Polycarbonate ester elastomer comprising anhydrosugar alcohol-based carbonate diol as polymerization unit of hard segment and preparation method therefor

Abstract

The present invention relates to a polycarbonate ester elastomer and a preparation method therefor and, more specifically, to a thermoplastic polycarbonate ester elastomer and a preparation method therefor, wherein the thermoplastic polycarbonate ester elastomer has a hard segment and a soft segment and comprises an anhydrosugar alcohol-based carbonate diol as a polymerization unit of the hard segment, thereby exhibiting improved heat resistance (i.e., increased glass transition temperature (Tg)) and / or excellent mechanical properties (e.g., tensile strength, elongation, etc.) compared to conventional thermoplastic polyether ester elastomer resins.

Description

Polycarbonate ester elastomer comprising anhydrous sugar alcohol-based carbonate diol as a polymerization unit of hard segments and a method for manufacturing the same

[0001] The present invention relates to a polycarbonate ester elastomer and a method for manufacturing the same, and more specifically, to a thermoplastic polycarbonate ester elastomer having a hard segment and a soft segment, and comprising an anhydrous sugar alcohol-based carbonate diol as a polymerization unit of the hard segment, which can exhibit improved heat resistance (i.e., elevated glass transition temperature (Tg)) and / or excellent mechanical properties (e.g., tensile strength, elongation, etc.) compared to conventional thermoplastic polyether ester elastomer resins, and a method for manufacturing the same.

[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. Among these, the demand for thermoplastic elastomers is rising significantly because, unlike rubber materials which cannot be recycled, they are easy to recycle.

[0003] 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.

[0004] Polyether ester elastomers are thermoplastic resins that possess properties similar to rubber and are used in various applications, such as elastic fibers and automotive interior materials. However, existing polyether ester elastomer resins need to be improved in terms of heat resistance and mechanical properties.

[0005] Hydrogenated sugars (also called “sugar alcohols”) refer to compounds obtained by adding hydrogen to the reducing terminal groups of sugars, generally HOCH2(CHOH) n It has the chemical formula CH2OH (where n is an integer from 2 to 5) and is classified into tetritol, pentitol, hexitol, and heptitol (with 4, 5, 6, and 7 carbon atoms, respectively) depending on the number of carbon atoms. Among these, hexitol, which has 6 carbon atoms, includes sorbitol, mannitol, iditol, galactitol, etc., and sorbitol and mannitol are particularly useful substances.

[0006] Anhydrous sugar alcohols are substances formed by removing one or more water molecules from within hydrogenated sugars; when one water molecule is removed, they take the form of tetraols with four hydroxyl groups within the molecule, and when two water molecules are removed, they take the form of diols with two hydroxyl groups within the molecule. They can be manufactured using hexitol derived from starch (e.g., Korean Registered Patent No. 10-1079518, Korean Published Patent Application No. 10-2012-0066904). Anhydrous sugar alcohols have long attracted significant interest as environmentally friendly substances derived from renewable natural resources, and research on their manufacturing methods has been ongoing. Among these anhydrous sugar alcohols, isosorbide produced from sorbitol currently has the widest range of industrial applications.

[0007] The applications of anhydrous sugar alcohol are highly diverse, ranging from the treatment of heart and vascular diseases and pharmaceuticals such as patches and mouthwashes to solvents in cosmetic compositions and emulsifiers in the food industry. Furthermore, it can raise the glass transition temperature of polymeric materials such as polyester, PET, polycarbonate, polyurethane, and epoxy resins, and improves their strength. As an eco-friendly material derived from natural sources, it is also highly useful in the plastics industry, including for bioplastics. Additionally, it is known to be usable as an adhesive, eco-friendly plasticizer, biodegradable polymer, and an eco-friendly solvent for water-soluble lacquers. As such, anhydrous sugar alcohol is receiving significant attention due to its diverse potential applications, and its utilization in actual industries is gradually increasing.

