A highly transparent wear-resistant thermoplastic polyurethane elastomer material and preparation method thereof

Abstract

The present invention discloses a highly transparent, wear-resistant thermoplastic polyurethane elastomer material and a preparation method thereof. The material is prepared from the following raw materials: A) 45-85% polyol; B) 10-45% polyisocyanate; C) 1-20% small molecule diol chain extender; D) 0.5-5% polypyrrole chain extender crosslinker. The present invention introduces a polypyrrole structure to increase more physical and chemical crosslinking points in the material itself, greatly improving the wear resistance while ensuring thermoplastic processing. At the same time, due to its steric effect, the regularity of the hard segment of the material is destroyed to a certain extent, so that the material has high transparency and can be used in the fields of sole materials, consumer electronics, industrial products, etc.

Description

Technical Field

[0001] The invention relates to the technical field of polyurethane elastomer preparation, in particular to a highly transparent and wear-resistant thermoplastic polyurethane elastomer and a preparation method thereof. Background Art

[0002] Thermoplastic polyurethane elastomer (TPU) is a type of polyurethane material that can be plasticized by heating, dissolved by solvents, and has little or no crosslinking in its chemical structure, which is between rubber and plastic. Due to its wide range of hardness and its performance advantages such as high modulus, high strength, and high wear resistance, it is widely used in various fields. In recent years, with the continuous improvement of living standards, people's performance requirements for TPU sole materials have become higher and higher. Traditional TPU materials can no longer meet the wear resistance requirements of sports soles such as basketball shoes, especially in terms of thermal friction.

[0003] Patent CN 102786652 A adds a composite additive of methyl silicone oil and molybdenum disulfide to the preparation of thermoplastic polyurethane elasticity, achieving a certain friction reduction effect;

[0004] Patent CN 111269552 A adds silicone resin, polytetrafluoroethylene powder, polyethylene wax powder or silicone resin as wear-resistant additives to thermoplastic elastomer materials to improve the wear-resistant effect of the composition;

[0005] Patent CN 112831175 A disperses a modified thermoplastic elastomer made of nitrile rubber vulcanized rubber particles in a polyurethane elastomer, which increases the friction coefficient and loss factor of the material surface and improves the wear resistance;

[0006] Patent CN 110283298 B uses polyols with silicone active end-capping and introduces benzoic acid glycol ester structure to form a micro-crosslinking structure to a certain extent, thus improving the wear resistance of the material;

[0007] Although the thermoplastic polyurethane prepared by the above method improves the wear resistance of the material to a certain extent, it has disadvantages such as poor transparency and poor processing performance, which limits its wide application. Summary of the invention

[0008] The present invention aims at solving the above-mentioned deficiencies in the prior art and provides a highly transparent and wear-resistant thermoplastic polyurethane elastomer material.

[0009] The technical solution adopted by the present invention to solve the above problems is as follows:

[0010] A highly transparent, wear-resistant thermoplastic polyurethane elastomer material, which comprises the following components in percentage by weight, based on the total mass of components AD being 100%:

[0011]

[0012] The number average molecular weight of the polyol of component A) is 800 to 4000 g / mol, preferably 1000 to 2500 g / mol.

[0013] The component A) polyol can be polyester polyol, polyether polyol, polycaprolactone polyol, polycarbonate polyol or a combination thereof;

[0014] The polyester polyol is prepared from a dibasic acid and a diol by a polyester polyol synthesis process known in the industry; wherein the dibasic acid is one or more of succinic acid, adipic acid, and sebacic acid, and the diol is one or more of ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, dipropylene glycol, and neopentyl glycol; preferably, the polyester polyol is one or more of polybutylene adipate, polyhexanediol adipate, and polyethylene glycol adipate;

[0015] The polyether polyol is prepared by ring-opening polymerization of an epoxy compound in the presence of an active hydrogen-containing compound as an initiator and a catalyst; wherein the epoxy compound is one or more of propylene oxide, tetrahydrofuran, and ethylene oxide, and preferably, the polyether polyol is polytetramethylene ether glycol;

[0016] The polycaprolactone polyol is prepared by ring-opening polymerization of ε-caprolactone monomer and an initiator, wherein the initiator is one or more of 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, diethylene glycol, and ethylene glycol; preferably, the initiator is neopentyl glycol;

[0017] The polycarbonate polyol is prepared by an ester exchange reaction between a small molecule diol and a small molecule carbonate; wherein the small molecule diol is one or more of 1,6-hexanediol, 1,4-butanediol, 1,4-cyclohexanedimethanol, 1,5-pentanediol, and 3-methylpentanediol, and preferably, the small molecule diol is 1,6-hexanediol; the small molecule carbonate is one or more of dimethyl carbonate, diethyl carbonate, dipropyl carbonate, diphenyl carbonate, ethylene carbonate, or propylene carbonate, and preferably, the small molecule carbonate is ethylene carbonate.

