Polyamide ether ester elastomer comprising anhydrosugar alcohol-based diamine as polymerization unit, and preparation method therefor

Abstract

The present invention relates to a polyamide ether ester elastomer and a preparation method therefor and, more specifically, to a thermoplastic polyamide ether ester elastomer and a preparation method therefor, the thermoplastic polyamide ether ester elastomer exhibiting both improved heat resistance and excellent mechanical properties (for example, tensile strength, elongation, and the like), by having a hard segment and a soft segment and comprising, as polymerization units, an aromatic dicarboxylic compound, an aliphatic diol for the hard segment, a polyol for the soft segment, and an anhydrosugar alcohol-based diamine.

Description

Polyamide ether ester elastomer comprising an anhydrous sugar alcohol-based diamine as a polymerization unit and a method for preparing the same

[0001] The present invention relates to a polyamide ether ester elastomer and a method for manufacturing the same, and more specifically, to a thermoplastic polyamide ether ester elastomer having a hard segment and a soft segment, and comprising an aromatic dicarboxylic compound, an aliphatic diol for the hard segment, a polyol for the soft segment, and an anhydrous sugar alcohol-based diamine as polymerization units, which can simultaneously exhibit improved heat resistance and excellent mechanical properties (e.g., tensile strength, elongation, etc.).

[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 objective of the present invention is to provide a thermoplastic polyamide ether ester elastomer, which is a thermoplastic elastomer material with improved heat resistance and mechanical properties (e.g., tensile strength, elongation, etc.), and a method for manufacturing the same.

[0009] One aspect of the present invention provides a thermoplastic polyamide ether ester elastomer having a hard segment and a soft segment, comprising, as polymerization units, an aromatic dicarboxylic compound, an aliphatic diol for the hard segment, a polyol for the soft segment, and an anhydrous sugar alcohol-based diamine.

[0010] Another aspect of the present invention provides a method for producing a thermoplastic polyamide ether ester elastomer having a hard segment and a soft segment, comprising: (1) reacting an aromatic dicarboxylic compound with an anhydrous sugar alcohol-based diamine; and (2) reacting the reaction product of step (1) with an aromatic dicarboxylic compound, an aliphatic diol for the hard segment, and a polyol for the soft segment in a condensation polymerization reaction.

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

[0012] The thermoplastic polyamide ether ester elastomer according to the present invention can simultaneously exhibit improved heat resistance (i.e., increased melting point (Tm) and / or increased thermal decomposition temperature (Td)) and excellent mechanical properties (e.g., tensile strength, elongation, etc.), and by using anhydrous sugar alcohol, which is an eco-friendly material, as a raw material, it can enhance the value of bio-materials and contribute to an eco-friendly environment.

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

[0014] The thermoplastic polyamide ether ester elastomer of the present invention has a hard segment and a soft segment, and comprises an aromatic dicarboxylic compound, an aliphatic diol for the hard segment, a polyol for the soft segment, and an anhydrous sugar alcohol-based diamine 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 one embodiment, the aliphatic diol for the hard segment may be, for example, a linear, branched, or cyclic aliphatic diol, more specifically a linear aliphatic diol having 2 to 8 carbon atoms, a branched aliphatic diol having 3 to 8 carbon atoms, or a cyclic aliphatic diol having 3 to 8 carbon atoms, and even 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 a combination thereof, but is not limited thereto.

[0018] In one embodiment, the polyol for the soft segment may be a polyalkylene ether glycol, and more specifically, a poly(C2-C 10 It may be an alkylene ether glycol, and more specifically, it may be selected from the group consisting of polyethylene ether glycol, polypropylene ether glycol, polytrimethylene ether glycol, polytetramethylene ether glycol, or a combination thereof, and more specifically, it may be polytrimethylene ether glycol, polytetramethylene ether glycol, or a combination thereof. In addition, the number average molecular weight of the polyol for the soft segment may be, for example, 600 to 3000 g / mol (more specifically 1000 to 2000 g / mol), but is not limited thereto.

[0019] The above anhydrous sugar alcohol-based diamine refers to a compound in which two terminal hydroxyl groups (-OH) of an anhydrous sugar alcohol are substituted with an amino group (-NH2) or a substituted amino group (-NHR, where R is an alkyl group (e.g., a C1-C6 alkyl group)), and more specifically, a compound in which two terminal hydroxyl groups (-OH) of an anhydrous sugar alcohol are substituted with an amino group (-NH2).

[0020] The above anhydrous alcohol may be a single anhydrous alcohol, a two-anhydrous alcohol, or a combination thereof.

[0021] 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.

