복실레이트, 디에틸-2,4-퓨란 디카르복실레이트, 디에틸-3,4-퓨란 디카르복실레이트, 디에틸-2,5-퓨란 디카르복실레이트, 디프로필-2,3-퓨란 디카르복실레이트, 디프로필-2,4-퓨란 디카르복실레이트, 디프로필-3,4-퓨란 디카르복실레이트, 디프로필-2,5-퓨란 디카르복실레이트 또는 이들 중 2 이상의 혼합물일 수 있고, 바람직하게는 디메틸-2,5-퓨란 디카르복실레이트, 디에틸-2,5-퓨란 디카르복실레이트, 디프로필-2,5-퓨란 디카르복실레이트, 2,5-퓨란 디카르복실산 또는 이들 중 2 이상의 혼합물일 수 있으나, 이에 한정되지 않는다. The furan dicarboxylic compound is, for example, dimethyl-2,3-furan dicarboxylate, dimethyl-2,4-furan dicarboxylate, dimethyl-3,4-furan dicarboxylate, dimethyl- 2,5-furan dicarboxylate, 2,3-furan dicarboxylic acid, 2,4-furan dicarboxylic acid, 3,4-furan dicarboxylic acid, 2,5-furan dicarboxylic acid, Diethyl-2,3-furan dicarboxylate, diethyl-2,4-furan dicarboxylate, diethyl-3,4-furan dicarboxylate, diethyl-2,5-furan dicarboxylate Late, dipropyl-2,3-furan dicarboxylate, dipropyl-2,4-furan dicarboxylate, dipropyl-3,4-furan dicarboxylate, dipropyl-2,5-furan dica Carboxylate or a mixture of two or more thereof, preferably dimethyl-2,5-furan dicarboxylate, diethyl-2,5-furan dicarboxylate, dipropyl-2,5-furan dica Reboxylate, 2,5-furan Dicar Acids, or may be a mixture of two or more of them, and the like.
일 구체예에서, 상기 퓨란족 디카르복실 화합물로는 친환경성을 향상시키기 위하여, 바이오매스 유래의 퓨란족 디카르복실 화합물을 사용할 수 있다. In one embodiment, in order to improve environmental friendliness, the furan group dicarboxylic compound may be a furan group dicarboxylic compound derived from biomass.
상기 방향족 디카르복실 화합물은 방향족 디카르복실산 또는 방향족 디카르복실레이트 화합물일 수 있으며, 보다 구체적으로는, 테레프탈산, 이소프탈산, 1,5-디나프탈렌 디카르복실산, 2,6-디나프탈렌 디카르복실산, 디메틸 테레프탈레이트, 디메틸 이소프탈레이트 또는 이의 조합으로 이루어진 군으로부터 선택되는 것일 수 있다.The aromatic dicarboxylic compound may be an aromatic dicarboxylic acid or an aromatic dicarboxylate compound, and more specifically, terephthalic acid, isophthalic acid, 1,5-dinaphthalene dicarboxylic acid, 2,6-dinaphthalene It may be selected from the group consisting of dicarboxylic acid, dimethyl terephthalate, dimethyl isophthalate or a combination thereof.
하드 세그먼트에 중합 단위로서 포함되는 상기 지방족 디올 성분은 선형 또는 환형 지방족 디올일 수 있고, 구체적으로는 탄소수 2 내지 8의 선형 지방족 디올 또는 탄소수 3 내지 8의 환형 지방족 디올일 수 있으며, 보다 구체적으로는, 에틸렌 글리콜, 프로필렌 글리콜, 1,4-부탄디올, 1,5-펜탄디올, 1,6-헥산디올, 1,4-사이클로헥산디메탄올 또는 이의 조합으로 이루어진 군으로부터 선택되는 것일 수 있다.The aliphatic diol component included as a polymer unit in the hard segment may be a linear or cyclic aliphatic diol, specifically a linear aliphatic diol having 2 to 8 carbon atoms or a cyclic aliphatic diol having 3 to 8 carbon atoms, and more specifically , Ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol or combinations thereof.
본 발명의 열가소성 폴리에테르 에스테르 엘라스토머를 구성하는 소프트 세그먼트는 중합 단위로서 디카르복실 화합물 및 글리콜 성분을 포함하며, 상기 글리콜 성분은 무수당 알코올-알킬렌 글리콜을 포함한다.The soft segment constituting the thermoplastic polyether ester elastomer of the present invention comprises a dicarboxylic compound and a glycol component as polymerized units, wherein the glycol component comprises anhydrosugar alcohol-alkylene glycol.
소프트 세그먼트에 중합 단위로서 포함되는 상기 디카르복실 화합물로는 앞서 하드 세그먼트에서 설명한 바와 같은 것을 사용할 수 있다.As said dicarboxyl compound contained in a soft segment as a polymerization unit, the thing similar to what was demonstrated previously in the hard segment can be used.
상기 무수당 알코올-알킬렌 글리콜은 무수당 알코올의 양 말단 또는 일 말단(바람직하게는 양 말단)의 히드록시기와 알킬렌 옥사이드를 반응시켜 얻어지는 부가물이다.The anhydrosugar alcohol-alkylene glycol is an adduct obtained by reacting an alkylene oxide with a hydroxyl group at both ends or at one end (preferably both ends) of the anhydrosugar alcohol.
