A self-matting thermoplastic polyurethane elastomer and its preparation method and application

Abstract

This invention discloses a self-matting thermoplastic polyurethane elastomer, its preparation method, and its applications, relating to the field of polymer materials technology. The self-matting thermoplastic polyurethane elastomer, by weight, comprises the following raw materials: 40-80 parts polyester polyol; 5-15 parts chain extender; 15-50 parts diisocyanate; 0.02-2 parts antioxidant; 0.01-1 part lubricant; and 0.001-0.01 parts catalyst. This invention, by adjusting the ratio of polyester polyol and chain extender, eliminates the need for matting agents or fogging agents, and can prepare self-matting TPU hot melt yarn through melt spinning. The prepared self-matting TPU hot melt yarn exhibits good matting effect and excellent mechanical properties, showing broad application prospects in fields such as flyknitted fabrics.

Description

Technical Field

[0001] The invention relates to the technical field of polymer materials, in particular to a self-matting thermoplastic polyurethane elastomer and a preparation method and application thereof. Background Art

[0002] Thermoplastic polyurethane hot melt wire (TPU hot melt wire) is made of thermoplastic polyurethane elastomer (TPU) through melt spinning process. It is widely used in fly-woven fabrics of shoe materials because of its high strength, wear resistance, good hot pressing 3D shaping / solidification, mildew resistance and antibacterial characteristics, giving the fabric excellent shape retention and wear resistance. However, due to the high transparency of TPU hot melt wire, it absorbs light weakly, causing the textile fabric containing the hot melt wire to reflect light, which will undoubtedly reduce the grade of the fabric. Based on this, fabric reflection has become one of the difficulties in using TPU hot melt wire in the textile industry.

[0003] To this end, patent CN103087505A reports that 5-20% (mass percentage) of silica, TiO2, MgO, Al2O3, etc. are added to TPU as matting agents respectively. During the melt extrusion process, each component melts, and the matting agent and other components are uniformly dispersed and doped, and synergistically act to achieve TPU modification. The 60° gloss of the modified TPU is about 10 (7.6-12.3), which is lower than the comparative example (70), and the matting effect is obviously achieved. In addition, patents such as CN 108102347 B, CN101599314A, CN10345662A, CN104497553A, and CN108102347A all add one of inorganic matting powders such as nano zinc oxide, aluminum oxide, magnesium oxide, or fumed silica, and organic polymer materials such as SEBS, SEPS, EPDM, NBR, and high-impact polystyrene as a matte regulator to TPU for mixing, and prepare TPU using a twin-screw extrusion process. Compared with the case without adding matte powder or matte regulator, the 60° glossiness is reduced, but the surface roughness of TPU is higher.

[0004] The addition of the above-mentioned inorganic matting powder or organic polymer matte regulator will undoubtedly increase the raw material cost of the newly manufactured TPU; the regranulation process will also reduce the molecular weight of TPU, thereby reducing its mechanical properties and increasing the process cost; the addition of matte regulator has problems such as poor distribution uniformity and high surface roughness, and even affects the subsequent hot melt quality and the wearing comfort of flywoven fabrics. Summary of the invention

[0005] In view of the problems existing in the above technologies, the present invention provides a self-matting thermoplastic polyurethane elastomer and its preparation method and application. The present invention obtains self-matting TPU by adjusting the formula components, and subsequently obtains a self-matting TPU hot melt yarn by using a specific melt spinning process.

[0006] To achieve the above object, the present invention provides the following solutions:

[0007] A self-matting thermoplastic polyurethane elastomer, comprising the following raw materials in parts by weight:

[0008] 40-80 parts of polyester polyol;

[0009] Chain extender 5-15 parts;

[0010] 15-50 parts of diisocyanate;

[0011] Antioxidant 0.02-2 parts;

[0012] Lubricant 0.01-1 part;

[0013] Catalyst 0.001-0.01 part;

[0014] The amount of chain extender added is not zero.

[0015] Furthermore, the polyester polyol includes polyethylene adipate polyol (PEA), polyethylene adipate 2-methyl 1,3 propanediol polyol (PMA) and polyethylene adipate 2-methyl 1,3 propanediol (PEMA).

[0016] Furthermore, the molecular weight of the polyester polyol is 800-4000, preferably 1200-3500.

[0017] Furthermore, based on 100% of the total amount of the polyester polyol, the mass fraction of the polyethylene adipate polyol (PEA) is 30-60%, the mass fraction of the polyethylene adipate 2-methyl 1,3 propanediol polyol (PMA) is 20-40%, and the mass fraction of the polyethylene adipate 2-methyl 1,3 propanediol polyol (PEMA) is 10-30%.