[0022] 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.

[0023] 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.

[0024] In one embodiment, the anhydrous sugar alcohol-based diamine may be obtained by reacting an anhydrous sugar alcohol with a hydroxy-protecting group-containing compound (e.g., tosyl(toluenesulfonyl) chloride), as shown in the reaction schematic diagram below, and then reacting the resulting product with an azide compound (e.g., sodium azide), and then reducing the resulting product, but is not limited thereto.

[0025]

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

[0027] [Chemical Formula 1]

[0028]

[0029] According to one embodiment, the total of the aromatic dicarboxylic compound, the aliphatic diol for the hard segment, the polyol for the soft segment, and the anhydrous sugar alcohol-based diamine (hereinafter referred to as the “total of raw materials”) may contain the anhydrous sugar alcohol-based diamine in an amount of 1 to 30 parts by weight within 100 parts by weight. If the content of the anhydrous sugar alcohol-based diamine within 100 parts by weight of the total of raw materials is lower than the above level, the heat resistance of the polyamide ether ester elastomer may be poor, and conversely, if the content of the anhydrous sugar alcohol-based diamine is higher than the above level, the mechanical properties (e.g., elongation) of the polyamide ether ester elastomer may be poor.

[0030] More specifically, the content of the anhydrous sugar alcohol-based diamine in the total of 100 parts by weight of the above raw material components may be 1 part by weight or more, 2 parts by weight or more, 3 parts by weight or more, 4 parts by weight or more, 5 parts by weight or more, 6 parts by weight or more, 7 parts by weight or more, or 8 parts by weight or more, and may also be 30 parts by weight or less, 29 parts by weight or less, 28 parts by weight or less, 27 parts by weight or less, or 26 parts by weight or less, but is not limited thereto.

[0031] According to one embodiment, the aromatic dicarboxylic compound may be included in an amount of 25 to 65 parts by weight within 100 parts by weight of the total of the above raw material components.

[0032] More specifically, the content of the aromatic dicarboxylic compound in 100 parts by weight of the total of the above raw materials may be 25 parts by weight or more, 26 parts by weight or more, 27 parts by weight or more, 28 parts by weight or more, 29 parts by weight or more, 30 parts by weight or more, 31 parts by weight or more, 32 parts by weight or more, or 33 parts by weight or more, and may also be 65 parts by weight or less, 64 parts by weight or less, 63 parts by weight or less, 62 parts by weight or less, 61 parts by weight or less, 60 parts by weight or less, or 59 parts by weight or less, but is not limited thereto.

[0033] According to one embodiment, within 100 parts by weight of the total of the above raw material components, the aliphatic diol for the hard segment may be included in an amount of 2 to 20 parts by weight.

[0034] More specifically, the content of the aliphatic diol for the hard segment within 100 parts by weight of the total of the above raw material components may be 2 parts by weight or more, 2.5 parts by weight or more, 3 parts by weight or more, 3.5 parts by weight or more, 4 parts by weight or more, or 4.5 parts by weight or more, and may also be 20 parts by weight or less, 19 parts by weight or less, 18 parts by weight or less, 17 parts by weight or less, 16 parts by weight or less, or 15 parts by weight or less, but is not limited thereto.

[0035] According to one embodiment, the polyol for the soft segment may be included in an amount of 3 to 70 parts by weight within 100 parts by weight of the total of the raw material components.

[0036] More specifically, the polyol content for the soft segment within 100 parts by weight of the total of the above raw material components may be 3 parts by weight or more, 3.5 parts by weight or more, 4 parts by weight or more, 4.5 parts by weight or more, 5 parts by weight or more, or 5.5 parts by weight or more, and may also be 70 parts by weight or less, 67 parts by weight or less, 65 parts by weight or less, 62 parts by weight or less, 60 parts by weight or less, 57 parts by weight or less, 55 parts by weight or less, or 52 parts by weight or less, but is not limited thereto.

[0037] According to one embodiment, the content of the anhydrous sugar alcohol-based diamine in 100 parts by weight of the total of the aliphatic diol for the hard segment, the polyol for the soft segment, and the anhydrous sugar alcohol-based diamine may be 5 to 70 parts by weight. If the content of the anhydrous sugar alcohol-based diamine in 100 parts by weight of the total of the aliphatic diol for the hard segment, the polyol for the soft segment, and the anhydrous sugar alcohol-based diamine is lower than the above level, the effect of improving the heat resistance and mechanical properties (e.g., strength) of the polyamide ether ester elastomer may be insufficient, and conversely, if it is higher than the above level, the properties of the elastomer may be degraded.