일 구체예에서, 상기 무수당 알코올은 이소소르비드, 이소만니드, 이소이디드 또는 이의 조합으로 이루어진 군으로부터 선택될 수 있으며, 바람직하게는 이소소르비드일 수 있다.In one embodiment, the anhydrosugar alcohol may be selected from the group consisting of isosorbide, isomannide, isoidide, or a combination thereof, preferably isosorbide.
일 구체예에서, 상기 알킬렌 옥사이드는 탄소수 2 내지 8의 선형 또는 탄소수 3 내지 8의 분지형 알킬렌 옥사이드일 수 있고, 보다 구체적으로는, 에틸렌 옥사이드, 프로필렌 옥사이드 또는 이의 조합일 수 있다.In one embodiment, the alkylene oxide may be linear or branched alkylene oxide of 2 to 8 carbon atoms, more specifically ethylene oxide, propylene oxide or a combination thereof.
일 구체예에서, 상기 무수당 알코올-알킬렌 글리콜은 하기 화학식 1로 표시되는 화합물일 수 있다.In one embodiment, the anhydrosugar alcohol-alkylene glycol may be a compound represented by the following formula (1).
[화학식 1][Formula 1]
Figure PCTKR2019004585-appb-I000001
Figure PCTKR2019004585-appb-I000001
상기 화학식 1에서,In Chemical Formula 1,
R1 및 R2는 각각 독립적으로 탄소수 2 내지 8의 선형 또는 탄소수 3 내지 8의 분지형 알킬렌기를 나타내고, R 1 and R 2 each independently represent a linear or branched alkylene group having 2 to 8 carbon atoms or 3 to 8 carbon atoms,
m 및 n은 각각 독립적으로 0 내지 15의 정수를 나타내며,m and n each independently represent an integer of 0 to 15,
m+n은 1 내지 30의 정수를 나타낸다.m + n represents the integer of 1-30.
보다 바람직하게는, 상기 화학식 1에서,More preferably, in Chemical Formula 1,
R1 및 R2는 각각 독립적으로 에틸렌기, 프로필렌기 또는 이소프로필렌기를 나타내고, 바람직하게는 R1 및 R2는 서로 동일하며,R 1 and R 2 each independently represent an ethylene group, a propylene group or an isopropylene group, preferably R 1 and R 2 are the same as each other,
m 및 n은 각각 독립적으로 1 내지 14의 정수를 나타내고,m and n each independently represent an integer of 1 to 14,
m+n은 2 내지 15의 정수를 나타낸다.m + n represents the integer of 2-15.
일 구체예에서, 상기 무수당 알코올-알킬렌 글리콜로는 하기 이소소르비드-프로필렌 글리콜, 이소소르비드-에틸렌 글리콜 또는 이들의 혼합물을 사용할 수 있다.In one embodiment, the following isosorbide-propylene glycol, isosorbide-ethylene glycol or a mixture thereof may be used as the anhydrosugar alcohol-alkylene glycol.
[이소소르비드-프로필렌 글리콜][Isosorbide-propylene glycol]
Figure PCTKR2019004585-appb-I000002
Figure PCTKR2019004585-appb-I000002
상기 화학식에서, a 및 b는 각각 독립적으로 0 내지 15의 정수를 나타내며, a+b는 1 내지 30의 정수일 수 있고, 더 바람직하게는 a 및 b는 각각 독립적으로 1 내지 14의 정수를 나타내며, a+b는 2 내지 15의 정수일 수 있다.In the above formula, a and b each independently represent an integer of 0 to 15, a + b may be an integer of 1 to 30, more preferably a and b each independently represent an integer of 1 to 14, a + b may be an integer from 2 to 15.
[이소소르비드-에틸렌 글리콜][Isosorbide-ethylene glycol]
Figure PCTKR2019004585-appb-I000003
Figure PCTKR2019004585-appb-I000003
상기 화학식에서, c 및 d는 각각 독립적으로 0 내지 15의 정수를 나타내며, c+d는 1 내지 30의 정수일 수 있고, 더 바람직하게는 c 및 d는 각각 독립적으로 1 내지 14의 정수를 나타내며, c+d는 2 내지 15의 정수일 수 있다.In the above formula, c and d each independently represent an integer of 0 to 15, c + d may be an integer of 1 to 30, more preferably c and d each independently represent an integer of 1 to 14, c + d may be an integer from 2 to 15.
본 발명의 열가소성 폴리에테르 에스테르 엘라스토머(TPEE) 100 중량% 내에는, 상기 이소소르비드-알킬렌 글리콜이, 1 중량% 이상, 2 중량% 이상, 3 중량% 이상, 5 중량% 이상, 8 중량% 이상, 10 중량% 이상 또는 15 중량% 이상으로 포함될 수 있고, 40 중량% 이하, 39 중량% 이하, 35 중량% 이하, 33 중량% 이하, 31 중량% 이하, 28 중량% 이하 또는 25 중량% 이하로 포함될 수 있다. 예컨대, 1 중량% 내지 40 중량%, 예컨대 3 내지 40 중량%, 예컨대 3 중량% 내지 39 중량%, 예컨대 3 중량% 내지 35중량%, 예컨대 3 중량% 내지 31중량%의 양으로 포함될 수 있다. TPEE 내의 이소소르비드-알킬렌 글리콜 함량이 상기 범위보다 낮은 경우에는 엘라스토머의 친환경성이 열악해지고, 반대로 함량이 너무 높은 경우에는 엘라스토머의 결정성 부분이 사라져 융점이 없어지게 된다.In 100% by weight of the thermoplastic polyether ester elastomer (TPEE) of the present invention, the isosorbide-alkylene glycol is 1% by weight, 2% by weight, 3% by weight, 5% by weight, 8% by weight. Or more, 10 wt% or more or 15 wt% or more, and 40 wt% or less, 39 wt% or less, 35 wt% or less, 33 wt% or less, 31 wt% or less, 28 wt% or less, or 25 wt% or less. It may be included as. For example, it may be included in an amount of 1 to 40% by weight, such as 3 to 40% by weight, such as 3 to 39% by weight, such as 3 to 35% by weight, such as 3 to 31% by weight. If the isosorbide-alkylene glycol content in the TPEE is lower than the above range, the eco-friendliness of the elastomer is poor, on the contrary, if the content is too high, the crystalline portion of the elastomer disappears and the melting point is lost.