[0018] Further, the chain extender includes ethylene glycol, 2-methyl-1,3-propanediol, 1,4-cyclohexanediol and hydroquinone-bis(β-hydroxyethyl) ether (HQEE).

[0019] Furthermore, the chain extender is a mixture of ethylene glycol, 2-methyl 1,3-propanediol, 1,4-cyclohexanediol and HQEE, wherein the mass percentage of 2-methyl 1,3-propanediol is 10-30%, the mass percentage of 1,4-cyclohexanediol is 10-25%, the mass percentage of hydroquinone-bis(β-hydroxyethyl) ether (HQEE) is 5-20%, and the balance is ethylene glycol, and the sum of the mass percentages of the above substances is 100%.

[0020] Furthermore, the isocyanate index of the diisocyanate is 0.85-1.04.

[0021] Furthermore, the diisocyanate is one or more of 4,4-diphenylmethane diisocyanate (MDI), toluene diisocyanate (TDI) and hexamethylene diisocyanate (HDI).

[0022] Furthermore, the antioxidant is A0-60, TNP, TP-10H and a combination thereof.

[0023] Furthermore, the lubricant is a lubricant fatty acid, fatty acid ester, fatty acid amide, fatty acid salt, bile wax or silicone oil lubricant, preferably EBS or E wax.

[0024] Furthermore, the catalyst is an organic tin catalyst, a titanate catalyst or a metal salt catalyst.

[0025] Furthermore, the number average molecular weight of the self-matting thermoplastic polyurethane elastomer is 70,000-90,000.

[0026] A method for preparing the self-matting thermoplastic polyurethane elastomer comprises the following steps:

[0027] Mix the polyester polyol, add antioxidant and catalyst, and adjust the temperature to 100-120°C;

[0028] Adjust the temperature of diisocyanate to 50-80°C;

[0029] Mix chain extender ethylene glycol, 2-methyl-1,3-propanediol and 1,4-cyclohexanediol and adjust the temperature to 56-80°C;

[0030] The temperature of the chain extender hydroquinone-bis(β-hydroxyethyl) ether (HQEE) was adjusted to 104-120°C;

[0031] The above four components are poured into a two-stage screw extruder at the same time in proportion for reaction, a lubricant is added to the exhaust port of the large screw, and then granulation is performed underwater to obtain a self-matting thermoplastic polyurethane elastomer (self-matting TPU).

[0032] Furthermore, the temperature of the first-stage screw extruder is 140-350°C, preferably 180-300°C, and the rotation speed is 150-500r / min, preferably 200-350r / min; the temperature of the second-stage screw extruder is 120-300°C, preferably 150-250°C, and the rotation speed is 50-300r / min, preferably 100-250r / min.

[0033] The self-matting thermoplastic polyurethane elastomer is used in preparing self-matting thermoplastic polyurethane hot melt wire.

[0034] A method for preparing the self-matting thermoplastic polyurethane hot melt wire: the self-matting TPU is dried and then enters the screw for plasticization, then enters the assembly for spinning through a metering pump, and undergoes side-blowing cooling, secondary stretching, oiling and winding to obtain a self-matting thermoplastic polyurethane hot melt wire (self-matting TPU hot melt wire) with a specification of 210D.

[0035] Furthermore, the screw temperature is set to 150-280°C, preferably 160-250°C, and the screw speed is set to 100-5000r / min, preferably 200-400r / min.

[0036] The present invention discloses the following technical effects:

[0037] The present invention selects polyethylene adipate polyol (PEA), poly(2-methyl 1,3-propylene adipate) polyol (PMA), and polyethylene adipate 2-methyl 1,3-propylene glycol (PEMA) to prepare a mixed polyester polyol in a certain proportion, uses ethylene glycol, 2-methyl 1,3-propylene glycol, 1,4-cyclohexanediol, and hydroquinone-bis(β-hydroxyethyl) ether (HQEE) four small molecule diol chain extenders to prepare a mixed chain extender in a certain proportion, reacts with isocyanate, prepares self-matting TPU, and further prepares the self-matting TPU hot melt fiber through a melt spinning process.

[0038] The preparation method of the invention is simple, does not need to add a matting agent or a matte agent, and the prepared self-matting TPU has good matting effect and excellent mechanical properties, and has broad application prospects in the fields of fly-woven fabrics and the like. DETAILED DESCRIPTION

[0039] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as limiting the present invention, but should be understood as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0040] It should be understood that the terms described in the present invention are only for describing a particular embodiment and are not intended to limit the present invention. In addition, for the numerical range in the present invention, it should be understood that each intermediate value between the upper and lower limits of the scope is also specifically disclosed. The intermediate value in any stated value or stated range, and each smaller range between any other stated value or intermediate value in the described range is also included in the present invention. The upper and lower limits of these smaller ranges can be independently included or excluded in the scope.

