Eco-friendly thermoplastic polyether ester elastomer resin comprising chemically recycled monomer and bio-derived monomer, and preparation method therefor

Abstract

The present invention relates to an eco-friendly thermoplastic polyether ester elastomer resin comprising a chemically recycled monomer and a bio-derived monomer, and a preparation method therefor and, more specifically, to a thermoplastic polyether ester elastomer resin and a preparation method therefor, wherein the thermoplastic polyether ester elastomer resin comprises, in a hard segment, a dicarboxylic acid component obtained by chemical recycling and a bio-derived aliphatic diol component, and comprises, in a soft segment, a glycol component comprising polytrimethylene ether glycol (PO3G) and anhydrosugar alcohol-alkylene glycol (alkylene oxide adduct of anhydrosugar alcohol), and thus can uniformly maintain mechanical properties such as tensile strength or elongation while readily adjusting the melting point variously required in a molding process of a final product, and in particular, can solve the problem of depletion of petroleum resources, which are finite resources, and can improve eco-friendliness.

Description

Eco-friendly thermoplastic polyether ester elastomer resin containing chemically recycled monomers and bio-derived monomers and a method for manufacturing the same

[0001] The present invention relates to an eco-friendly thermoplastic polyether ester elastomer resin comprising chemically recycled monomers and bio-derived monomers, and a method for manufacturing the same. More specifically, the invention relates to a thermoplastic polyether ester elastomer resin and a method for manufacturing the same, wherein the hard segment contains a dicarboxylic acid component obtained by chemical recycling and a bio-derived aliphatic diol component, and the soft segment contains a glycol component comprising polytrimethylene ether glycol (PO3G) and anhydrous sugar alcohol-alkylene glycol (alkylene oxide adduct of anhydrous sugar alcohol), thereby allowing for easy control of the melting point required in the molding process of the final product while maintaining uniform mechanical properties such as tensile strength and elongation, and particularly, can solve the problem of depletion of petroleum resources, which are finite resources, and improve eco-friendliness.

[0002] Due to their unique elastic properties, elastomers are used in a wide range of applications, including packaging containers, automotive interiors, and elastic fibers. In particular, the usage of thermoplastic polyether ester copolymers is increasing due to their broad range of elastic properties. Furthermore, unlike rubber materials that cannot be recycled, elastomers are easy to recycle, leading to a significant increase in demand.

[0003] Thermoplastic elastomers are polymers that possess two distinct properties: the thermoplastic ability to reform upon heating and the elastic properties of elastomers, which are rubbery polymers. Thermoplastic elastomers exist as a type of block copolymer, generally composed of hard segment blocks that exhibit thermoplastic characteristics and soft segment blocks that exhibit the elastic properties of elastomers, thereby displaying both distinct characteristics simultaneously.

[0004] It is a known fact that polyether ester copolymers, in which polybutylene terephthalate-based polyester is used as the hard segment and polybutylene ether ester is used as the soft segment, exhibit excellent elastic properties, and polyethylene ether ester is also used as the soft segment to lower manufacturing costs.

[0005] U.S. Patent No. 3,023,192 discloses a hard segment / soft segment copolymer polyester and an elastomer prepared therefrom. The hard segment / soft segment copolymer polyester is prepared from (1) a dicarboxylic acid or an ester-forming derivative, (2) a polyethylene glycol ether, and (3) a dihydroxy compound selected from bisphenol and lower aliphatic glycols. Polyethers used as soft segments together with polyethylene glycol include polypropylene glycol, polytetramethylene glycol, polyhexamethylene glycol, etc., and polyethers with a molecular weight of about 350 to 6,000 are used.

[0006] 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. A hard segment constitutes 10 to 30 parts by weight of the elastomer, of which poly(1,3-propylene terephthalate) is 95 to 100 parts by weight. It is disclosed that the molecular weight of the poly(alkylene oxide) glycol is about 1,500 to about 5,000, and the carbon-to-oxygen ratio is 2 to 4.3.