[0008] The object of the present invention is to provide a thermoplastic polycarbonate ester elastomer, which is a thermoplastic elastomer material with improved heat resistance and / or mechanical properties compared to conventional thermoplastic polyether ester elastomer resins, and a method for manufacturing the same.

[0009] One aspect of the present invention provides a thermoplastic polycarbonate ester elastomer having a hard segment and a soft segment, wherein the polymerization units comprise an aromatic dicarboxylic compound and a polyol, wherein the polyol comprises an aliphatic diol component for the hard segment and a polyol component for the soft segment, and the aliphatic diol component for the hard segment comprises an anhydrous sugar alcohol-based carbonate diol.

[0010] Another aspect of the present invention provides a method for manufacturing a thermoplastic polycarbonate ester elastomer having hard segments and soft segments, comprising a condensation polymerization reaction between an aromatic dicarboxylic compound and a polyol, wherein the polyol comprises an aliphatic diol component for the hard segment and a polyol component for the soft segment, and the aliphatic diol component comprises an anhydrous sugar alcohol-based carbonate diol.

[0011] Another aspect of the present invention provides a molded article comprising the thermoplastic polycarbonate ester elastomer of the present invention.

[0012] The thermoplastic polycarbonate ester elastomer according to the present invention can exhibit improved heat resistance (i.e., elevated glass transition temperature (Tg)) and / or excellent mechanical properties (e.g., tensile strength, elongation, etc.) compared to conventional thermoplastic polyether ester elastomer resins, and can also enhance the value of biomaterials and contribute to environmental sustainability by using anhydrous sugar alcohol, which is an eco-friendly material, as a raw material.

[0013] The present invention will be described in detail below.

[0014] The thermoplastic polycarbonate ester elastomer of the present invention has a hard segment and a soft segment, and comprises an aromatic dicarboxylic compound and a polyol as polymerization units.

[0015] In the present invention, the dicarboxyl compound is included as a polymerization unit in both the hard segment and the soft segment.

[0016] In one embodiment, the 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-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, dimethyl terephthalate, diethyl terephthalate, dimethyl isophthalate, diethyl isophthalate, or a combination thereof.

[0017] In the present invention, the polyol comprises an aliphatic diol component for a hard segment and a polyol component for a soft segment, wherein the aliphatic diol component for the hard segment comprises an anhydrous sugar alcohol-based carbonate diol.

[0018] In one embodiment, the anhydrous sugar alcohol-based carbonate diol may be the result of an esterification reaction between an anhydrous sugar alcohol and a carbonate-based compound.

[0019] The above anhydrous alcohol may be a single anhydrous alcohol, a two-anhydrous alcohol, or a combination thereof.

[0020] The above-mentioned anhydrous sugar alcohol is an anhydrous sugar alcohol formed by removing one water molecule from the interior of a hydrogenated sugar, and has a tetraol form with four hydroxyl groups within the molecule. Specifically, the above-mentioned anhydrous sugar alcohol may be anhydrous sugar hexitol, and more specifically, may be 1,4-anhydrohexitol, 3,6-anhydrohexitol, 2,5-anhydrohexitol, 1,5-anhydrohexitol, 2,6-anhydrohexitol, or a mixture of two or more of these.

[0021] The above-mentioned dianhydrogenated sugar alcohol is an anhydrogenated sugar alcohol formed by removing two water molecules from the interior of a hydrogenated sugar, has a diol form with two hydroxyl groups within the molecule, and can be prepared using hexitol derived from starch. Specifically, the above-mentioned dianhydrogenated sugar alcohol may be dianhydrogenated sugar hexitol, and more specifically, may be 1,4:3,6-dianhydrohexitol.

[0022] In one embodiment, the anhydrous sugar alcohol may be a dihydrous sugar alcohol, more specifically a dihydrous sugar hexitol, more specifically a 1,4:3,6-dianhydrohexitol, more specifically selected from the group consisting of isosorbide, isomandide, isoidide, or a combination thereof, and preferably isosorbide.