[0038] More specifically, the content of the anhydrous sugar alcohol-based diamine in the total of 100 parts by weight of the aliphatic diol for the hard segment, the polyol for the soft segment, and the anhydrous sugar alcohol-based diamine may be 5 parts by weight or more, 6 parts by weight or more, 7 parts by weight or more, 8 parts by weight or more, 9 parts by weight or more, 10 parts by weight or more, 11 parts by weight or more, 12 parts by weight or more, 13 parts by weight or more, 14 parts by weight or more, or 15 parts by weight or more, and may also be 70 parts by weight or less, 69 parts by weight or less, 68 parts by weight or less, 67 parts by weight or less, 66 parts by weight or less, 65 parts by weight or less, 64 parts by weight or less, 63 parts by weight or less, 62 parts by weight or less, 61 parts by weight or less, or 60 parts by weight or less, but is not limited thereto.

[0039] According to one embodiment, the content of the anhydrous sugar alcohol-based diamine in the total of 100 parts by weight of the polyol for the soft segment and the anhydrous sugar alcohol-based diamine may be 1 to 90 parts by weight.

[0040] More specifically, the content of the anhydrous sugar alcohol-based diamine in the total of 100 parts by weight of the polyol for soft segments and the anhydrous sugar alcohol-based diamine may be 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 7 parts by weight or more, 10 parts by weight or more, 13 parts by weight or more, 15 parts by weight or more, or 17 parts by weight or more, and may also be 90 parts by weight or less, 89 parts by weight or less, 88 parts by weight or less, 87 parts by weight or less, 86 parts by weight or less, 85 parts by weight or less, 84 parts by weight or less, 83 parts by weight or less, 82 parts by weight or less, or 81 parts by weight or less, but is not limited thereto.

[0041] In one embodiment, the thermoplastic polyamide ether ester elastomer of the present invention may further comprise a structure derived from a branching agent as needed. Such branching agents may include, for example, polyhydric alcohols having three or more hydroxyl groups or polyhydric acids having three or more carboxylic acid groups, and specifically, glycerol, trimethylolpropane, trimellitic anhydride, etc. may be used alone or in combination, but are not limited thereto.

[0042] In one embodiment, the amount of the branching agent used may be, for example, 0.01 to 3 parts by weight, more specifically 0.01 to 1 part by weight, based on 100 parts by weight of the total of the raw material components, but is not limited thereto.

[0043] In one embodiment, the thermoplastic polyamide ether ester elastomer of the present invention may have a structure represented by the following chemical formula 2:

[0044] [Chemical Formula 2]

[0045]

[0046] In the above chemical formula 2, n is determined according to the molecular weight of the polytetramethylene ether glycol used as a polyol for the soft segment, and may be, for example, an integer from 11 to 23.

[0047] According to another aspect of the present invention, a method for producing a thermoplastic polyamide ether ester elastomer having a hard segment and a soft segment is provided, comprising: (1) reacting an aromatic dicarboxylic compound with an anhydrous sugar alcohol-based diamine; and (2) reacting the reaction product of step (1) with an aromatic dicarboxylic compound, an aliphatic diol for the hard segment, and a polyol for the soft segment in a condensation polymerization reaction.

[0048] In the method for manufacturing a thermoplastic polyamide ether ester elastomer of the present invention, the aromatic dicarboxylic compound, the aliphatic diol for the hard segment, the polyol for the soft segment, and the anhydrous sugar alcohol-based diamine are as described above.

[0049] In one embodiment, the reaction of step (1) above may be carried out at about 70 to 120°C in an ethanol solvent, for example, with or without a catalyst, optionally, but is not limited thereto.

[0050] In one embodiment, the condensation reaction of step (2) above may be carried out in the presence of a branching agent as needed, and such a branching agent is as described above.

[0051] The polycondensation reaction of step (2) above can be carried out under reduced pressure, for example, at a temperature of 180 to 270°C, in the presence of a catalyst.

[0052] The thermoplastic polyamide ether ester elastomer of the present invention can simultaneously exhibit improved heat resistance and excellent mechanical properties (e.g., tensile strength, elongation, etc.) compared to conventional thermoplastic polyether ester elastomer resins, and by using anhydrous sugar alcohol, which is an eco-friendly material, as a raw material, it can enhance the value of biomaterials and contribute to an eco-friendly environment.

[0053] Accordingly, according to another aspect of the present invention, a molded article comprising the thermoplastic polyamide ether ester elastomer of the present invention is provided.