[0007] Thermoplastic elastomers based on the examples of the prior art primarily use polytetramethylene glycol ether, copolymers of tetrahydrofuran and 3-alkyltetrahydrofuran, polyethylene glycol ether, polytrimethylene glycol ether, and copolymers thereof as soft segments. 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. When polyalkylene glycol ethers with high molecular weight are used to exhibit tough physical properties and elastic properties, the melting point increases, making it unsuitable for processes requiring a low melting point. Furthermore, when polyethylene glycol ether is formed as a soft segment, thermal stability decreases rapidly if the content of the soft segment is added at 20 weight% or more.

[0008] Furthermore, active research on eco-friendly biomass is garnering attention as part of efforts to reduce carbon dioxide emissions, a major cause of global warming, and to replace limited and expensive petroleum resources. There is a strong demand for a transition from conventional petroleum-derived plastics to plant-derived plastics that impose a lower environmental burden.

[0009] In order to solve the above-mentioned problems, the present invention aims to provide a thermoplastic polyether ester elastomer resin and a method for manufacturing the same, which can easily control the melting point required in the molding process of the final product while maintaining mechanical properties such as tensile strength and elongation uniformly, and in particular can solve the problem of depletion of petroleum resources, which are finite resources, and improve eco-friendliness.

[0010] A first aspect of the present invention provides a thermoplastic polyether ester elastomer comprising a hard segment and a soft segment, wherein the hard segment comprises an aromatic dicarboxylic compound and an aliphatic diol component as polymerization units, and the soft segment comprises an aromatic dicarboxylic compound and a glycol component as polymerization units, wherein the glycol component comprises polytrimethylene ether glycol (PO3G) and anhydrous sugar alcohol-alkylene glycol.

[0011] A second aspect of the present invention provides a method for manufacturing a thermoplastic polyether ester elastomer, comprising a condensation polymerization reaction between an aromatic dicarboxylic compound and a polyol, wherein the polyol comprises an aliphatic diol component and a glycol component, and the glycol component comprises polytrimethylene ether glycol (PO3G) and anhydrous sugar alcohol-alkylene glycol.

[0012] A third aspect of the present invention provides a molded article comprising a thermoplastic polyether ester elastomer according to the first aspect of the present invention.

[0013] The thermoplastic polyether ester elastomer (TPEE) according to the present invention comprises a dicarboxylic acid component obtained by chemical recycling and a bio-derived aliphatic diol component in the hard segment, and a glycol component comprising polytrimethylene ether glycol (PO3G) and anhydrous sugar alcohol-alkylene glycol (alkylene oxide adduct of anhydrous sugar alcohol) in the soft segment, thereby allowing for easy control of the melting point required in the molding process of the final product while maintaining uniform mechanical properties such as tensile strength and elongation, and in particular, can solve the problem of depletion of petroleum resources, which are finite resources, and improve eco-friendliness.

[0014] The present invention will be described in more detail below.

[0015] The hard segment constituting the thermoplastic polyether ester elastomer of the present invention comprises an aromatic dicarboxylic compound and an aliphatic diol component as polymerization units.

[0016] The above aromatic dicarboxylic acid compound is a chemically recycled compound, and the above aliphatic diol component is a bio-based aliphatic diol. In addition, polytrimethylene ether glycol (PO3G) and anhydrous sugar alcohol-alkylene glycol, which are glycol components included in the soft segment, are also bio-based polyols. By using these components, the problem of depletion of petroleum resources, which are finite resources, can be solved and environmental friendliness can be improved.

[0017] The above aromatic dicarboxylic compound may be an aromatic dicarboxylic acid or an aromatic dicarboxylate compound, and more specifically, may be selected from the group consisting of terephthalic acid, isophthalic acid, 1,5-dinaphthalene dicarboxylic acid, 2,6-dinaphthalene dicarboxylic acid, dimethyl terephthalate, dimethyl isophthalate, and combinations thereof.

[0018] The aliphatic diol component included as a polymerization 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, may be selected from the group consisting of ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol and combinations thereof.