[0023] In one embodiment, the carbonate compound may be one or more selected from the group consisting of aliphatic carbonate compounds, alicyclic carbonate compounds, aromatic carbonate compounds, or combinations thereof.

[0024] More specifically, the aliphatic carbonate compound may be one or more selected from the group consisting of dimethyl carbonate, diethyl carbonate, din-propyl carbonate, diisopropyl carbonate, din-butyl carbonate, diisobutyl carbonate, dit-butyl carbonate, dihexyl carbonate, dicyclohexyl carbonate, dicaprylyl carbonate, diallyl carbonate, dimethyl dicarbonate, diethyl dicarbonate, din-propyl dicarbonate, diisopropyl dicarbonate, din-butyl dicarbonate, diisobutyl dicarbonate, dit-butyl dicarbonate, dihexyl dicarbonate, dicyclohexyl dicarbonate, dicaprylyl dicarbonate, diallyl dicarbonate, or combinations thereof; The above cycloaliphatic carbonate compound may be one or more selected from the group consisting of ethylene carbonate, propylene carbonate, trimethylene carbonate, butylene carbonate, or combinations thereof; the above aromatic carbonate compound may be diphenyl carbonate, but is not limited thereto.

[0025] In one embodiment, the esterification reaction of the anhydrous sugar alcohol and the carbonate-based compound may be carried out in the presence of a catalyst selected from the group consisting of organic base compounds, inorganic base compounds, or combinations thereof, such as, for example, organic base compounds such as triethylamine, pyridine, imidazole, guanidine; inorganic base compounds such as sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, aluminum hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, etc.; or combinations thereof, but is not limited thereto.

[0026] In one embodiment, the anhydrous sugar alcohol-based carbonate diol may have a structure represented by the following chemical formula 1:

[0027] [Chemical Formula 1]

[0028]

[0029] In the above chemical formula 1, n is an integer from 1 to 10, preferably an integer from 1 to 5.

[0030] In one embodiment, the aliphatic diol component for the hard segment may further include an additional aliphatic diol (hereinafter “additional aliphatic diol”) different from the anhydrous sugar alcohol-based carbonate diol described above.

[0031] These additional aliphatic diols may be, for example, linear, branched, or cyclic aliphatic diols, more specifically, linear aliphatic diols having 2 to 8 carbon atoms, branched aliphatic diols having 3 to 8 carbon atoms, or cyclic aliphatic diols 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, or combinations thereof, but are not limited thereto.

[0032] In one embodiment, the polyol component for the soft segment may be polyalkylene ether glycol, more specifically poly(C2-C8)alkylene ether glycol, more specifically may be selected from the group consisting of polyethylene ether glycol, polypropylene ether glycol, polytetramethylene ether glycol or a combination thereof, and more specifically may be polytetramethylene ether glycol.

[0033] In one embodiment, the polyol component for the hard segment does not include anhydrous sugar alcohol as an independent component.

[0034] In one embodiment, the polyol component for the soft segment does not include the anhydrous sugar alcohol-based carbonate diol mentioned above.

[0035] In one embodiment, the anhydrous sugar alcohol-based carbonate diol may be included in an amount of 8 to 70 mol% within the total 100 mol% of the polyol. If the content of the anhydrous sugar alcohol-based carbonate diol within the total 100 mol% of the polyol is lower than the above level, the glass transition temperature of the hard segment may be lowered, and the heat resistance of the polycarbonate ester elastomer may be poor; conversely, if the content of the anhydrous sugar alcohol-based carbonate diol is higher than the above level, the glass transition temperature of the soft segment may be lowered, and the heat resistance of the polycarbonate ester elastomer may also be poor.