소프트 세그먼트에 중합 단위로서 포함되는 글리콜 성분은 폴리알킬렌 에테르 글리콜을 추가로 포함할 수 있다.The glycol component included as polymerized units in the soft segment may further comprise polyalkylene ether glycol.
상기 폴리알킬렌 에테르 글리콜은 폴리(C2-C8)알킬렌 에테르 글리콜일 수 있으며, 바람직하게는 폴리에틸렌 에테르 글리콜, 폴리프로필렌 에테르 글리콜, 폴리테트라메틸렌 에테르 글리콜 또는 이의 조합으로 이루어진 군으로부터 선택될 수 있고, 보다 바람직하게는 폴리테트라메틸렌 에테르 글리콜일 수 있다.The polyalkylene ether glycol may be poly (C 2 -C 8 ) alkylene ether glycol, preferably selected from the group consisting of polyethylene ether glycol, polypropylene ether glycol, polytetramethylene ether glycol or combinations thereof. More preferably polytetramethylene ether glycol.
본 발명의 열가소성 폴리에테르 에스테르 엘라스토머(TPEE) 100 중량% 내에는 상기 소프트 세그먼트가, 예컨대, 5 중량% 내지 75 중량% 포함될 수 있고, 보다 바람직하게는 30 중량% 내지 70 중량%의 양으로 포함될 수 있다. TPEE 내의 소프트 세그먼트 함량이 상기한 범위 내인 것이 블로우 성형 가공성, 기계적 강도 및 유연성 등의 측면에서 바람직하다. TPEE 내의 소프트 세그먼트 함량이 상기한 수준보다 너무 적으면 경도가 높아져 유연성을 기대하기 어려우며, 반대로 너무 많으면 높은 내열성을 기대하기 어렵다.Within 100% by weight of the thermoplastic polyether ester elastomer (TPEE) of the present invention, the soft segment may be included, for example, from 5% by weight to 75% by weight, more preferably from 30% by weight to 70% by weight. have. It is preferable that the soft segment content in the TPEE be within the above range in view of blow molding processability, mechanical strength and flexibility. If the content of the soft segment in the TPEE is too small than the above-mentioned level, the hardness becomes high, so that it is difficult to expect flexibility, and on the contrary, too much, it is difficult to expect high heat resistance.
본 발명의 다른 측면에 따르면, 디카르복실 화합물과 폴리올을 축중합 반응시키는 것을 포함하며, 여기서, 상기 폴리올이 지방족 디올 성분과 글리콜 성분을 포함하고, 상기 글리콜 성분이 무수당 알코올-알킬렌 글리콜을 포함하며, 상기 디카르복실 화합물이 퓨란족 디카르복실 화합물, 또는 퓨란족 디카르복실 화합물과 방향족 디카르복실 화합물의 조합인, 열가소성 폴리에테르 에스테르 엘라스토머의 제조 방법이 제공된다.According to another aspect of the present invention, it comprises a polycondensation reaction of a dicarboxylic compound and a polyol, wherein the polyol comprises an aliphatic diol component and a glycol component, the glycol component is an anhydrosugar alcohol-alkylene glycol A method for producing a thermoplastic polyether ester elastomer is provided, wherein the dicarboxylic compound is a furan dicarboxyl compound, or a combination of a furan dicarboxyl compound and an aromatic dicarboxyl compound.
상기 디카르복실 화합물로는 앞서 하드 세그먼트에서 설명한 바와 같은 것을 사용할 수 있다.As the dicarboxylic compound, those as described above in the hard segment may be used.
상기 중축합 반응은, 임의로 촉매의 존재 하에, 예컨대, 210~250℃의 온도 조건 하에서, 감압 하에 수행될 수 있다.The polycondensation reaction can be carried out under reduced pressure, optionally in the presence of a catalyst, for example under temperature conditions of 210 to 250 ° C.
본 발명의 열가소성 폴리에테르 에스테르 엘라스토머는 블로우, 압출, 사출 등의 성형가공에 적합하며, 엘라스토머의 중요한 특성인 탄성 특성과 물리적 특성(예를 들어, 경도 및 열분해온도 등)을 우수하게 유지하면서도 최종 제품의 성형 공정에서 다양하게 요구되는 융점을 용이하게 조절할 수 있다.The thermoplastic polyether ester elastomer of the present invention is suitable for molding processing such as blow, extrusion, injection, and the like, while maintaining excellent elastic properties and physical properties (for example, hardness and pyrolysis temperature, etc.), which are important properties of the elastomer, and the final product. Melting point required in the molding process of the various can be easily adjusted.