[0019] The soft segment constituting the thermoplastic polyether ester elastomer of the present invention comprises an aromatic dicarboxylic compound and a glycol component as polymerization units, and the glycol component comprises polytrimethylene ether glycol (PO3G), which is one of the polyalkylene ether glycol components, and anhydrous sugar alcohol-alkylene glycol.

[0020] As the aromatic dicarboxylic compound included as a polymerization unit in the soft segment, the same as that described above in the hard segment may be used.

[0021] The above anhydrous sugar alcohol-alkylene glycol is an adduct obtained by reacting the hydroxyl group at both ends or one end (preferably both ends) of an anhydrous sugar alcohol with an alkylene oxide.

[0022] In one embodiment, the anhydrous sugar alcohol may be selected from the group consisting of isosorbide, isomandide, isoidide, and combinations thereof, and preferably may be isosorbide.

[0023] In one embodiment, the alkylene oxide may be a linear alkylene oxide having 2 to 8 carbon atoms or a branched alkylene oxide having 3 to 8 carbon atoms, and more specifically, may be ethylene oxide, propylene oxide, or a combination thereof.

[0024] In one embodiment, the anhydrous sugar alcohol-alkylene glycol may be a compound represented by the following chemical formula 1.

[0025] [Chemical Formula 1]

[0026]

[0027] In the above chemical formula 1,

[0028] R 1 and R 2 Each independently represents a linear alkylene group having 2 to 8 carbon atoms or a branched alkylene group having 3 to 8 carbon atoms, and

[0029] m and n each independently represent integers from 0 to 15, and

[0030] m+n represents an integer from 1 to 30.

[0031] More preferably, in the above formula 1,

[0032] R 1 and R 2Each independently represents an ethylene group, a propylene group, or an isopropylene group, preferably R 1 and R 2 are identical to each other,

[0033] m and n each independently represent integers from 1 to 14, and

[0034] m+n represents an integer from 2 to 15.

[0035] In one embodiment, the anhydrous sugar alcohol-alkylene glycol may be the following isosorbide-propylene glycol, isosorbide-ethylene glycol, or a mixture thereof.

[0036]

[0037] [Isosorbide-propylene glycol]

[0038] In the above chemical formula, a+b may be an integer from 1 to 30, and more preferably an integer from 2 to 15.

[0039]

[0040] [Isosorbide-ethylene glycol]

[0041] In the above chemical formula, c+d may be an integer from 1 to 30, and more preferably an integer from 2 to 15.

[0042] The thermoplastic polyether ester elastomer of the present invention may further comprise a branching agent selected from the group consisting of trimethylol ethane, sorbitol, pentaerythritol, 1,1,4,4-tetrakis(hydroxymethyl)cyclohexane, trimethylolpropane, 1,2,6-hexanetriol, hemimellitic acid, trimellitic acid, trimespyromellitic acid, 1,1,2,2-ethanetetracarboxylic acid, 1,1,2-ethanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, and combinations thereof.

[0043] The content of the branching agent may be 0.05 wt% or more, 0.06 wt% or more, 0.07 wt% or more, 0.08 wt% or more, 0.09 wt% or more, or 0.1 wt% or more, based on 100 wt% of the thermoplastic polyether ester elastomer of the present invention, and may be 1 wt% or less, 0.8 wt% or less, 0.6 wt% or less, 0.5 wt% or less, 0.4 wt% or less, or 0.3 wt% or less, for example, 0.05 to 1 wt%, 0.06 to 0.8 wt%, or 0.08 to 0.5 wt%. When the content of the branching agent is within the above range, the standard deviation of the tensile strength and elongation of the molded article may be lowered.

[0044] The content of anhydrous sugar alcohol-alkylene glycol in the thermoplastic polyether ester elastomer (TPEE) of the present invention may be 25 mol% or more, 26 mol% or more, 27 mol% or more, 28 mol% or more, 29 mol% or more, or 30 mol% or more, based on 100 mol% of the total of polytrimethylene ether glycol (PO3G) and anhydrous sugar alcohol-alkylene glycol of the soft segment, and may be 95 mol% or less, 94.8 mol% or less, 94.6 mol% or less, 94.5 mol% or less, 94.2 mol% or less, or 94 mol% or less, for example, 25 to 95 mol%, 26 to 94.8 mol%, or 28 to 94.5 mol%. When the content of anhydrous sugar alcohol-alkylene glycol is within the above range, the melting point of the molded article is easily controlled, and the standard deviation of tensile strength and elongation is reduced, thereby enabling the achievement of uniform mechanical properties.

