KR102289472B1 - Thermoplastic polyester ester elastomer comprising anhydrosugar alcohol derivative and polyester polyol and method for preparing the same - Google Patents

Abstract

The present invention relates to a thermoplastic polyester ester elastomer (TPEE) having a hard segment and a soft segment and a method for manufacturing the same, and more particularly, to anhydrosugar alcohol with improved reactivity derived from biomass in the soft segment. It contains a derivative-derived unit and a polyester polyol-derived unit, and by controlling the content of anhydrosugar alcohol derivative and polyester polyol, it has excellent heat resistance and mechanical properties, and is easy to process due to its low melting point (processing temperature). It relates to a thermoplastic polyester ester elastomer capable of solving the problem of depletion of petroleum resources, which is a resource, and improving eco-friendliness, and a method for manufacturing the same.

Description

Thermoplastic polyester ester elastomer comprising anhydrosugar alcohol derivative and polyester polyol, and method for preparing the same

The present invention relates to a thermoplastic polyester ester elastomer (TPEE) having a hard segment and a soft segment and a method for manufacturing the same, and more particularly, to anhydrosugar alcohol with improved reactivity derived from biomass in the soft segment. It contains a derivative-derived unit and a polyester polyol-derived unit, and by controlling the content of anhydrosugar alcohol derivative and polyester polyol, it has excellent heat resistance and mechanical properties, and is easy to process due to its low melting point (processing temperature). It relates to a thermoplastic polyester ester elastomer capable of solving the problem of depletion of petroleum resources, which is a resource, and improving eco-friendliness, and a method for manufacturing the same.

Elastomers are used in many applications such as packaging containers, automobile interior materials, and elastic fibers due to their unique elastic properties. In particular, in the case of thermoplastic polyether ester copolymers, their usage is increasing due to a wide range of elastic properties. In addition, elastomers, unlike rubber materials that cannot be recycled, are easily recyclable, so the demand for them is greatly increasing.

Thermoplastic elastomers are polymers that have the properties of rubber-like viscoelasticity while having a thermoplastic that can be re-formed when heated. The thermoplastic elastomer is a kind of block copolymer, and is generally composed of a soft segment block that can exhibit viscous properties and a hard segment block that can exhibit elastic properties, and exhibits two different properties at the same time.

In general, it is a known fact that a polyether ester copolymer using polybutylene terephthalate-based polyester as the hard segment and polybutylene ether ester as the soft segment exhibits excellent elastic properties. It is also used as a soft segment.

U.S. Patent No. 3,023,192 discloses hard segment/soft segment copolyesters and elastomers prepared therefrom. The hard segment/soft segment copolyesters are prepared from (1) dicarboxylic acids or ester forming derivatives, (2) polyethylene glycol ethers, and (3) dihydroxy compounds selected from bisphenols and lower aliphatic glycols. Polyethers used as the soft segment together 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 a thermoplastic polyether ester elastomer comprising at least 70 parts by weight of a soft segment derived from poly(alkylene oxide)glycol and terephthalic acid. The hard segment constitutes 10 to 30 parts by weight of the elastomer, and in the hard segment, 95 to 100 parts by weight of poly(1,3-propylene terephthalate). It is suggested that poly(alkylene oxide) glycols have a molecular weight of from about 1,500 to about 5,000 and a carbon to oxygen ratio of from 2 to 4.3.

Thermoplastic elastomers based on those exemplified in the prior art are mainly polytetramethylene glycol ethers, copolymers of tetrahydrofuran and 3-alkyltetrahydrofuran, polyethylene glycol ethers, polytrimethylene glycol ethers and copolymers thereof as soft segments. use The melting point and physical properties of these copolymers are determined by the molecular weight and composition ratio of the polyalkylene glycol ether used as the soft segment. In the case of using a polyalkylene glycol ether having a high molecular weight in order to express strong physical and elastic properties, it cannot be applied to a process requiring a low melting point manufacturing process because the melting point is increased.