따라서, 본 발명의 또 다른 측면에 따르면, 상기 본 발명의 열가소성 폴리에테르 에스테르 엘라스토머를 포함하는 성형품이 제공된다.Thus, according to another aspect of the present invention, there is provided a molded article comprising the thermoplastic polyether ester elastomer of the present invention.
이하, 실시예 및 비교예를 통하여 본 발명을 보다 상세하게 설명한다. 그러나, 본 발명의 범위가 이들로 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the scope of the present invention is not limited to these.
[[ 실시예Example ]]
<무수당 알코올-알킬렌 글리콜의 제조><Preparation of sugar-free alcohol-alkylene glycol>
제조예Production Example A1 A1 : 이소소르비드-: Isosorbide 에틸렌 글리콜Ethylene glycol (이소소르비드의 에틸렌 (Ethylene of isosorbide 옥사이드Oxide 5몰 부가물)의 제조 5 mole adduct)
이소소르비드 73.1g(0.5 mol), 에틸렌 옥사이드 110g(2.5 mol) 및 촉매로서의 수산화나트륨 0.2g을, 질소 가스관 및 냉각장치가 설치된 컬럼, 교반기, 온도계 및 히터를 구비하고 가압이 가능한 반응 장치에 넣고 서서히 승온시켰다. 120℃ 내지 160℃의 온도에서 2시간 내지 4시간 동안 유지하면서 반응시켜 이소소르비드 양 말단의 히드록시기의 수소가 히드록시에틸기로 치환된 형태인 이소소르비드-에틸렌 글리콜(이소소르비드의 에틸렌 옥사이드 5몰 부가물)을 제조하였다.73.1 g (0.5 mol) of isosorbide, 110 g (2.5 mol) of ethylene oxide and 0.2 g of sodium hydroxide as catalyst were placed in a pressurized reactor equipped with a nitrogen gas pipe and a column equipped with a chiller, a stirrer, a thermometer and a heater. The temperature was raised slowly. Isosorbide-ethylene glycol (ethylene oxide 5 of isosorbide) in the form where hydrogen of the hydroxyl group at both ends of the isosorbide is substituted with a hydroxyethyl group by reacting while maintaining for 2 to 4 hours at a temperature of 120 ° C to 160 ° C. Mole adduct).
제조예Production Example A2 A2 : 이소소르비드-: Isosorbide 에틸렌 글리콜Ethylene glycol (이소소르비드의 에틸렌 (Ethylene of isosorbide 옥사이드Oxide 10몰 부가물) 의 제조 10 mole adduct)
이소소르비드 73.1g(0.5 mol), 에틸렌 옥사이드 220g(5 mol) 및 촉매로서의 수산화나트륨 0.2g을, 질소 가스관 및 냉각장치가 설치된 컬럼, 교반기, 온도계 및 히터를 구비하고 가압이 가능한 반응 장치에 넣고 서서히 승온시켰다. 120℃ 내지 160℃의 온도에서 2시간 내지 4시간 동안 유지하면서 반응시켜 이소소르비드 양 말단의 히드록시기의 수소가 히드록시에틸기로 치환된 형태인 이소소르비드-에틸렌 글리콜(이소소르비드의 에틸렌 옥사이드 10몰 부가물)을 제조하였다.73.1 g (0.5 mol) of isosorbide, 220 g (5 mol) of ethylene oxide and 0.2 g of sodium hydroxide as a catalyst were placed in a pressurized reactor equipped with a nitrogen gas pipe and a column equipped with a chiller, a stirrer, a thermometer and a heater. The temperature was raised slowly. Isosorbide-ethylene glycol (ethylene oxide 10 of isosorbide) in a form in which hydrogen of the hydroxy group at both ends of the isosorbide is substituted with a hydroxyethyl group by reacting at a temperature of 120 ° C. to 160 ° C. for 2 to 4 hours. Mole adduct).
제조예Production Example B1 B1 : 이소소르비드-프로필렌 글리콜(이소소르비드의 프로필렌 : Isosorbide propylene glycol (propylene of isosorbide 옥사이드Oxide 5몰 부가물)의 제조 5 mole adduct)
이소소르비드 73.1g(0.5 mol), 프로필렌 옥사이드 145g(2.5 mol) 및 촉매로서의 수산화나트륨 0.2g을, 질소 가스관 및 냉각장치가 설치된 컬럼, 교반기, 온도계 및 히터를 구 비하고 가압이 가능한 반응 장치에 넣고 서서히 승온시켰다. 120℃ 내지 160℃의 온도에서 2시간 내지 4시간 동안 유지하면서 반응시켜 이소소르비드 양 말단의 히드록시기의 수소가 히드록시프로필기로 치환된 형태인 이소소르비드-프로필렌 글리콜(이소소르비드의 프로필렌 옥사이드 5몰 부가물)을 제조하였다.73.1 g of isosorbide (0.5 mol), 145 g (2.5 mol) of propylene oxide and 0.2 g of sodium hydroxide as a catalyst were placed in a pressurized reactor equipped with a nitrogen gas pipe and a column, agitator, thermometer and heater equipped with a cooling system. The mixture was gradually heated up. Isosorbide-propylene glycol (propylene oxide 5 of isosorbide) in a form where hydrogen of the hydroxyl group at both ends of the isosorbide is substituted with a hydroxypropyl group by reacting for 2 to 4 hours at a temperature of 120 ° C to 160 ° C. Mole adduct).