[0045] The soft segment may be included in, for example, 20% to 90% by weight of 100% by weight of the thermoplastic polyether ester elastomer (TPEE) of the present invention, and may be included in an amount of, for example, 25% to 85%, 28% to 82% by weight, or 30% to 80% by weight. It is preferable that the content of the soft segment in the TPEE be within the above-mentioned range in terms of blow molding processability, mechanical strength, and flexibility. If the content of the soft segment in the TPEE is too low compared to the above-mentioned level, the hardness increases, making it difficult to expect flexibility; conversely, if it is too high, it is difficult to expect high heat resistance.

[0046] According to another aspect of the present invention, a method for manufacturing a thermoplastic polyether ester elastomer is provided, comprising a condensation polymerization reaction between an aromatic dicarboxylic compound and a polyol, wherein the polyol comprises an aliphatic diol component and a glycol component, and the glycol component comprises polytrimethylene ether glycol (PO3G) and anhydrous sugar alcohol-alkylene glycol.

[0047] The above polycondensation reaction may optionally be carried out in the presence of a catalyst, for example, under reduced pressure at a temperature of 210 to 250°C.

[0048] The thermoplastic polyether ester elastomer of the present invention is suitable for molding processes such as blow molding, extrusion, and injection molding, and while maintaining excellent elastic properties and physical properties (e.g., hardness, etc.), which are important characteristics of the elastomer, it is possible to easily control the melting point required in various ways during the molding process of the final product.

[0049] The thermoplastic polyether ester elastomer of the present invention has the characteristic of providing uniform properties with a significantly low standard deviation in mechanical properties such as tensile strength and elongation.

[0050] Accordingly, according to another aspect of the present invention, a molded article comprising the thermoplastic polyether ester elastomer of the present invention is provided.

[0051] The above-mentioned molded article may have a melting point of 190°C or lower, 185°C or lower, 180°C or lower, 175°C or lower, 170°C or lower, 165°C or lower, 160°C or lower, or 155°C or lower, and may be 140°C or higher, 145°C or higher, 150°C or higher, 155°C or higher, 160°C or higher, 165°C or higher, 170°C or higher, for example, 140°C to 190°C.

[0052] In addition, the above-mentioned molded article may have a standard deviation of tensile strength of 18 or less, 17 or less, for example, 10 to 18 or 10 to 17, and a standard deviation of elongation of 25 or less, 24 or less, 23 or less, 22 or less, for example, 15 to 22.

[0053]

[0054] The present invention will be explained in more detail below through examples and comparative examples. However, the scope of the present invention is not limited to these.

[0055]

[0056] [Example]

[0057] Preparation of Anhydrous Sugar Alcohol-Alkylene Glycol

[0058] Preparation Example: Preparation of isosorbide-ethylene glycol (isosorbide 5 molar ethylene oxide adduct)

[0059] 73.1 g (0.5 mol) of isosorbide, 110 g (2.5 mol) of ethylene oxide, and 0.2 g of sodium hydroxide as a catalyst were placed in a pressurized reaction apparatus equipped with a column with a nitrogen gas tube and a cooling device, a stirrer, a thermometer, and a heater, and the temperature was gradually increased. The reaction was carried out while maintaining the temperature at 120°C to 160°C for 2 to 4 hours to produce isosorbide-ethylene glycol (a 5 molar adduct of isosorbide with ethylene oxide), in which the hydrogens of the hydroxyl groups at both ends of the isosorbide are substituted with hydroxyethyl groups.