[0041] Unless otherwise indicated, all technical and scientific terms used herein have the same meanings as those generally understood by those skilled in the art. Although the present invention describes only preferred methods and materials, any methods and materials similar or equivalent to those described herein may also be used in the implementation or testing of the present invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials associated with the documents. In the event of a conflict with any incorporated document, the content of this specification shall prevail.

[0042] It will be apparent to those skilled in the art that various modifications and variations may be made to the specific embodiments of the present invention description without departing from the scope or spirit of the present invention. Other embodiments derived from the present invention description will be apparent to those skilled in the art. The present invention description and examples are exemplary only.

[0043] The words “include,” “including,” “have,” “contain,” etc. used in this document are open-ended terms, meaning including but not limited to.

[0044] The raw materials of the present invention are all obtained by purchase.

[0045] The embodiment of the present invention provides a self-matting thermoplastic polyurethane elastomer, which comprises the following raw materials in parts by weight:

[0046] 40-80 parts of polyester polyol;

[0047] Chain extender 5-15 parts;

[0048] 15-50 parts of diisocyanate;

[0049] Antioxidant 0.02-2 parts;

[0050] Lubricant 0.01-1 part;

[0051] Catalyst 0.001-0.01 part;

[0052] In an embodiment of the present invention, the polyester polyol includes polyethylene adipate polyol (PEA), polyethylene 2-methyl 1,3 propanediol adipate polyol (PMA) and polyethylene 2-methyl 1,3 propanediol adipate (PEMA).

[0053] In an embodiment of the present invention, the molecular weight of the polyester polyol is 800-4000, preferably 1200-3500.

[0054] In an embodiment of the present invention, based on 100% of the total amount of the polyester polyol, the mass fraction of polyethylene adipate polyol (PEA) is 30-60%, the mass fraction of poly(2-methyl-1,3-propylene adipate) polyol (PMA) is 20-40%, and the mass fraction of polyethylene adipate polyol (PEMA) is 10-30%.

[0055] In an embodiment of the present invention, the chain extender includes ethylene glycol, 2-methyl-1,3-propanediol, 1,4-cyclohexanediol and hydroquinone-bis(β-hydroxyethyl) ether (HQEE).

[0056] In an embodiment of the present invention, the chain extender is a mixture of ethylene glycol, 2-methyl-1,3-propanediol, 1,4-cyclohexanediol and HQEE, wherein the mass percentage of 2-methyl-1,3-propanediol is 10-30%, the mass percentage of 1,4-cyclohexanediol is 10-25%, the mass percentage of hydroquinone-bis(β-hydroxyethyl) ether (HQEE) is 5-20%, and the balance is ethylene glycol, and the sum of the mass percentages of the above substances is 100%.

[0057] In an embodiment of the present invention, the isocyanate index of the diisocyanate is 0.85-1.04.

[0058] In an embodiment of the present invention, the diisocyanate is one or more of 4,4-diphenylmethane diisocyanate, toluene diisocyanate, and hexamethylene diisocyanate.

[0059] In an embodiment of the present invention, the antioxidant is A0-60, TNP, TP-10H and a combination thereof.

[0060] In an embodiment of the present invention, the lubricant is a lubricant fatty acid, fatty acid ester, fatty acid amide, fatty acid salt, bile wax or silicone oil lubricant, preferably EBS or E wax.

[0061] In an embodiment of the present invention, the catalyst is an organotin catalyst, a titanate catalyst or a metal salt catalyst.

[0062] In an embodiment of the present invention, the number average molecular weight of the self-matting thermoplastic polyurethane elastomer is 70,000-90,000.

[0063] An embodiment of the present invention provides a method for preparing the self-matting thermoplastic polyurethane elastomer, comprising the following steps:

[0064] Mix the polyester polyols, add the catalyst, and adjust the temperature to 100-120°C;

[0065] Adjust the temperature of diisocyanate to 50-80°C;

[0066] Mix chain extender ethylene glycol, 2-methyl-1,3-propanediol and 1,4-cyclohexanediol and adjust the temperature to 56-80°C;

[0067] The temperature of the chain extender hydroquinone-bis(β-hydroxyethyl) ether (HQEE) was adjusted to 104-120°C;

[0068] The above four components are poured into a two-stage screw extruder at the same time in proportion for reaction, a lubricant is added to the exhaust port of the large screw, and then granulation is performed underwater to obtain a self-matting thermoplastic polyurethane elastomer (self-matting TPU).