제조예Production Example B2 B2 : 이소소르비드-프로필렌 글리콜(이소소르비드의 프로필렌 : Isosorbide propylene glycol (propylene of isosorbide 옥사이드Oxide 8몰 부가물)의 제조 8 mole adduct)
이소소르비드 73.1g(0.5 mol), 프로필렌 옥사이드 232g(4 mol) 및 촉매로서의 수산화나트륨 0.2g을, 질소 가스관 및 냉각장치가 설치된 컬럼, 교반기, 온도계 및 히터를 구 비하고 가압이 가능한 반응 장치에 넣고 서서히 승온시켰다. 120℃ 내지 160℃의 온도에서 2시간 내지 4시간 동안 유지하면서 반응시켜 이소소르비드 양 말단의 히드록시기의 수소가 히드록시프로필기로 치환된 형태인 이소소르비드-프로필렌 글리콜(이소소르비드의 프로필렌 옥사이드 8몰 부가물)을 제조하였다.73.1 g (0.5 mol) of isosorbide, 232 g (4 mol) of propylene oxide, and 0.2 g of sodium hydroxide as a catalyst were placed in a pressurized reactor equipped with a nitrogen gas pipe and a column equipped with a chiller, a stirrer, a thermometer and a heater. The mixture was gradually heated up. Isosorbide-propylene glycol (propylene oxide 8 of isosorbide) in the form where hydrogen of the hydroxyl group at both ends of the isosorbide is substituted with a hydroxypropyl group by reacting for 2 to 4 hours at a temperature of 120 ° C to 160 ° C. Mole adduct).
<열가소성 폴리에테르 에스테르 엘라스토머의 제조>Preparation of Thermoplastic Polyether Ester Elastomers
실시예 1 내지 9Examples 1-9
15L의 용융 축합 반응기에 하기 표 1에 나타낸 조성의 반응물을 넣고, 산 성분(FDME; 또는 FDME와 DMT의 조합)을 기준으로 700ppm의 티타늄계 촉매를 첨가한 후, 온도를 210℃까지 상승시키면서 부산물로 생성되는 알코올을 제거하고, 300ppm의 티타늄계 촉매를 첨가하여 245℃까지 온도를 상승시키면서 반응계의 압력을 1 mmHg까지 서서히 감압하여 실시예 1 내지 9에 따른 열가소성 폴리에테르 에스테르 엘라스토머를 제조하였다.Into a 15 L melt condensation reactor, the reactants of the composition shown in Table 1 were added, and based on the acid component (FDME; or a combination of FDME and DMT), 700 ppm of titanium-based catalyst was added thereto, and the by-products were raised to 210 ° C. The resulting alcohol was removed, and a 300 ppm titanium catalyst was added to increase the temperature to 245 ° C. while gradually reducing the pressure of the reaction system to 1 mmHg, thereby preparing thermoplastic polyether ester elastomers according to Examples 1 to 9.
[표 1]TABLE 1
Figure PCTKR2019004585-appb-I000004
Figure PCTKR2019004585-appb-I000004
비교예 1 내지 3Comparative Examples 1 to 3
15L의 용융 축합 반응기에 하기 표 2에 나타낸 조성의 반응물을 넣고, 산 성분(FDME; 또는 FDME와 DMT의 조합)을 기준으로 700ppm의 티타늄계 촉매를 첨가한 후, 온도를 210℃까지 상승시키면서 부산물로 생성되는 알코올을 제거하고, 300ppm의 티타늄계 촉매를 첨가하여 245℃까지 온도를 상승시키면서 반응계의 압력을 1 mmHg까지 서서히 감압하여 비교예 1 내지 3에 따른 열가소성 폴리에테르 에스테르 엘라스토머를 제조하였다.The reactant of the composition shown in Table 2 was added to a 15 L melt condensation reactor, and 700 ppm titanium-based catalyst was added based on the acid component (FDME; or a combination of FDME and DMT), and then the temperature was increased to 210 ° C by-product. The resulting alcohol was removed, and a 300 ppm titanium catalyst was added to increase the temperature to 245 ° C. while gradually reducing the pressure of the reaction system to 1 mmHg to prepare a thermoplastic polyether ester elastomer according to Comparative Examples 1 to 3.
[표 2]TABLE 2
Figure PCTKR2019004585-appb-I000005
Figure PCTKR2019004585-appb-I000005
상기 표 1 및 2의 결과로부터 알 수 있는 바와 같이, 본 발명에 따른 실시예 1 내지 9 의 열가소성 폴리에테르 에스테르 엘라스토머(디카르복실 화합물로서 퓨란족 디카르복실 화합물, 또는 퓨란족 디카르복실 화합물과 방향족 디카르복실 화합물의 조합을 포함하고, 1 내지 40 중량%의 범위 내에서 무수당 알코올-알킬렌 글리콜을 함유하는 TPEE)는 경도 및 열분해온도 등의 물리적 특성은 동등 수준으로 유지하면서도, 친환경성을 더욱 향상시키고, 엘라스토머의 융점이 보다 낮은 범위에서 용이하게 조절됨을 확인할 수 있다. As can be seen from the results of Tables 1 and 2, the thermoplastic polyether ester elastomers of Examples 1 to 9 according to the present invention (furan dicarboxylic compound or furan dicarboxylic compound as a dicarboxylic compound and TPEE) containing a combination of aromatic dicarboxyl compounds and containing anhydrosugar alcohol-alkylene glycol within a range of 1 to 40% by weight, while maintaining physical properties such as hardness and pyrolysis temperature, It is further improved, and it can be seen that the melting point of the elastomer is easily adjusted in the lower range.