In addition, as part of an effort to reduce the emission of carbon dioxide, a major cause of global warming, and to replace limited expensive petroleum resources, active research on eco-friendly biomass is attracting attention. Conversion from conventional petroleum-derived plastics to plant-derived plastics with a small environmental load is actively demanded.

In addition, there is a demand for development of plastics having better heat resistance and mechanical properties, and therefore, it is necessary to improve the physical properties of thermoplastic elastomers that can be used for various purposes.

In order to solve the above problems, the present invention has excellent heat resistance and mechanical properties and is easy to process because of its low melting point (processing temperature). An object of the present invention is to provide a thermoplastic polyester ester elastomer and a method for producing the same.

In order to solve the above technical problem, the present invention provides a thermoplastic polyester ester elastomer comprising a hard segment and a soft segment, wherein the hard segment comprises an aromatic dicarboxyl compound and an aliphatic diol component as polymerized units, and the soft segment is polymerized An aromatic dicarboxyl compound and a polyol component are included as units, the polyol component includes a polyester polyol and anhydrosugar alcohol-alkylene glycol, and the content of the polyester polyol is based on the total weight of the thermoplastic polyester ester elastomer , 8 to 45% by weight, and the content of the anhydrosugar alcohol-alkylene glycol is 3 to 15% by weight, based on the total weight of the thermoplastic polyester ester elastomer, to provide a thermoplastic polyester ester elastomer.

According to another aspect of the present invention, it comprises a polycondensation reaction of an aromatic dicarboxyl compound and a polyol, wherein the polyol component comprises an aliphatic diol, a polyester polyol and anhydrosugar alcohol-alkylene glycol, and the polyol The content of the ester polyol is 8 to 45% by weight based on the total weight of the thermoplastic polyester ester elastomer, and the content of the anhydrosugar alcohol-alkylene glycol is 3 to 15 based on the total weight of the thermoplastic polyester ester elastomer % by weight of a thermoplastic polyester ester elastomer.

According to another aspect of the present invention, there is provided a molded article comprising the thermoplastic polyester ester elastomer of the present invention.

The thermoplastic polyester ester elastomer (TPEE) according to the present invention consists of a hard segment and a soft segment, and anhydrosugar alcohol-alkylene glycol (anhydrosugar alcohol of alkylene oxide adduct) and polyester polyol, and by controlling the content of anhydrosugar alcohol derivative and polyester polyol, it exhibits excellent heat resistance and mechanical properties, and is easy to process due to its low melting point (processing temperature), In particular, the problem of depletion of petroleum resources, which is a finite resource, can be solved, and eco-friendliness can be improved.

Hereinafter, the present invention will be described in detail.

The hard segment constituting the thermoplastic polyester ester elastomer of the present invention includes an aromatic dicarboxyl compound and an aliphatic diol component as polymerized units.

The aromatic dicarboxyl compound may be an aromatic dicarboxylic acid or an aromatic dicarboxylate compound, and more specifically, terephthalic acid, isophthalic acid, 1,5-dinaphthalene dicarboxylic acid, and 2,6-dinaphthalene. It may be one selected from the group consisting of dicarboxylic acid, dimethyl terephthalate, dimethyl isophthalate, and combinations thereof.

The aliphatic diol component included in the hard segment as a polymerization unit 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, more specifically , ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, and combinations thereof.

The soft segment constituting the thermoplastic polyester ester elastomer of the present invention includes an aromatic dicarboxyl compound and a polyol component as polymerized units, and the polyol component includes a polyester polyol and anhydrosugar alcohol-alkylene glycol.

As the aromatic dicarboxyl compound included as a polymerization unit in the soft segment, the same as those described above in the hard segment may be used.

Among polyols included as a polymerization unit of the soft segment, the polyester polyol is prepared from polycondensation of an aliphatic dicarboxyl compound and an aliphatic diol.