[0036] More specifically, the content of the anhydrous sugar alcohol-based carbonate diol in the total 100 mol% of the polyol may be 8 mol% or more, 9 mol% or more, 10 mol% or more, 11 mol% or more, 12 mol% or more, 13 mol% or more, 14 mol% or more, 15 mol% or more, or 16 mol% or more, and may also be 70 mol% or less, 69 mol% or less, 68 mol% or less, 67 mol% or less, 66 mol% or less, 65 mol% or less, 64 mol% or less, 63 mol% or less, or 62 mol% or less, but is not limited thereto.

[0037] In one embodiment, when the aliphatic diol component for the hard segment further comprises the additional aliphatic diol described above, it may be included in an amount of 18 to 82 mol% within the total 100 mol% of the polyol.

[0038] More specifically, the content of the additional aliphatic diol in the total 100 mol% of the polyol may be 18 mol% or more, 19 mol% or more, 20 mol% or more, 21 mol% or more, 22 mol% or more, 23 mol% or more, 24 mol% or more, 25 mol% or more, or 26 mol% or more, and may also be 82 mol% or less, 81 mol% or less, 80 mol% or less, 79 mol% or less, 78 mol% or less, or 77 mol% or less, but is not limited thereto.

[0039] In one embodiment, the polyol component for the soft segment may be included in an amount of 4 to 29 mol% within the total 100 mol% of the polyol.

[0040] More specifically, the content of the polyol component for the soft segment within the total 100 mol% of the polyol may be 4 mol% or more, 5 mol% or more, 6 mol% or more, or 7 mol% or more, and may also be 29 mol% or less, 28 mol% or less, 27 mol% or less, 26 mol% or less, 25 mol% or less, 24 mol% or less, 23 mol% or less, 22 mol% or less, 21 mol% or less, 20 mol% or less, 19 mol% or less, 18 mol% or less, or 17 mol% or less, but is not limited thereto.

[0041] In one embodiment, the thermoplastic polycarbonate ester elastomer of the present invention may further comprise a structure derived from a branching agent as needed. Such a branching agent may be, for example, glycerol, but is not limited thereto.

[0042] In one embodiment, when the thermoplastic polycarbonate ester elastomer of the present invention further comprises the branching agent-derived structure described above, it may be included in an amount of, for example, 0.1 to 0.5 mol%, more specifically 0.1 to 0.3 mol% based on 100 mol% of the total polyol, but is not limited thereto.

[0043] According to another aspect of the present invention, a method for manufacturing a thermoplastic polycarbonate ester elastomer having a hard segment and a soft segment comprises a condensation polymerization reaction between an aromatic dicarboxylic compound and a polyol, wherein the polyol comprises an aliphatic diol component for the hard segment and a polyol component for the soft segment, and the aliphatic diol component comprises an anhydrous sugar alcohol-based carbonate diol.

[0044] In the method for manufacturing a thermoplastic polycarbonate ester elastomer of the present invention, the aromatic dicarboxylic compound, the aliphatic diol component for the hard segment, the polyol component for the soft segment, and the anhydrous sugar alcohol-based carbonate diol are as described above.

[0045] In one embodiment, the condensation reaction may be carried out in the presence of a branching agent as needed, and such a branching agent is as described above.

[0046] The above polycondensation reaction may optionally be carried out in the presence of a catalyst, for example, under reduced pressure at a temperature of 180 to 250°C.

[0047] The thermoplastic polycarbonate ester elastomer of the present invention can exhibit improved heat resistance (i.e., elevated glass transition temperature (Tg)) and / or excellent mechanical properties (e.g., tensile strength, elongation, etc.) compared to conventional thermoplastic polyether ester elastomer resins, and can also enhance the value of biomaterials and contribute to environmental sustainability by using anhydrous sugar alcohol, which is an eco-friendly material, as a raw material.

[0048] Accordingly, according to another aspect of the present invention, a molded article comprising the thermoplastic polycarbonate ester elastomer of the present invention is provided.

[0049] 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.