즉, 본 발명에 따른 실시예 1 내지 9의 경우, 엘라스토머의 중요한 특성인 점도, 탄성 특성 및 물리적 특성(예를 들어, 경도 및 열분해온도 등)을 동등 수준으로 유지하고, 친환경성을 향상시키면서, 최종 제품의 성형 공정에서 다양하게 요구되는 융점을 용이하게 조절할 수 있으나, 본 발명에 따르지 않는 비교예 1의 경우(퓨란족 디카르복실 화합물 및 무수당 알코올-알킬렌 글리콜을 함유하지 않는 TPEE)에는 친환경성이 현저하게 열악하였고, 융점이 매우 높았으며, 비교예 2 의 경우(퓨란족 디카르복실 화합물을 함유하지 않는 TPEE)에는 융점이 매우 높았고, 비교예 3의 경우(40 중량% 초과의 범위로 무수당 알코올-알킬렌 글리콜을 함유하는 TPEE)에는 결정성 부분이 사라져 융점이 측정되지 않음을 확인할 수 있다. That is, in Examples 1 to 9 according to the present invention, while maintaining the viscosity, elasticity and physical properties (for example, hardness and pyrolysis temperature, etc.), which are important properties of the elastomer at the same level, while improving environmental friendliness, The melting point required in the molding process of the final product can be easily controlled, but in the case of Comparative Example 1 (TPEE not containing a furan dicarboxylic compound and anhydrosugar alcohol-alkylene glycol) according to the present invention The environmental friendliness was remarkably poor, the melting point was very high, and in Comparative Example 2 (TPEE containing no furan dicarboxylic compound), the melting point was very high, and in Comparative Example 3 (range of more than 40% by weight). TPEE) containing anhydrosugar alcohol-alkylene glycol, the crystalline portion disappears, it can be seen that the melting point is not measured.
상기 실시예 및 비교예에서 제조된 열가소성 엘라스토머의 물성 측정은 다음과 같이 진행하였다.Measurement of physical properties of the thermoplastic elastomer prepared in Examples and Comparative Examples was carried out as follows.
(1) 친환경성(wt%): 폴리에테르 에스테르 엘라스토머 총 중량 기준으로, 친환경 모노머인 무수당 알코올(이소소르비드)의 중량%를 측정하였다.(1) Eco-friendliness (wt%): Based on the total weight of the polyether ester elastomer, the weight% of the anhydrous sugar alcohol (isosorbide), which is an eco-friendly monomer, was measured.
(2) 극한점도(IV): 폴리에테르 에스테르 엘라스토머를 페놀/테트라클로로에탄 (중량비 50/50)에 녹여 0.5 중량% 용액을 만든 후, 우베로드 점도계로 35℃에서 측정하였다.(2) Intrinsic Viscosity (IV): The polyether ester elastomer was dissolved in phenol / tetrachloroethane (weight ratio 50/50) to form a 0.5 wt% solution, and then measured at 35 ° C. with a Uberod viscometer.
(3) 융점: 열시차 주사 열량계(DSC)를 이용하여 분당 10℃의 승온 속도로 승온 후 냉각하고 다시 승온하여 측정하였다. (3) Melting | fusing point: It measured after heating up after cooling up at the temperature increase rate of 10 degreeC per minute using a thermal differential scanning calorimeter (DSC).
(4) 경도: Handpi 사의 Showa D 경도계로 측정하였다.(4) Hardness: The hardness was measured by a Showa D hardness tester manufactured by Handpi.
(5) Td(℃): 열중량 분석기기(Perkin-Elmer사의 TGA-7)을 사용하여 5 중량% 감소하였을 때의 온도를 측정하였다. (5) T d (° C.): The temperature at the time of 5% by weight reduction was measured using a thermogravimetric analyzer (TGA-7 from Perkin-Elmer).

Claims (17)

  1. 하드 세그먼트 및 소프트 세그먼트로 이루어지는 열가소성 폴리에테르 에스테르 엘라스토머로서, A thermoplastic polyether ester elastomer composed of hard and soft segments,
    상기 하드 세그먼트는 중합 단위로서 디카르복실 화합물 및 지방족 디올 성분을 포함하고, The hard segment comprises a dicarboxylic compound and an aliphatic diol component as polymerized units,
    상기 소프트 세그먼트는 중합 단위로서 디카르복실 화합물 및 글리콜 성분을 포함하며, The soft segment comprises a dicarboxylic compound and a glycol component as polymerized units,
    상기 글리콜 성분이 무수당 알코올-알킬렌 글리콜을 포함하고, The glycol component comprises anhydrosugar alcohol-alkylene glycol,
    상기 디카르복실 화합물이 퓨란족 디카르복실 화합물, 또는 퓨란족 디카르복실 화합물과 방향족 디카르복실 화합물의 조합인,Wherein the dicarboxyl compound is a furan dicarboxylic compound or a combination of a furan dicarboxylic compound and an aromatic dicarboxyl compound,
    열가소성 폴리에테르 에스테르 엘라스토머.Thermoplastic polyether ester elastomers.