[0069] In an embodiment of the present invention, the temperature of the first-stage screw extruder is 140-350°C, preferably 180-300°C, and the rotation speed is 150-500r / min, preferably 200-350r / min; the temperature of the second-stage screw extruder is 120-300°C, preferably 150-250°C, and the rotation speed is 50-300r / min, preferably 100-250r / min.

[0070] The self-matting thermoplastic polyurethane elastomer is used for preparing self-matting thermoplastic polyurethane hot melt wire.

[0071] An embodiment of the present invention provides a method for preparing a self-matting thermoplastic polyurethane hot melt wire: the self-matting TPU is dried and then enters a screw for plasticization, then enters a component for spinning through a metering pump, and undergoes side-blowing cooling, secondary stretching, oiling and winding to obtain a self-matting thermoplastic polyurethane hot melt wire (self-matting TPU hot melt wire) with a specification of 210D.

[0072] Furthermore, the screw temperature is set to 150-280°C, preferably 160-250°C, and the screw speed is set to 100-500r / min, preferably 200-400r / min.

[0073] The polyester polyol synthesis process of the present invention adopts the polyester polyol synthesis process disclosed in the industry. The operation modes of the equipment involved in the present invention are all conventional operation modes in the art. The raw materials of the present invention can all be purchased.

[0074] Performance test of the present invention:

[0075] The hardness of self-matting TPU was tested using a Shore durometer (A standard, ASTM D2240);

[0076] The tensile strength and elongation of self-matting TPU were tested using a universal tensile testing machine (ASTM D412);

[0077] The self-extinguishing TPU rebound is tested using an intelligent rubber rebound tester.

[0078] The prepared self-matting TPU hot-melt yarn was tested with reference to the standard FZ / T 54010-2014 spandex filament.

[0079] Matting test: A TPU test piece of 160×130×30 mm was prepared by an injection molding machine; a fly-woven fabric was prepared from TPU hot-melt yarn by a knitting process; and the surface gloss of the test piece and the fly-woven fabric was tested by a MN268 gloss meter (ASTM D523).

[0080] The present invention selects polyethylene adipate polyol (PEA), polypropylene adipate 2-methyl 1,3 glycol polyol (PMA), polyethylene adipate 2-methyl 1,3 glycol ester (PEMA) to prepare a mixed polyester polyol in a certain proportion, uses ethylene glycol, 2-methyl 1,3 glycol, 1,4-cyclohexanediol, hydroquinone-bis (β-hydroxyethyl) ether (HQEE) four small molecule diol chain extenders to prepare a mixed chain extender in a certain proportion, reacts with isocyanate, prepares a self-matting TPU, and further prepares a self-matting TPU hot melt by a melt spinning process. The preparation method of the present invention is simple, and the crystallinity of the soft segment and the hard segment is greatly improved by optimizing the TPU formula and strictly controlling the synthesized molecular weight, so there is no need to add a matting agent or a matte agent, and the prepared self-matting TPU has a good matting effect and excellent mechanical properties, and has broad application prospects in the fields of fly-woven fabrics.

[0081] Example 1

[0082] Accurately weigh the raw materials according to the following weight parts:

[0083] 60.297 parts of mixed polyester polyol with a molecular weight of 1500 (the mass ratio of PEA-1500, PMA-1500 and PEMA-1500 is 3:1:1), 0.06 parts of antioxidant 1010, 0.05 parts of antioxidant TNP, and 0.001 parts of tetrabutyl titanate were added to kettle A, and the temperature was set to 100°C. After mixing evenly, they were kept warm. 31.998 parts of MDI (isocyanate index 1.00) were added to kettle B, and the temperature was set to 80°C; 2.639 parts of ethylene glycol, 2.262 parts of 2-methyl 1,3-propylene glycol, and 1.885 parts of 1,4-cyclohexanediol were added to kettle C1, and the kettle temperature was set to 80°C. After mixing evenly, they were kept warm; 0.754 parts of hydroquinone-bis(β-hydroxyethyl) ether (HQEE) small molecule chain extender was added to kettle C2, and the kettle temperature was set to 120 ℃; after the material temperature in the A, B, C1 and C2 kettles reaches the set temperature, the components in the above four kettles are poured into a two-stage screw extruder for reaction, the temperature of the first-stage screw extruder is set to 300℃, and the speed is 200r / min; the temperature of the second-stage screw extruder is set to 150℃, and the speed is 100r / min, 0.02 parts of EBS are added at the exhaust port of the second-stage screw, and then underwater granulation is performed to obtain a self-matting thermoplastic polyurethane elastomer (self-matting TPU).

[0084] After drying, the self-matting TPU enters the screw for plasticization, the screw temperature is set at 160°C, and the speed is 200r / min. Then it enters the assembly for spinning through a metering pump, and undergoes side-blowing cooling, secondary stretching, oiling and winding to obtain a TPU hot melt wire with a specification of 210D.