[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] [Example]

[0056] Examples 1–5: Preparation of thermoplastic polyamide ether ester elastomers

[0057] (1) As a step reaction, dimethyl terephthalate (DMT) as an aromatic dicarboxylic compound and an anhydrous sugar alcohol-based diamine of Formula 1 were reacted (salting reaction) at 75°C while stirring in an ethanol solvent according to the composition shown in Table 1 below. Subsequently, as a step reaction (2), the reaction product (salt) from step (1) and the remaining raw materials were placed in a 5L melt condensation reactor according to the composition shown in Table 1 below, and a titanium-based catalyst at 700 ppm based on the acid component (DMT) was added, and the temperature was raised to 210°C while removing the alcohol produced as a byproduct. When more than 80% of the theoretical amount of alcohol was released, a titanium-based catalyst at 300 ppm based on the acid component (DMT) was added, and the temperature was raised to 260°C while the pressure of the reaction system was gradually reduced to 1 mmHg to produce a thermoplastic polyamide ether ester elastomer. The physical properties of the manufactured thermoplastic polyamide ether ester elastomer were evaluated, and the results are shown in Table 1 below.

[0058] [Chemical Formula 1]

[0059]

[0060] Comparative Examples 1 and 3: Preparation of Thermoplastic Polyether Ester Elastomers

[0061] According to the composition shown in Table 1 below, raw materials were placed into a 5L melt condensation reactor, and a titanium-based catalyst at a concentration of 700 ppm based on the acid component (DMT) was added. The temperature was then raised to 210°C to remove alcohol generated as a byproduct. When more than 80% of the theoretical amount of alcohol had been released, a titanium-based catalyst at a concentration of 300 ppm based on the acid component (DMT) was added. The temperature was then raised to 250°C while the pressure of the reaction system was gradually reduced to 1 mmHg to produce a thermoplastic polyether ester elastomer. The physical properties of the produced thermoplastic polyether ester elastomer were evaluated, and the results are shown in Table 1 below.

[0062] Comparative Example 2: Preparation of Thermoplastic Polyamide Ester Elastomer

[0063] (1) As a step reaction, dimethyl terephthalate (DMT) as an aromatic dicarboxylic compound and an anhydrous sugar alcohol-based diamine of Formula 1 were reacted (salting reaction) at 75°C while stirring in an ethanol solvent according to the composition shown in Table 1 below. Subsequently, as a step reaction (2), the reaction product (salt) from step (1) and the remaining raw material components were placed in a 5L melt condensation reactor according to the composition shown in Table 1 below, and a titanium-based catalyst at 700 ppm based on the acid component (DMT) was added, and the temperature was raised to 210°C while removing the alcohol produced as a byproduct. When more than 80% of the theoretical amount of alcohol was released, a titanium-based catalyst at 300 ppm based on the acid component (DMT) was added, and the temperature was raised to 260°C while the pressure of the reaction system was gradually reduced to 1 mmHg to produce a thermoplastic polyamide ester elastomer. The physical properties of the manufactured thermoplastic polyamide ester elastomer were evaluated, and the results are shown in Table 1 below.

[0064] Explanation of abbreviations for ingredients used

[0065] - ISB-amine: Anhydrous sugar alcohol (isosorbide)-based diamine of Chemical Formula 1

[0066] - Chain-extended ISB-AO: Chain-extended isosorbide-ethylene glycol prepared using isosorbide-ethylene glycol and polyisocyanate, prepared by the following method.

[0067] 292 g (2.0 mol) of isosorbide, 881 g (20.0 mol) of ethylene oxide, and 0.2 g of sodium hydroxide as a catalyst were added to a pressurized reaction apparatus equipped with a column, a stirrer, a thermometer, and a heater, a column equipped with a nitrogen gas tube and a cooling device, and the temperature was gradually increased. The reaction was carried out at a temperature of 120°C to 160°C for 2 to 4 hours to produce 770 g of isosorbide-ethylene glycol (10 mol ethylene oxide adduct of isosorbide), in which the hydrogens of the hydroxyl groups at both ends of the isosorbide are substituted with hydroxyethyl groups. Subsequently, 500 g of the obtained isosorbide-ethylene glycol and 0.11 g of dibutyltin dilaurate as a catalyst were added to a reactor and purged with nitrogen gas for 30 minutes while stirring. Subsequently, 106 g of 4,4'-methylene diphenyl diisocyanate (MDI) was added dropwise over a period of 1 to 2 hours under a nitrogen atmosphere. During this process, the internal reaction temperature was controlled so as not to exceed 70°C. If an exothermic reaction occurred during the reaction, the reaction temperature was adjusted to 60°C, and the reaction was carried out while stirring for 1 to 2 hours. After the reaction was completed, the reaction was cooled to room temperature to obtain 533 g of isosorbide-ethylene glycol with chain extended by MDI.