  2. 제1항에 있어서, 퓨란족 디카르복실 화합물이 디메틸-2,3-퓨란 디카르복실레이트, 디메틸-2,4-퓨란 디카르복실레이트, 디메틸-3,4-퓨란 디카르복실레이트, 디메틸-2,5-퓨란 디카르복실레이트, 2,3-퓨란 디카르복실산, 2,4-퓨란 디카르복실산, 3,4-퓨란 디카르복실산, 2,5-퓨란 디카르복실산, 디에틸-2,3-퓨란 디카르복실레이트, 디에틸-2,4-퓨란 디카르복실레이트, 디에틸-3,4-퓨란 디카르복실레이트, 디에틸-2,5-퓨란 디카르복실레이트, 디프로필-2,3-퓨란 디카르복실레이트, 디프로필-2,4-퓨란 디카르복실레이트, 디프로필-3,4-퓨란 디카르복실레이트, 디프로필-2,5-퓨란 디카르복실레이트, 또는 이들 중 2 이상의 혼합물인, 열가소성 폴리에테르 에스테르 엘라스토머.The method of claim 1, wherein the furan dicarboxylic compound is dimethyl-2,3-furan dicarboxylate, dimethyl-2,4-furan dicarboxylate, dimethyl-3,4-furan dicarboxylate, dimethyl -2,5-furan dicarboxylate, 2,3-furan dicarboxylic acid, 2,4-furan dicarboxylic acid, 3,4-furan dicarboxylic acid, 2,5-furan dicarboxylic acid , Diethyl-2,3-furan dicarboxylate, diethyl-2,4-furan dicarboxylate, diethyl-3,4-furan dicarboxylate, diethyl-2,5-furan dicar Carboxylate, dipropyl-2,3-furan dicarboxylate, dipropyl-2,4-furan dicarboxylate, dipropyl-3,4-furan dicarboxylate, dipropyl-2,5-furan A thermoplastic polyether ester elastomer, which is a dicarboxylate, or a mixture of two or more thereof.
  3. 제1항에 있어서, 방향족 디카르복실 화합물이 테레프탈산, 이소프탈산, 1,5-디나프탈렌 디카르복실산, 2,6-디나프탈렌 디카르복실산, 디메틸 테레프탈레이트, 디메틸 이소프탈레이트 또는 이의 조합으로 이루어진 군으로부터 선택되는, 열가소성 폴리에테르 에스테르 엘라스토머.The method of claim 1 wherein the aromatic dicarboxyl compound is terephthalic acid, isophthalic acid, 1,5-dinaphthalene dicarboxylic acid, 2,6-dinaphthalene dicarboxylic acid, dimethyl terephthalate, dimethyl isophthalate or a combination thereof. A thermoplastic polyether ester elastomer, selected from the group consisting of:
  4. 제1항에 있어서, 지방족 디올 성분이 탄소수 2 내지 8의 선형 지방족 디올 또는 탄소수 3 내지 8의 환형 지방족 디올인, 열가소성 폴리에테르 에스테르 엘라스토머.The thermoplastic polyether ester elastomer according to claim 1, wherein the aliphatic diol component is a linear aliphatic diol having 2 to 8 carbon atoms or a cyclic aliphatic diol having 3 to 8 carbon atoms.
  5. 제1항에 있어서, 지방족 디올 성분이 에틸렌 글리콜, 프로필렌 글리콜, 1,4-부탄디올, 1,5-펜탄디올, 1,6-헥산디올, 1,4-사이클로헥산디메탄올 또는 이의 조합으로 이루어진 군으로부터 선택되는, 열가소성 폴리에테르 에스테르 엘라스토머.The group of claim 1 wherein the aliphatic diol component consists of ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, or a combination thereof. Thermoplastic polyether ester elastomer.
  6. 제1항에 있어서, 무수당 알코올-알킬렌 글리콜이, 무수당 알코올의 양 말단 또는 일 말단의 히드록시기와 알킬렌 옥사이드를 반응시켜 얻어지는 부가물인, 열가소성 폴리에테르 에스테르 엘라스토머.The thermoplastic polyether ester elastomer according to claim 1, wherein the anhydrosugar alcohol-alkylene glycol is an adduct obtained by reacting a hydroxyl group and an alkylene oxide at both or one ends of the anhydrosugar alcohol.
  7. 제6항에 있어서, 무수당 알코올이 이소소르비드, 이소만니드, 이소이디드 또는 이의 조합으로 이루어진 군으로부터 선택되는, 열가소성 폴리에테르 에스테르 엘라스토머.The thermoplastic polyether ester elastomer of claim 6, wherein the anhydrosugar alcohol is selected from the group consisting of isosorbide, isomannide, isoidide or combinations thereof.
  8. 제6항에 있어서, 알킬렌 옥사이드가 탄소수 2 내지 8의 선형 또는 탄소수 3 내지 8의 분지형 알킬렌 옥사이드인, 열가소성 폴리에테르 에스테르 엘라스토머.7. The thermoplastic polyether ester elastomer of claim 6, wherein the alkylene oxide is a linear or branched alkylene oxide of 2 to 8 carbon atoms.