[0050] [Example]

[0051] Preparation Example 1: Preparation of anhydrous sugar alcohol-based carbonate diol

[0052] 4.11 mol of isosorbide, 1.87 mol of diphenyl carbonate, and 0.246 mmol of sodium carbonate were placed in a 1 L reactor equipped with a thermometer and a heater connected to a stirrer, a nitrogen gas tube, and a vacuum pump for depressurization, and heated to 100°C under a nitrogen stream. Once the melting of the reaction raw materials was confirmed, the mixture was heated to 160°C while maintaining a nitrogen atmosphere. Upon reaching the set temperature, the reaction was continued after confirming that phenol, which is generated as a byproduct during the reaction, was being released. When the amount of phenol generated reached 80–90% of the theoretical generation amount, the reaction temperature was raised to 180°C to 200°C, and the reaction was carried out over 30 minutes to 1 hour while gradually reducing the pressure from atmospheric pressure to 15 torr, thereby producing the isosorbide-carbonate diol of Chemical Formula 1 below.

[0053] [Chemical Formula 1]

[0054]

[0055] Examples 1–9 and Comparative Examples 1–6: Preparation of Thermoplastic Polycarbonate Ester Elastomers

[0056] A reaction mixture with the composition shown in Table 1 below was placed in a 1L melt condensation reactor, and a titanium-based catalyst at a concentration of 550 ppm based on the acid component (dimethyl terephthalate, DMT) was added. The esterification reaction was carried out while raising the temperature to 210°C, and the alcohol produced as a byproduct was removed. When more than 80% of the theoretical amount of alcohol had been released, a titanium-based catalyst and an antioxidant at a concentration of 750 ppm based on the acid component (DMT) were added. The polycarbonate ester elastomer was prepared by raising the temperature to 245°C while gradually reducing the pressure of the reaction system to 1 mmHg. The physical properties of the prepared thermoplastic polycarbonate ester elastomer were evaluated, and the results are shown in Table 1 below.

[0057] Explanation of abbreviations for ingredients used

[0058] - DMT: Dimethyl terephthalate

[0059] - 1,4-BDO: 1,4-butanediol

[0060] - ICD: Isosorbide-carbonate diol prepared in Preparation Example 1

[0061] - ISB: Isosorbide

[0062] - PTMEG 2000: Polytetramethylene ether glycol with a number average molecular weight (Mn) of 2,000 g / mol

[0063] - PTMEG 1000: Polytetramethylene ether glycol with a number average molecular weight (Mn) of 1,000 g / mol

[0064] - Gly: Glycerol

[0065] - SONG1010: Antioxidant

[0066] Measurement and evaluation of physical properties

[0067] The physical properties of each of the polycarbonate ester elastomers of Examples 1 to 9 and Comparative Examples 1 to 6 were measured and evaluated by the following method, and the results are shown in Table 1 below.

[0068] (1) Hardness (Shore D): Hardness was measured using a Shore D hardness tester from Handpi.

[0069] (2) Intrinsic viscosity (IV: dl / g): A 0.5 wt% solution was prepared by dissolving the polycarbonate ester elastomer in a mixture of phenol and tetrachloroethane (weight ratio = 50:50), and the intrinsic viscosity was measured at 35°C using an Ubérod viscometer.

[0070] (3) Melting point (°C): Using a differential scanning calorimeter (DSC), the temperature was raised at a rate of 10°C or less, then cooled to remove the thermal history, and then raised again to measure the melting point.

[0071] (4) Glass transition temperature (Tg 1 and Tg 2 : ℃): Glass transition temperature (Tg) of polycarbonate ester elastomer 1 and Tg 2 ) was measured using a dynamic mechanical analyzer (DMA) in tension mode with a heating rate of 5°C / min and a frequency of 1 Hz, and the loss modulus of elasticity (E'') and the temperature of the maximum relaxation region peak of the tangent delta (tan δ) of the polycarbonate ester elastomer were Tg, respectively. 1 and Tg 2 It was written as.