[0068] - DMT: Dimethyl terephthalate

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

[0070] - PTMEG 1000: Polytetramethylene ether glycol with a number average molecular weight (Mn) of 1,000 g / mol

[0071] - PTMEG 2000: Polytetramethylene ether glycol with a number average molecular weight (Mn) of 2,000 g / mol

[0072] - PO3G 1000: Polytrimethylene ether glycol with a number average molecular weight (Mn) of 1,000 g / mol

[0073] - Gly: Glycerol

[0074] Measurement and evaluation of physical properties

[0075] The physical properties of each of the elastomers of Examples 1 to 5 and Comparative Examples 1 to 3 were measured and evaluated by the following method, and the results are shown in Table 1 below.

[0076] (1) Hardness (Shore D): Hardness was measured using a Shore D hardness tester from Handpi.

[0077] (2) Intrinsic viscosity (IV: dL / g): After preparing a 0.5 wt% solution by dissolving the elastomer in a mixture of phenol and 1,1,2,2-tetrachloroethane (weight ratio = 50:50), the intrinsic viscosity was measured at 35°C using an Ubérod viscometer.

[0078] (3) Tensile elongation (%): Measured using a universal testing machine (UTM) in accordance with ASTM D638.

[0079] (4) Tensile strength (kgf / cm²) 2 ): Measured using a universal testing machine (UTM) in accordance with ASTM D638.

[0080] (5) Melting point (Tm: °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.

[0081] (6) Thermal decomposition temperature (Td: ℃): The temperature was measured when the weight of the sample decreased by 5% by weight compared to the initial weight using a thermogravimetric analyzer (Perkin-Elmer TGA-7).

[0082] (7) Heat resistance evaluation (intrinsic viscosity change rate): After preparing the elastomer in pellet form, 1 g of the prepared pellet was placed on an aluminum dish and left in an oven at 65°C for 72 hours. After removing it, the heat history was removed at room temperature and the intrinsic viscosity was measured. The change rate (%) of the intrinsic viscosity relative to the initial intrinsic viscosity was calculated, and the heat resistance was evaluated according to the following criteria.

[0083]

[0084]

[0085] As can be seen from Table 1 above, the thermoplastic polyamide ether ester elastomers of Examples 1 to 5 according to the present invention were able to simultaneously exhibit improved heat resistance (i.e., increased melting point (Tm) and / or increased thermal decomposition temperature (Td)) and excellent mechanical properties (tensile strength, elongation, etc.), whereas the elastomers of the comparative examples were inferior to the examples in one or more of the evaluated property items.

Claims

1. As a thermoplastic polyamide ether ester elastomer having hard segments and soft segments, Comprising aromatic dicarboxylic compounds, aliphatic diols for hard segments, polyols for soft segments, and anhydrous sugar alcohol-based diamines as polymerization units, Thermoplastic polyamide ether ester elastomer.

2. A thermoplastic polyamide ether 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 combinations thereof.

3. A thermoplastic polyamide ether ester elastomer according to claim 1, wherein the aliphatic diol for the hard segment is selected from the group consisting of ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, or a combination thereof.

4. In claim 1, the polyol for the soft segment is poly(C2-C 10 A thermoplastic polyamide ether ester elastomer, which is an alkylene ether glycol.

5. A thermoplastic polyamide ether ester elastomer according to claim 1, wherein the anhydrous sugar alcohol-based diamine is a compound in which two terminal hydroxyl groups (-OH) of the anhydrous sugar alcohol are substituted with amino groups (-NH2).

6. A thermoplastic polyamide ether ester elastomer according to paragraph 5, wherein the anhydrous sugar alcohol is dianhydrous sugar hexitol.

7. A thermoplastic polyamide ether ester elastomer according to claim 1, wherein the anhydrous sugar alcohol-based diamine has a structure represented by the following chemical formula 1:

8. A method for manufacturing a thermoplastic polyamide ether ester elastomer having hard segments and soft segments, (1) a step of reacting an aromatic dicarboxylic acid compound with an anhydrous sugar alcohol-based diamine; and (2) a step of condensing the reaction product of step (1) with an aromatic dicarboxylic acid compound, an aliphatic diol for the hard segment, and a polyol for the soft segment; comprising, Method for manufacturing a thermoplastic polyamide ether ester elastomer.

9. A molded article comprising a thermoplastic polyamide ether ester elastomer according to any one of claims 1 to 7.

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