  9. 제6항에 있어서, 무수당 알코올이 이소소르비드이고, 알킬렌 옥사이드가 에틸렌 옥사이드, 프로필렌 옥사이드 또는 이의 조합인, 열가소성 폴리에테르 에스테르 엘라스토머.The thermoplastic polyether ester elastomer of claim 6, wherein the anhydrosugar alcohol is isosorbide and the alkylene oxide is ethylene oxide, propylene oxide or a combination thereof.
  10. 제1항에 있어서, 무수당 알코올-알킬렌 글리콜이 하기 화학식 1로 표시되는 화합물인, 열가소성 폴리에테르 에스테르 엘라스토머:The thermoplastic polyether ester elastomer according to claim 1, wherein the anhydrosugar alcohol-alkylene glycol is a compound represented by the following general formula (1):
    [화학식 1][Formula 1]
    Figure PCTKR2019004585-appb-I000006
    Figure PCTKR2019004585-appb-I000006
    상기 화학식 1에서,In Chemical Formula 1,
    R1 및 R2는 각각 독립적으로 탄소수 2 내지 8의 선형 또는 탄소수 3 내지 8의 분지형 알킬렌기를 나타내고, R 1 and R 2 each independently represent a linear or branched alkylene group having 2 to 8 carbon atoms or 3 to 8 carbon atoms,
    m 및 n은 각각 독립적으로 0 내지 15의 정수를 나타내며,m and n each independently represent an integer of 0 to 15,
    m+n은 1 내지 30의 정수를 나타낸다.m + n represents the integer of 1-30.
  11. 제10항에 있어서, R1 및 R2는 각각 독립적으로 에틸렌기, 프로필렌기 또는 이소프로필렌기를 나타내고, m 및 n은 각각 독립적으로 1 내지 14의 정수를 나타내며, m+n은 2 내지 15의 정수를 나타내는, 열가소성 폴리에테르 에스테르 엘라스토머.The compound according to claim 10, wherein R 1 and R 2 each independently represent an ethylene group, a propylene group or an isopropylene group, m and n each independently represent an integer of 1 to 14, and m + n is an integer of 2 to 15 Thermoplastic polyether ester elastomers.
  12. 제1항에 있어서, 열가소성 폴리에테르 에스테르 엘라스토머 100 중량% 내의 이소소르비드-알킬렌 글리콜 함량이 1 중량% 내지 40 중량%인, 열가소성 폴리에테르 에스테르 엘라스토머.The thermoplastic polyether ester elastomer of claim 1, wherein the isosorbide-alkylene glycol content in 100 wt% of the thermoplastic polyether ester elastomer is 1 wt% to 40 wt%.
  13. 제1항에 있어서, 소프트 세그먼트에 중합 단위로서 포함되는 글리콜 성분이 폴리알킬렌 에테르 글리콜을 추가로 포함하는, 열가소성 폴리에테르 에스테르 엘라스토머.The thermoplastic polyether ester elastomer of claim 1, wherein the glycol component included as polymerized units in the soft segment further comprises polyalkylene ether glycol.
  14. 제13항에 있어서, 폴리알킬렌 에테르 글리콜이 폴리에틸렌 에테르 글리콜, 폴리프로필렌 에테르 글리콜, 폴리테트라메틸렌 에테르 글리콜 또는 이의 조합으로 이루어진 군으로부터 선택되는, 열가소성 폴리에테르 에스테르 엘라스토머.The thermoplastic polyether ester elastomer of claim 13, wherein the polyalkylene ether glycol is selected from the group consisting of polyethylene ether glycol, polypropylene ether glycol, polytetramethylene ether glycol or combinations thereof.
  15. 제1항에 있어서, 열가소성 폴리에테르 에스테르 엘라스토머 100 중량% 내의 소프트 세그먼트 함량이 5 중량% 내지 75 중량%인, 열가소성 폴리에테르 에스테르 엘라스토머.The thermoplastic polyether ester elastomer of claim 1, wherein the soft segment content in 100 wt% of the thermoplastic polyether ester elastomer is from 5 wt% to 75 wt%.
  16. 디카르복실 화합물과 폴리올을 축중합 반응시키는 것을 포함하며, Polycondensation reaction of the dicarboxylic compound and the polyol,
    여기서, here,
    상기 폴리올이 지방족 디올 성분과 글리콜 성분을 포함하고, The polyol comprises an aliphatic diol component and a glycol component,
    상기 글리콜 성분이 무수당 알코올-알킬렌 글리콜을 포함하며, The glycol component comprises anhydrosugar alcohol-alkylene glycol,
    상기 디카르복실 화합물이 퓨란족 디카르복실 화합물, 또는 퓨란족 디카르복실 화합물과 방향족 디카르복실 화합물의 조합인,Wherein the dicarboxyl compound is a furan dicarboxylic compound or a combination of a furan dicarboxylic compound and an aromatic dicarboxyl compound,
    열가소성 폴리에테르 에스테르 엘라스토머의 제조 방법.Process for the preparation of thermoplastic polyether ester elastomers.
  17. 제1항 내지 제15항 중 어느 한 항에 따른 열가소성 폴리에테르 에스테르 엘라스토머를 포함하는 성형품.A molded article comprising the thermoplastic polyether ester elastomer according to any one of claims 1 to 15.
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