The aliphatic dicarboxyl compound may be an aliphatic dicarboxylic acid or an aliphatic dicarboxylate compound, and more specifically, adipic acid, succinic acid, sebacic acid, dodecanedicarboxylic acid, or an ester thereof (eg, dimethyl adi Pate, diethyl adipate, dimethyl succinate, diethyl succinate, dimethyl sebacate, diethyl sebacate, dimethyl dodecanedicarboxylate, diethyl dodecanedicarboxylate) or a mixture of two or more and the aliphatic diol is ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-1,3-propanediol, 3 -One selected from methyl-1,5-pentanediol, 2-methylpentanediol, 2,2,4-trimethyl-1,6-hexanediol or 2,3,5-trimethyl-1,6-hexanediol Or it may be a mixture of two or more types.

The content of the polyester polyol is 8 wt% or more, 10 wt% or more, 12 wt% or more, 13 wt% or more, 15 wt% or more, 20 wt% or more, based on the total weight of the thermoplastic polyester ester elastomer (TPEE); 25 wt% or more or 30 wt% or more, 45 wt% or less, 42 wt% or less, 40 wt% or less, 38 wt% or less, 35 wt% or less, 30 wt% or less or 25 wt% or less, e.g. For example, it may be 8 to 45% by weight, 10 to 45% by weight, 12 to 42% by weight or 15 to 38% by weight. When the content of the polyester polyol is adjusted within the above range, blockiness may occur and exhibit properties specific to TPEE, and if it exceeds 45% by weight, blockiness is not maintained and crystallinity is lowered, and the melting point and tensile strength are lowered. can be very low.

A polyether polyol (eg, polytetramethylene ether glycol (PTMEG)) used as a monomer for the soft segment of the conventional thermoplastic polyether ester elastomer has an ether linkage, whereas it is used as a monomer for the soft segment of the TPEE of the present invention. Since the polyester polyol has an ester bond, the glass transition temperature and tensile strength are increased compared to the conventional thermoplastic polyether ester elastomer. Here, as the anhydrosugar alcohol-alkylene glycol was added to a specific content range, the glass transition temperature was further increased and the tensile strength was further improved.

Anhydrosugar alcohol-alkylene glycol in the polyol included as a polymerization unit of the soft segment is an adduct obtained by reacting an alkylene oxide with hydroxyl groups at both ends or one terminal (preferably both ends) of the anhydrosugar alcohol.

In one embodiment, the anhydrosugar alcohol may be selected from the group consisting of isosorbide, isomannide, isoidide or a combination thereof, preferably isosorbide.

In one embodiment, the alkylene oxide may be a linear or branched alkylene oxide having 2 to 8 carbon atoms or a branched alkylene oxide having 3 to 8 carbon atoms, and more specifically, ethylene oxide, propylene oxide, or a combination thereof.

In one embodiment, the anhydrosugar alcohol-alkylene glycol may be a compound represented by Formula 1 below.

[Formula 1]

In Formula 1,

R ¹ and R ² each independently represent a linear or branched alkylene group having 2 to 8 carbon atoms or a branched alkylene group having 3 to 8 carbon atoms,

m and n each independently represent an integer of 0 to 15, provided that m+n represents an integer of 1 to 30.

More preferably, in Formula 1,

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 and n each independently represent an integer of 1 to 14, provided that m+n represents an integer of 2 to 15.

In one embodiment, as the anhydrosugar alcohol-alkylene glycol, the following isosorbide-propylene glycol, isosorbide-ethylene glycol, or a mixture thereof may be used.

[Isosorbide-Propylene Glycol]

In the above formula, a and b each independently represent an integer of 0 to 15, with the proviso that a+b may be an integer of 1 to 30, and more preferably a and b are each independently an integer of 1 to 14. with the proviso that a+b may be an integer from 2 to 15.