[0085] Comparative Example 1

[0086] Accurately weigh the raw materials according to the following weight parts:

[0087] 60.93 parts of PEMA with a molecular weight of 1500, 0.06 parts of antioxidant 1010, 0.05 parts of antioxidant TNP, and 0.001 parts of tetrabutyl titanate were added to kettle A, and the temperature was set to 100°C. After mixing evenly, they were kept warm. 31.314 parts of MDI (isocyanate index 1.00) were added to kettle B, and the temperature was set to 80°C; 2.639 parts of butanediol were added to kettle C, and the kettle temperature was set to 80°C. After the material temperature in kettles A, B, and C reached the set temperature, the above components were poured into a two-stage screw extruder for reaction. The temperature of the first-stage screw extruder was set to 300°C and the speed was 200r / min; the temperature of the second-stage screw extruder was set to 150°C and the speed was 100r / min. 0.02 parts of EBS were added at the exhaust port of the second-stage screw, and then underwater granulation was performed to obtain self-matting TPU.

[0088] After drying, the self-matting TPU enters the screw for plasticization, the screw temperature is set at 160°C, and the speed is 200r / min. Then it enters the assembly for spinning through a metering pump, and undergoes side-blowing cooling, secondary stretching, oiling and winding to obtain a TPU hot melt wire with a specification of 210D.

[0089] Example 2

[0090] Accurately weigh the raw materials according to the following weight parts:

[0091] Add 70 parts of mixed polyester polyol with a molecular weight of 2000 (the mass ratio of PEA-2000, PMA-2000 and PEMA-2000 is 3:4:3), 0.05 parts of antioxidant 1010, 0.10 parts of antioxidant TP-10H, and 0.001 parts of dibutyltin dilaurate into kettle A, set the temperature to 120°C, mix well and keep warm. 24.505 parts of TDI (isocyanate index 0.88) were added to kettle B, and the kettle temperature was set to 50°C; 2.979 parts of ethylene glycol, 0.496 parts of 2-methyl 1,3-propylene glycol, and 0.496 parts of 1,4-cyclohexanediol were added to kettle C1, and the kettle temperature was set to 56°C. After mixing evenly and keeping warm, 0.993 parts of HQEE small molecule chain extender were added to kettle C2, and the kettle temperature was set to 104°C; after the material temperature in kettles A, B, C1 and C2 reached the set temperature, the above components were poured into a two-stage screw extruder for reaction, and the temperature of the first-stage screw extruder was set to 180°C and the speed was 350r / min; the temperature of the second-stage screw extruder was set to 250°C and the speed was 250r / min. 0.1 parts of EBS were added at the exhaust port of the second-stage screw, and then underwater granulation was performed to obtain self-matting TPU.

[0092] After drying, the self-matting TPU enters the screw for plasticization, and the screw temperature is set at 250°C and the speed is 400r / min. Then it enters the assembly for spinning through a metering pump, and undergoes side-blowing cooling, secondary stretching, oiling and winding to obtain a TPU hot melt wire with a specification of 210D.

[0093] Comparative Example 2

[0094] Weigh the raw materials accurately according to the following weight fractions:

[0095] PMA with a molecular weight of 2000, 0.05 parts of antioxidant 1010, 0.10 parts of antioxidant TP-10H, and 0.001 parts of dibutyltin dilaurate were added to kettle A, and the temperature was set to 120°C. After mixing evenly, they were kept warm. 25.578 parts of TDI (isocyanate index 0.88) were added to kettle B, and the kettle temperature was set to 50°C; 4.172 parts of ethylene glycol were added to kettle C1, and the kettle temperature was set to 56°C, and kept warm; after the material temperature in kettles A, B, and C reached the set temperature, the above components were poured into a two-stage screw extruder for reaction, and the temperature of the first-stage screw extruder was set to 180°C and the speed was 350r / min; the temperature of the second-stage screw extruder was set to 250°C and the speed was 250r / min. 0.1 parts of EBS were added to the exhaust port of the second-stage screw, and then underwater granulation was performed to obtain self-matting TPU.

[0096] After drying, the self-matting TPU enters the screw for plasticization, and the screw temperature is set at 250°C and the speed is 400r / min. Then it enters the assembly for spinning through a metering pump, and undergoes side-blowing cooling, secondary stretching, oiling and winding to obtain a TPU hot melt wire with a specification of 210D.