[0072] Tg 1 : Glass transition temperature of the soft segment (°C)

[0073] Tg 2 : Glass transition temperature of the hard segment (°C)

[0074] (5) Evaluation of heat resistance (rate of change in intrinsic viscosity): Polycarbonate ester elastomer was prepared in the form of pellets, 1 g of the prepared pellets was placed on an aluminum dish, and after being left in an oven at 65°C for 72 hours, the pellets were removed and the intrinsic viscosity was measured after removing the heat history at room temperature. The rate of change (%) of intrinsic viscosity relative to the initial intrinsic viscosity was calculated, and the heat resistance was evaluated according to the following criteria.

[0075]

[0076] (6) Tensile strength (kgf / cm²) 2 ): Measured according to ASTM D638.

[0077] (7) Tensile elongation (%): Measured according to ASTM D638.

[0078]

[0079]

[0080] As can be seen from Table 1 above, the thermoplastic polycarbonate ester elastomers of Examples 1 to 9 according to the present invention were able to exhibit improved heat resistance (i.e., elevated glass transition temperature (Tg)) and excellent mechanical properties (e.g., tensile strength, elongation, etc.), whereas the polycarbonate ester elastomers of the comparative examples were inferior to the examples in one or more of the evaluated properties.

Claims

1. As a thermoplastic polycarbonate ester elastomer having hard segments and soft segments, It includes aromatic dicarboxylic compounds and polyols as polymerization units, The above polyol comprises an aliphatic diol component for the hard segment and a polyol component for the soft segment, and The aliphatic diol component for the hard segment described above comprises an anhydrous sugar alcohol-based carbonate diol, Thermoplastic polycarbonate ester elastomer.

2. A thermoplastic polycarbonate ester elastomer according to claim 1, wherein the aromatic dicarboxylic compound is selected from the group consisting of terephthalic acid, isophthalic acid, 1,5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, dimethyl terephthalate, diethyl terephthalate, dimethyl isophthalate, diethyl isophthalate, or a combination thereof.

3. A thermoplastic polycarbonate ester elastomer according to claim 1, wherein the anhydrous sugar alcohol-based carbonate diol is the product of an esterification reaction between an anhydrous sugar alcohol and a carbonate-based compound.

4. A thermoplastic polycarbonate ester elastomer according to paragraph 3, wherein the anhydrous sugar alcohol is dianhydrous sugar hexitol, and the carbonate compound is one or more selected from the group consisting of aliphatic carbonate compounds, alicyclic carbonate compounds, aromatic carbonate compounds, or combinations thereof.

5. A thermoplastic polycarbonate ester elastomer according to claim 1, wherein the anhydrous sugar alcohol-based carbonate diol has a structure represented by the following chemical formula 1: [Chemical Formula 1] In the above chemical formula 1, n is an integer from 1 to 10.

6. A thermoplastic polycarbonate ester elastomer according to claim 1, wherein the aliphatic diol component for the hard segment further comprises an additional aliphatic diol different from the anhydrous sugar alcohol-based carbonate diol.

7. A thermoplastic polycarbonate ester elastomer according to claim 1, wherein the polyol component for the hard segment does not include anhydrous sugar alcohol as an independent component.

8. A thermoplastic polycarbonate ester elastomer according to claim 1, wherein the polyol component for the soft segment does not contain an anhydrous sugar alcohol-based carbonate diol.

9. A method for manufacturing a thermoplastic polycarbonate ester elastomer having hard segments and soft segments, It includes polycondensation reaction of an aromatic dicarboxylic acid compound and a polyol, and Here, the polyol comprises an aliphatic diol component for the hard segment and a polyol component for the soft segment, and the aliphatic diol component comprises an anhydrous sugar alcohol-based carbonate diol. Method for manufacturing a thermoplastic polycarbonate ester elastomer.

10. A molded article comprising a thermoplastic polycarbonate ester elastomer according to any one of claims 1 to 8.

Images