[0060]

[0061] <Manufacture of Thermoplastic Polyether Ester Elastomers>

[0062] Examples 1 to 13 and Comparative Examples 1 to 17

[0063] A reaction product with the composition shown in Table 1 below was placed in a 15L melt condensation reactor, and 700 ppm of a titanium-based catalyst was added based on the acid component (dimethyl terephthalate, DMT). Then, the temperature was raised to 210°C to remove alcohols produced as byproducts, and 300 ppm of a titanium-based catalyst was added while raising the temperature to 245°C and gradually reducing the pressure of the reaction system to 1 mmHg to produce thermoplastic polyether ester elastomers according to Examples 1 to 13 and Comparative Examples 1 to 17.

[0064]

[0065]

[0066] HS: Hard Segment

[0067] SS: Soft segment

[0068] Chemically Recycled DMT: Chemically Recycled Dimethyl Terephthalate

[0069] Bio-derived 1,4-BDO: Bio-derived 1,4-butanediol

[0070] Bio-derived polyols: Polytrimethylene ether glycol, anhydrous sugar alcohol-alkylene glycol

[0071] DMT: Dimethyl terephthalate

[0072] 1,4-BDO: 1,4-butanediol

[0073] EI 5: Isosorbide-ethylene glycol (5 molar adduct of ethylene oxide of isosorbide)

[0074] PO3G 2000: Polytrimethylene ether glycol 2000

[0075] PO3G 1000: Polytrimethylene ether glycol 1000

[0076] PTMG 2000: Polytetramethylene ether glycol 2000

[0077] PTMG 1000: Polytetramethylene Ether Glycol 1000

[0078] Antioxidant: Irganox 1010

[0079]

[0080] As can be seen from the results of Tables 1 and 2 above, the thermoplastic polyether ester elastomers of Examples 1 to 13 according to the present invention (TPEE comprising polytrimethylene ether glycol (PO3G) and anhydrous sugar alcohol-alkylene glycol as glycol components) have excellent processability with a melting point lowered to 190°C or lower, and as eco-friendly plastics using plant-derived raw materials, it can be confirmed that uniform mechanical properties of the elastomer can be achieved by significantly lowering the standard deviation of mechanical properties such as tensile strength and elongation. In addition, it can be confirmed that uniform mechanical properties can be achieved by using trimethylol ethane as a branching agent, which significantly reduces the standard deviation of mechanical properties such as tensile strength and elongation.

[0081] That is, in the case of Examples 1 to 13 according to the present invention, mechanical properties such as tensile strength and elongation can be maintained uniformly, and while improving eco-friendliness, the melting point required for various purposes in the molding process of the final product can be easily controlled; however, in the case of Comparative Examples 9, 12, 16, and 17 not according to the present invention (TPEE not containing PO3G), mechanical properties such as intrinsic viscosity and melt index were poor, or the standard deviation of tensile strength and elongation increased, so mechanical properties could not be maintained uniformly.

[0082] In the case of Comparative Examples 1, 2, 5 to 8, 14 and 15 (TPEE not containing anhydrous sugar alcohol-alkylene glycol) or Comparative Examples 3, 4, 10, 11 and 13 (TPEE containing anhydrous sugar alcohol-alkylene glycol in excess or insufficient amounts, or not containing trimethylol ethane as a branching agent), it was confirmed that the melting point was not easy to control or the standard deviation of tensile strength and elongation increased, making it impossible to maintain uniform mechanical properties.

[0083]

[0084] The physical properties of the thermoplastic elastomers prepared in the above examples and comparative examples were measured as follows.

[0085] (1) Hardness: Measured using a Showa D hardness tester from Handpi.

[0086] (2) Intrinsic viscosity (IV): Polyether ester elastomer was dissolved in phenol / tetrachloroethane (weight ratio 50 / 50) to make a 0.5 wt% solution, and then measured at 35°C using an Uberod viscometer.

[0087] (3) Melt index: Measured at 190°C and a load of 2.16 kg in accordance with ASTM D1238. However, 1) The item was measured at 220℃ and 2.16kg.

[0088] (4) Melting point: Measured by heating at a rate of 10°C per minute using a differential scanning calorimeter (DSC), then cooling and heating again.