[0097] Example 3

[0098] Accurately weigh the raw materials according to the following weight parts:

[0099] 50 parts of mixed polyester polyol with a molecular weight of 3500 (the mass ratio of PEA-3500, PMA-3500 and PEMA-3500 is 5:3:2), 0.1 parts of antioxidant 1010, 0.05 parts of antioxidant TNP, and 0.002 parts of tetrabutyl titanate were added to kettle A, and the temperature was set to 110°C. After mixing evenly, the mixture was kept warm. 38.464 parts of HDI (isocyanate index 0.90) were added to kettle B, and the kettle temperature was set to 60°C. 5.444 parts of ethylene glycol, 2.722 parts of 2-methyl 1,3-propylene glycol, and 2.178 parts of 1,4-cyclohexanediol were added to the C1 kettle, and the kettle temperature was set to 70°C. The mixture was evenly mixed and kept warm. 0.544 parts of HQEE small molecule chain extender was added to the C2 kettle, and the kettle temperature was set to 108°C. After the material temperature in the A, B, C1 and C2 kettles reached the set temperature, the above four components were poured into a two-stage screw extruder for reaction. The temperature of the first-stage screw extruder was set to 200°C and the speed was 250r / min; the temperature of the second-stage screw extruder was set to 200°C and the speed was 150r / min. 0.497 parts of EBS were added at the exhaust port of the second-stage screw, and then underwater granulation was performed to obtain self-matting TPU.

[0100] After drying, the self-matting TPU enters the screw for plasticization, and the screw temperature is set at 200°C and the speed is 300r / min. Then it enters the assembly for spinning through a metering pump, and undergoes side-blowing cooling, secondary stretching, oiling and winding to obtain a TPU hot melt wire with a specification of 210D.

[0101] Comparative Example 3

[0102] Accurately weigh the raw materials according to the following weight parts:

[0103] Add 50 parts of mixed polyester polyol with a molecular weight of 3500 (the mass ratio of PEA-3500, PMA-3500 and PEMA-3500 is 5:3:2), 0.1 parts of antioxidant 1010, 0.05 parts of antioxidant TNP, and 0.002 parts of tetrabutyl titanate to kettle A, set the temperature to 110°C, mix evenly and keep warm. Add 37.232 parts of HDI (isocyanate index 0.90) to kettle B, and set the kettle temperature to 60°C. Add 12.120 parts of butanediol to kettle C1, set the kettle temperature to 70°C, mix evenly and keep warm; after the material temperature in kettles A, B, and C reaches the set temperature, pour the above components into a two-stage screw extruder for reaction, the temperature of the first-stage screw extruder is set to 200°C, and the speed is 250r / min; the temperature of the second-stage screw extruder is set to 200°C, and the speed is 150r / min. 0.497 parts of EBS were added at the exhaust port of the second-stage screw, followed by underwater granulation to obtain self-matting TPU.

[0104] After drying, the self-matting TPU enters the screw for plasticization, and the screw temperature is set at 200°C and the speed is 300r / min. Then it enters the assembly for spinning through a metering pump, and undergoes side-blowing cooling, secondary stretching, oiling and winding to obtain a TPU hot melt wire with a specification of 210D.

[0105] Comparative Example 4

[0106] Accurately weigh the raw materials according to the following weight parts:

[0107] 60.297 parts of mixed polyester polyol with a molecular weight of 1500 (the mass ratio of PEA-1500, PMA-1500 and PEMA-1500 is 3:1:1), 0.06 parts of antioxidant 1010, 0.05 parts of antioxidant TNP, and 0.001 parts of tetrabutyl titanate were added to kettle A, and the temperature was set to 100°C. After mixing evenly, they were kept warm. 31.998 parts of MDI (isocyanate index 1.05) were added to kettle B, and the temperature was set to 80°C; 2.639 parts of ethylene glycol, 2.262 parts of 2-methyl-1,3-propylene glycol, and 1.885 parts of 1,4-cyclohexanediol, three small molecule chain extenders, were added to kettle C1, and the kettle temperature was set to 80°C. After mixing evenly, they were kept warm; 0.754 parts of hydroquinone-bis(β-hydroxyethyl) ether (HQEE) small molecule chain extender was added to kettle C2, and the kettle temperature was set to 120℃; after the material temperature in the A, B, C1 and C2 kettles reaches the set temperature, the components in the above four kettles are poured into a two-stage screw extruder for reaction, the temperature of the first-stage screw extruder is set to 300℃, and the speed is 200r / min; the temperature of the second-stage screw extruder is set to 150℃, and the speed is 100r / min, 0.02 parts of EBS are added at the exhaust port of the second-stage screw, and then underwater granulation is performed to obtain a thermoplastic polyurethane elastomer (TPU).

[0108] After drying, the self-matting TPU enters the screw for plasticization, the screw temperature is set at 160°C, and the speed is 200r / min. Then it enters the assembly for spinning through a metering pump, and undergoes side-blowing cooling, secondary stretching, oiling and winding to obtain a TPU hot melt wire with a specification of 210D.