[Isosorbide-ethylene glycol]

In the above formula, c and d each independently represent an integer of 0 to 15, with the proviso that c+d may be an integer of 1 to 30, more preferably c and d are each independently an integer of 1 to 14 with the proviso that c+d may be an integer from 2 to 15.

The content of anhydrosugar alcohol-alkylene glycol may be 3 wt% or more, 4 wt% or more, 5 wt% or more, 6 wt% or more, or 8 wt% or more, based on the total weight of the thermoplastic polyester ester elastomer (TPEE) and , 15 wt% or less, 12 wt% or less, 11 wt% or less, 10 wt% or less, 9 wt% or less, 7 wt% or less, or 5 wt% or less, 3 to 15 wt%, 3 to 12 wt%, 4 to 11% by weight or 5 to 9% by weight. When the content of the anhydrosugar alcohol-alkylene glycol is adjusted within the above range, heat resistance and mechanical strength can be improved, and when it exceeds 15 wt%, it is difficult to maintain a certain level of physical properties due to phase separation during polymerization , the tensile strength may be poor.

In 100 wt% of the thermoplastic polyester ester elastomer (TPEE) of the present invention, the soft segment may be included, for example, in an amount of 5 wt% to 70 wt%, more preferably in an amount of 10 wt% to 60 wt% there is. It is preferable in terms of blow molding processability, mechanical strength, flexibility, etc. that the soft segment content in the TPEE is within the above range. If the content of the soft segment in the TPEE is too less than the above level, it is difficult to expect flexibility due to high hardness.

The thermoplastic polyester ester elastomer (TPEE) of the present invention may further comprise a branching agent. The branching agent serves to increase the reaction rate and melt viscosity, and the branching agent includes, for example, glycerol, pentaerythritol, trimellitic anhydride, trimellitic acid, It may be selected from trimethylol propane, neopentyl glycol, or a mixture thereof.

The content of the branching agent may be 0.01 to 0.1 wt% based on the total weight of the thermoplastic polyester ester elastomer (TPEE). If the content of the branching agent is less than 0.01% by weight, it is difficult to expect the effect of adding the branching agent, and if it exceeds 0.1% by weight, the effect of adding the branching agent is too excessive and may break the blocking property of the TPEE.

According to another aspect of the present invention, it comprises a polycondensation reaction of an aromatic dicarboxyl compound and a polyol, wherein the polyol component comprises an aliphatic diol, a polyester polyol and anhydrosugar alcohol-alkylene glycol, and the polyol The content of the ester polyol is 8 to 45% by weight based on the total weight of the thermoplastic polyester ester elastomer, and the content of the anhydrosugar alcohol-alkylene glycol is 3 to 15 based on the total weight of the thermoplastic polyester ester elastomer % by weight of a thermoplastic polyester ester elastomer.

In the production method of the present invention, the aromatic dicarboxyl compound, the aliphatic diol, the polyester polyol and the anhydrosugar alcohol-alkylene glycol are as described for the thermoplastic polyester ester elastomer of the present invention.

The polycondensation reaction may be carried out under reduced pressure, optionally in the presence of a catalyst, for example, under a temperature condition of 210 to 250°C.

The type of the catalyst is not particularly limited, and any type of catalyst may be used as long as it is used for a polycondensation catalyst, for example, one or a mixture of two or more selected from a titanium-based catalyst, an antimony-based catalyst, or a magnesium-based catalyst. Can be used.

The thermoplastic polyester ester elastomer of the present invention is suitable for molding processes such as blow, extrusion, and injection, and in particular, it has excellent heat resistance and mechanical properties, and is easy to process because of its low melting point (processing temperature).

Accordingly, according to another aspect of the present invention, there is provided a molded article including the thermoplastic polyester ester elastomer of the present invention.

Hereinafter, the present invention will be described in more detail through Examples and Comparative Examples. However, the scope of the present invention is not limited thereto.