[0089] (5) Eco-friendliness (wt%): Based on the total weight of the polyether ester elastomer, the weight percentage of the eco-friendly monomer, chemically recycled monomer (chemically recycled DMT), and the weight percentage of the bio-derived monomer (bio-derived 1,4-BDO, bio-polyol (PO3G, EI 5)) were measured.

[0090] (6) Tensile strength and standard deviation: Strength was measured according to ASTM D638, and the standard deviation was calculated as the standard deviation of 5 measurements.

[0091] (7) Elongation and standard deviation: Elongation was measured according to ASTM D638, and the standard deviation was calculated as the standard deviation of 5 measurements.

Claims

1. A thermoplastic polyether ester elastomer composed of hard segments and soft segments, The above hard segment comprises aromatic dicarboxylic compounds and aliphatic diol components as polymerization units, and The above soft segment comprises an aromatic dicarboxylic compound and a glycol component as polymerization units, and The above glycol component comprises polytrimethylene ether glycol (PO3G) and anhydrous sugar alcohol-alkylene glycol, Thermoplastic polyether ester elastomer.

2. A thermoplastic polyether ester elastomer according to claim 1, wherein the anhydrous sugar alcohol-alkylene glycol is represented by the following chemical formula 1: [Chemical Formula 1] In the above chemical formula 1, R 1 and R 2 Each independently represents a linear alkylene group having 2 to 8 carbon atoms or a branched alkylene group having 3 to 8 carbon atoms, and m and n each independently represent integers from 0 to 15, and m+n represents an integer from 1 to 30.

3. In paragraph 2, R in chemical formula 1 1 and R 2 A thermoplastic polyether ester elastomer, each independently representing an ethylene group, a propylene group, or an isopropylene group.

4. A thermoplastic polyether ester elastomer according to claim 1, wherein the aromatic dicarboxylic compound is a chemical recycling compound selected from the group consisting of terephthalic acid, isophthalic acid, 1,5-dinaphthalene dicarboxylic acid, 2,6-dinaphthalene dicarboxylic acid, dimethyl terephthalate, dimethyl isophthalate, and combinations thereof.

5. A thermoplastic polyether ester elastomer according to claim 1, wherein the aliphatic diol component is a bio-based aliphatic diol, which is a linear aliphatic diol having 2 to 8 carbon atoms or a cyclic aliphatic diol having 3 to 8 carbon atoms.

6. A thermoplastic polyether ester elastomer according to claim 1, wherein the aliphatic diol component is selected from the group consisting of ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, and combinations thereof.

7. The thermoplastic polyether ester elastomer of claim 1, further comprising a branching agent selected from the group consisting of trimethylol ethane, sorbitol, pentaerythritol, 1,1,4,4-tetrakis(hydroxymethyl)cyclohexane, trimethylolpropane, 1,2,6-hexanetriol, hemimellitic acid, trimellitic acid, trimespyromellitic acid, 1,1,2,2-ethanetetracarboxylic acid, 1,1,2-ethanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, and combinations thereof.

8. A thermoplastic polyether ester elastomer according to claim 1, wherein anhydrous sugar alcohol-alkylene glycol is contained in an amount of 25 to 95 mol% based on 100 mol% of the total of polytrimethylene ether glycol (PO3G) and anhydrous sugar alcohol-alkylene glycol of the soft segment.

9. A thermoplastic polyether ester elastomer according to claim 1, wherein the soft segment content in 100 weight% of the thermoplastic polyether ester elastomer is 20 weight% to 90 weight%.

10. A method for manufacturing a thermoplastic polyether ester elastomer, It includes polycondensation reaction of an aromatic dicarboxylic acid compound and a polyol, and Here, The above polyol comprises an aliphatic diol component and a glycol component, and The above glycol component comprises polytrimethylene ether glycol (PO3G) and anhydrous sugar alcohol-alkylene glycol, Method for manufacturing a thermoplastic polyether ester elastomer.

11. A molded article comprising a thermoplastic polyether ester elastomer according to any one of claims 1 to 9.

12. A molded article according to claim 11, having a melting point of 140°C to 190°C.

13. A molded article according to Clause 11, wherein the standard deviation of tensile strength is 18 or less and the standard deviation of elongation is 15 to 22.

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