[0109] Comparative Example 5

[0110] Accurately weigh the raw materials according to the following weight parts:

[0111] 71.6 parts of mixed polyester polyol with a molecular weight of 1500 (the mass ratio of PEA-1500, PMA-1500 and PEMA-1500 is 3:1:1), 0.06 parts of antioxidant 1010, 0.05 parts of antioxidant TNP, and 0.001 parts of tetrabutyl titanate were added to kettle A, and the temperature was set to 100°C. After mixing evenly, they were kept warm. 23.7 parts of MDI (isocyanate index 1.02) were added to kettle B, and the temperature was set to 80°C; 1.889 parts of ethylene glycol, 1.200 parts of 2-methyl-1,3-propylene glycol, and 0.870 parts of 1,4-cyclohexanediol, three small molecule chain extenders, were added to kettle C1, and the kettle temperature was set to 80°C. After mixing evenly, they were kept warm; 0.630 parts of hydroquinone-bis(β-hydroxyethyl) ether (HQEE) small molecule chain extender was added to kettle C2, and the kettle temperature was set to 1 20℃; after the material temperature in the A, B, C1 and C2 kettles reaches the set temperature, the components in the above four kettles are poured into a two-stage screw extruder for reaction, the temperature of the first-stage screw extruder is set to 300℃, and the speed is 200r / min; the temperature of the second-stage screw extruder is set to 150℃, and the speed is 100r / min, 0.02 parts of EBS are added at the exhaust port of the second-stage screw, and then underwater granulation is performed to obtain a thermoplastic polyurethane elastomer (TPU).

[0112] After drying, the self-matting TPU is put into the screw for plasticization, and the screw temperature is set at 160°C and the speed is 200r / min. Then it is put into the assembly for spinning through a metering pump, and after being cooled by side air blowing in the tunnel, a TPU hot melt wire with a specification of 210D is obtained through stretching, oiling and winding.

[0113] Comparative Example 6

[0114] Accurately weigh the raw materials according to the following weight parts:

[0115] 60.297 parts of mixed polyester polyol with a molecular weight of 1500 (the mass ratio of PEA-1500, PMA-1500 and PEMA-1500 is 3:1:1), 0.06 parts of antioxidant 1010, 0.05 parts of antioxidant TNP, and 0.001 parts of tetrabutyl titanate were added to kettle A, and the temperature was set to 100°C. After mixing evenly, they were kept warm. 31.998 parts of MDI (isocyanate index 1.00) were added to kettle B, and the temperature was set to 80°C; 2.639 parts of ethylene glycol, 2.262 parts of 2-methyl-1,3-propanediol, and 1.885 parts of 1,4-cyclohexanediol, three small molecule chain extenders, were added to kettle C1, and the kettle temperature was set to 80°C. After mixing evenly, they were kept warm; 0.754 parts of hydroquinone-bis(β-hydroxyethyl) ether (HQEE) small molecule chain extender was added to kettle C2, and the kettle temperature was set to 120℃; after the material temperature in the A, B, C1 and C2 kettles reaches the set temperature, the components in the above four kettles are poured into a two-stage screw extruder for reaction, the temperature of the first-stage screw extruder is set to 300℃, and the speed is 200r / min; the temperature of the second-stage screw extruder is set to 150℃, and the speed is 100r / min, 0.02 parts of EBS are added at the exhaust port of the second-stage screw, and then underwater granulation is performed to obtain a thermoplastic polyurethane elastomer (TPU).

[0116] The self-matting TPU is dried and then put into the screw for plasticization, the screw temperature is set at 150°C and the speed is 400r / min. Then it is put into the assembly for spinning through the metering pump, and after the side blowing cooling, oiling and winding, the TPU hot melt wire with the specification of 210D is obtained.

[0117] The properties of the TPU prepared in Examples 1-3 and Comparative Examples 1-6 were tested, and the results are shown in Table 1.

[0118] Table 1

[0119]

[0120] The properties of the TPU hot melt wires prepared in Examples 1-3 and Comparative Examples 1-6 were tested, and the results are shown in Table 2.

[0121] Table 2

[0122]

[0123] It can be seen from Table 1 and Table 2 that compared with the embodiments, the 60° gloss of TPU and hot melt in Comparative Examples 1-3 is very high, mainly because the formula uses a single polyester polyol or a single small molecule chain extender, which promotes the separation of the two phases and improves the transparency. The strength of TPU and hot melt in Comparative Example 4 is slightly improved, the 60° gloss is greatly improved, and the extinction is lost. The reason is that the number average molecular weight of Comparative Example 4 is increased to 91456, which improves the strength but reduces the crystallinity of the hard segment. The 60° gloss of TPU and hot melt in Comparative Example 5 is very high, reaching 51.0 and 46.2 respectively, and its strength has a slight decrease. The main reason is that the proportion of small molecule chain extender is 4.7%, which reduces the hard segment content and hardness, promotes the separation of the two phases, and thus improves the transparency. The process for preparing TPU monofilament in Comparative Example 6 uses a conventional melt spinning process without a secondary stretching process, so the prepared TPU monofilament has a large elongation of 350%, which is not suitable for fly woven fabrics.