[ Example ]

<Thermoplastic polyester ester elastomer ( TPEE ) manufacturing>

Example 1 to 6

Put the reactants of the composition shown in Table 1 below in a 15L melt-condensation reactor, and after adding 700 ppm of a titanium-based catalyst based on an acid component (dimethyl terephthalate, DMT), the temperature is raised to 210° C. and produced as a by-product The alcohol used was removed, and the pressure of the reaction system was gradually reduced to 1 mmHg while raising the temperature to 245° C. by adding 300 ppm of a titanium-based catalyst, thereby preparing thermoplastic polyester ester elastomers according to Examples 1 to 6. Physical properties were evaluated for the thermoplastic polyester ester elastomers prepared in Examples 1 to 6, and the results are shown in Table 1 below.

[Table 1]

comparative example 1 to 7

Put the reactants of the composition shown in Table 2 below in a 15L melt-condensation reactor, and after adding 700 ppm of a titanium-based catalyst based on an acid component (dimethyl terephthalate, DMT), the temperature is raised to 210 ° C. and produced as a by-product The alcohol used was removed, and the pressure of the reaction system was gradually reduced to 1 mmHg while raising the temperature to 245° C. by adding 300 ppm of a titanium-based catalyst to prepare thermoplastic polyester ester elastomers according to Comparative Examples 1 to 7. Physical properties were evaluated for the thermoplastic polyester ester elastomers prepared in Comparative Examples 1 to 7, and the results are shown in Table 2 below.

[Table 2]

<Evaluation of physical properties>

(1) Intrinsic Viscosity (IV)

After dissolving a thermoplastic polyester ester elastomer in a mixture of phenol and tetrachloroethane (weight ratio = 50:50) to prepare a 0.5 wt% solution, the intrinsic viscosity was measured at 35°C with an Uberod viscometer.

(2) hardness

Hardness was measured using a Showa D hardness tester manufactured by Handpi.

(3) Melting point (Tm)

Using a thermal differential scanning calorimeter (DSC), the temperature was raised at a temperature increase rate of 10° C. per minute, cooled, and then the temperature was increased again to measure the melting point.

(4) Glass transition temperature (Tg)

The tanδ (tangent delta) value measured at 0.1 Hz in the range of -50°C to 150°C using DMA (Dynamic Mechanical Analyzer) was compared as the glass transition temperature.

(5) Tensile strength

Tensile strength was evaluated according to ASTM D638.

As shown in Table 1, the thermoplastic polyester ester elastomers (TPEE) of Examples 1 to 6 according to the present invention have a lower melting point compared to the TPEE of Comparative Example having an equivalent level of hardness, so that processing is easy, and Tg is - Heat resistance was excellent at 1°C or higher, and mechanical strength was also excellent with a tensile strength of 250 kg cm/cm or higher. (Comparison of physical properties of Comparative Examples 1, 3, 4, 6 and Examples 2 and 6 with 40D hardness, Comparison of physical properties of Comparative Example 7 with 55D hardness and Examples 1, 4, and 5 / Comparative Example 5 and Example with 65D hardness Comparison of physical properties in 3)

In the case of Comparative Example 1, the content of anhydrosugar alcohol-alkylene glycol was small, so there was no effect of improving the physical properties of the glass transition temperature and tensile strength. , the melting point was too low, the tensile strength was very poor, and in Comparative Example 3, the content of the polyester polyol was very small, so there was little effect of improving the physical properties of the glass transition temperature and tensile strength, and in the case of Comparative Example 4, no sugar Since the alcohol-alkylene glycol content was excessive, phase separation occurred, which made it difficult to maintain a certain level of physical properties and deteriorated tensile strength. In Comparative Example 6, polyester polyol was not used, so glass transition temperature and tensile strength There was no effect of improving the physical properties of strength.

Claims (15)

A thermoplastic polyester ester elastomer comprising a hard segment and a soft segment, comprising:
The hard segment includes an aromatic dicarboxyl compound and an aliphatic diol component as polymerized units,
The soft segment includes an aromatic dicarboxyl compound and a polyol component as polymerized units,
The polyol component comprises a polyester polyol and anhydrosugar alcohol-alkylene glycol,
The content of the polyester polyol is 12 to 42% by weight based on the total weight of the thermoplastic polyester ester elastomer,
The content of the anhydrosugar alcohol-alkylene glycol is 3 to 11% by weight based on the total weight of the thermoplastic polyester ester elastomer,
Thermoplastic polyester ester elastomer. 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 polyester ester elastomer selected from the group consisting of. The thermoplastic polyester 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. The group of claim 1, wherein the aliphatic diol component is ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol or a combination thereof. A thermoplastic polyester ester elastomer selected from The thermoplastic polyester ester elastomer of claim 1 , wherein the polyester polyol is prepared from polycondensation of an aliphatic dicarboxyl compound and an aliphatic diol. The thermoplastic polyester ester elastomer according to claim 5, wherein the aliphatic dicarboxyl compound is one or a mixture of two or more selected from the group consisting of adipic acid, succinic acid, sebacic acid, dodecanedicarboxylic acid, or esters thereof. 6. The method of claim 5, wherein the aliphatic diol is ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-1,3-propanediol; from the group consisting of 3-methyl-1,5-pentanediol, 2-methylpentanediol, 2,2,4-trimethyl-1,6-hexanediol or 2,3,5-trimethyl-1,6-hexanediol A thermoplastic polyester ester elastomer, which is one or a mixture of two or more selected. The thermoplastic polyester ester elastomer according to claim 1, wherein the anhydrosugar alcohol-alkylene glycol is an adduct obtained by reacting an alkylene oxide with a hydroxyl group at both ends or one terminal of the anhydrosugar alcohol. The thermoplastic polyester ester elastomer of claim 8 , wherein the anhydrosugar alcohol is selected from the group consisting of isosorbide, isomannide, isoidide, or combinations thereof. The thermoplastic polyester ester elastomer according to claim 8, wherein the alkylene oxide is a linear or branched alkylene oxide having 2 to 8 carbon atoms or 3 to 8 carbon atoms. The thermoplastic polyester ester elastomer of claim 8 , wherein the anhydrosugar alcohol is isosorbide and the alkylene oxide is ethylene oxide, propylene oxide, or a combination thereof. The thermoplastic polyester ester elastomer according to claim 1, wherein the anhydrosugar alcohol-alkylene glycol is a compound represented by the following formula (1):
[Formula 1]

In Formula 1,
R ¹ and R ² each independently represent a linear or branched alkylene group having 2 to 8 carbon atoms or a branched alkylene group having 3 to 8 carbon atoms,
m and n each independently represent an integer of 0 to 15, provided that m+n represents an integer of 1 to 30. According to claim 1, glycerol, pentaerythritol (pentaerythritol), trimellitic anhydride (trimellitic anhydride), trimellitic acid (trimellitic acid), trimethylol propane (trimethylol propane), neopentyl glycol (neopentyl glycol) or these A thermoplastic polyester ester elastomer further comprising a branching agent selected from mixtures. It comprises a polycondensation reaction of an aromatic dicarboxyl compound and a polyol,
Here, the polyol component includes an aliphatic diol, a polyester polyol and anhydrosugar alcohol-alkylene glycol,
The content of the polyester polyol is 12 to 42% by weight based on the total weight of the thermoplastic polyester ester elastomer,
The content of the anhydrosugar alcohol-alkylene glycol is 3 to 11% by weight based on the total weight of the thermoplastic polyester ester elastomer,
A method of making a thermoplastic polyester ester elastomer. A molded article comprising the thermoplastic polyester ester elastomer according to any one of claims 1 to 13.