[0124] The embodiments described above are only descriptions of the preferred modes of the present invention, and are not intended to limit the scope of the present invention. Without departing from the design spirit of the present invention, various modifications and improvements made to the technical solutions of the present invention by ordinary technicians in this field should all fall within the protection scope determined by the claims of the present invention.

Claims

1. A self-matting thermoplastic polyurethane elastomer, characterized in that: According to weight parts, it includes the following raw materials: 40-80 parts of polyester polyol; Chain extender 5-15 parts; 15-50 parts of diisocyanate; Antioxidant 0.02-2 parts; Lubricant 0.01-1 part; Catalyst 0.001-0.01 part; The polyester polyol is polyethylene adipate polyol, polyethylene adipate-2-methyl-1,3-propylene glycol ester polyol and polyethylene adipate-2-methyl-1,3-propylene glycol ester polyol, the molecular weight of the polyester polyol is 800-4000, and the molecular weights of polyethylene adipate polyol, polyethylene adipate-2-methyl-1,3-propylene glycol ester polyol and polyethylene adipate-2-methyl-1,3-propylene glycol ester polyol are the same; The chain extender includes ethylene glycol, 2-methyl-1,3-propylene glycol, 1,4-cyclohexanediol and hydroquinone-bis(β-hydroxyethyl) ether; Based on 100% of the total amount of the polyester polyol, the mass fraction of the polyethylene adipate polyol is 30-60%, the mass fraction of the polyethylene adipate-2-methyl-1,3-propylene glycol ester polyol is 20-40%, and the mass fraction of the polyethylene adipate-2-methyl-1,3-propylene glycol ester polyol is 10-30%; The number average molecular weight of the self-matting thermoplastic polyurethane elastomer is 70,000-90,000; The isocyanate index of the diisocyanate is 0.85-1.04; The method for preparing the self-matting thermoplastic polyurethane elastomer comprises the following steps: Mix the polyester polyol, add antioxidant and catalyst, and adjust the temperature to 100-120°C; Adjust the temperature of diisocyanate to 50-80°C; Mix chain extender ethylene glycol, 2-methyl-1,3-propanediol and 1,4-cyclohexanediol and adjust the temperature to 56-80°C; Adjust the chain extender hydroquinone-bis(β-hydroxyethyl) ether temperature to 104-120°C; The above four components are poured into a two-stage screw extruder at the same time according to proportion for reaction, a lubricant is added to the exhaust port of the large screw, and then granulation is performed underwater to obtain a self-matting thermoplastic polyurethane elastomer.

2. A self-matting thermoplastic polyurethane elastomer according to claim 1, characterized in that: The antioxidants are A0-60, TNP, TP-10H and combinations thereof.

3. The self-matting thermoplastic polyurethane elastomer according to claim 1, characterized in that: The catalyst is an organic tin catalyst, a titanate catalyst or a metal salt catalyst.

4. A method for preparing the self-matting thermoplastic polyurethane elastomer according to any one of claims 1 to 3, characterized in that: The steps include: Mix the polyester polyol, add antioxidant and catalyst, and adjust the temperature to 100-120°C; Adjust the temperature of diisocyanate to 50-80°C; Mix chain extender ethylene glycol, 2-methyl-1,3-propanediol and 1,4-cyclohexanediol and adjust the temperature to 56-80°C; Adjust the chain extender hydroquinone-bis(β-hydroxyethyl) ether temperature to 104-120°C; The above four components are poured into a two-stage screw extruder at the same time according to proportion to react, a lubricant is added, and then underwater granulation is performed to obtain a self-matting thermoplastic polyurethane elastomer.

5. Use of the self-matting thermoplastic polyurethane elastomer according to any one of claims 1 to 3 in the preparation of self-matting thermoplastic polyurethane hot melt wire, characterized in that: The preparation method of self-matting thermoplastic polyurethane hot melt wire is as follows: the self-matting thermoplastic polyurethane elastomer is dried and then enters the screw for plasticization, and then enters the component spinning through a metering pump, and is cooled by side blowing in the channel, stretched twice, oiled and wound to obtain the self-matting thermoplastic polyurethane hot melt wire with a specification of 210D.

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