[0018] The component B) polyisocyanate is one or more of toluene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, p-phenylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, 3,3-dimethyl-4,4-biphenyl diisocyanate, cyclohexane dimethylene diisocyanate, 4,4-dicyclohexylmethane diisocyanate, and 3,3-dimethyl-4,4-diphenylmethane diisocyanate; preferably one or more of toluene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, p-phenylene diisocyanate, xylylene diisocyanate, 3,3-dimethyl-4,4-biphenyl diisocyanate, and 3,3-dimethyl-4,4-diphenylmethane diisocyanate.

[0019] The component C) small molecule diol chain extender is selected from one or more of ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, 1,2-propylene glycol, methyl propanediol, methyl pentanediol, 1,4-cyclohexanediol, neopentyl glycol, and terephthalic acid; preferably one or more of 1,3-propylene glycol, 1,4-butanediol, and 1,6-hexanediol.

[0020] The general structural formula of the component D) polypyrrole chain extender crosslinker is as follows:

[0021]

[0022] Wherein, R1 and R2 are selected from any one of H, OH, and CH2OH, respectively.

[0023] Wherein, n is a natural number of 0-10, preferably n is a natural number of 0-4.

[0024] The thermoplastic polyurethane elastomer material may also be added with one or a mixture of more than one of methyl titanate, ethyl titanate, propyl titanate, butyl titanate, stannous octoate, dibutyltin dilaurate and triethylenediamine as a catalyst for the polymerization reaction.

[0025] The thermoplastic polyurethane elastomer material may also contain processing aids such as antioxidants, light stabilizers, ultraviolet absorbers, lubricants, etc.

[0026] The thermoplastic polyurethane elastomer material comprises the following preparation steps:

[0027] The polyol, polyisocyanate, small molecule diol chain extender, polypyrrole chain extender crosslinker and optional auxiliary agent / catalyst are uniformly mixed in a stirrer, and then the uniformly mixed materials are fed into a reactive twin-screw extruder, and the particles of thermoplastic polyurethane elastomer are obtained after reactive extrusion, underwater pelletizing and hopper drying, wherein the temperature of the twin-screw extruder is between 120-250° C., the screw speed is 800-1200 RPM, the granulation water temperature is 30-60° C., the drying temperature is 40-80° C., and the drying time is 30 min-2 h.

[0028] The thermoplastic polyurethane elastomer material of the present invention can be used in the fields of shoe sole materials, consumer electronics, industrial products, etc.

[0029] The beneficial effects of the present invention are:

[0030] The present invention introduces a polypyrrole structure, which not only allows the material itself to form controllable chemical micro-crosslinks, but also increases a large number of physical crosslinking points through hydrogen bonding, thereby greatly improving the wear resistance while ensuring thermoplastic processing. At the same time, due to its steric effect, the regularity of the hard segment of the material is destroyed to a certain extent, so that the material has high transparency and can be used in the fields of sole materials, consumer electronics, industrial products, etc. DETAILED DESCRIPTION

[0031] The principles and features of the present invention are described below in conjunction with examples. The examples are only used to explain the present invention and are not used to limit the scope of the present invention.

[0032] The raw materials used in the practice of the present invention are all commercially available conventional products.

[0033] The materials used are as follows:

[0034] A) Polyols:

[0035] PBA (polybutylene adipate), molecular weight 1000 g / mol, Wanhua Chemical Group Co., Ltd.;

[0036] PEHA (polyethylene glycol adipate), molecular weight 1500 g / mol, Wanhua Chemical Group Co., Ltd.;

[0037] PEBA (polyethylene glycol adipate butanediol), molecular weight 1500g / mol, Wanhua Chemical Group Co., Ltd.

[0038] PPA (polypropylene adipate), molecular weight 2000 g / mol, Wanhua Chemical Group Co., Ltd.;

[0039] PTMG (polytetramethylene glycol), molecular weight 1000 g / mol, BASF Chemical Co., Ltd.;

[0040] NPG-PCL (neopentyl glycol initiated polycaprolactone), molecular weight 1500, Wanhua Chemical Group Co., Ltd.;

[0041] B) Polyisocyanate:

[0042] MDI (diphenylmethane diisocyanate), HDI (hexamethylene diisocyanate), and HMDI (4,4-dicyclohexylmethane diisocyanate) are all from Wanhua Chemical Group Co., Ltd.;

[0043] C) Small molecule diol chain extender:

[0044] EG (ethylene glycol), PDO (1,3-propylene glycol), BDO (1,4-butanediol), and HDO (1,6-hexanediol) were all purchased from Aladdin;

[0045] D) Polypyrrole chain extender crosslinker:

[0046] Polypyrrole chain extenders D-1 to D-6 were purchased from TCI:

[0047] Its general structure and specific structure are as follows:

[0048]

[0049] D-1: n=0, R1 and R2 are both OH, and its structure is as follows:

[0050]

[0051] D-2: n=0, R1 and R2 are both CH2OH, and its structure is as follows:

[0052]

[0053] D-3: n = 1, R1 and R2 are both CH2OH, and its structure is as follows:

[0054]

[0055] D-4: n=2, R1 and R2 are both H, and its structure is as follows:

[0056]

[0057] D-5: n=3, R1 is H, R2 is CH2OH, and its structure is as follows:

[0058]

[0059] Examples 1-8

[0060] Example 1

[0061] A thermoplastic polyurethane elastomer, the components of which are measured by weight: 60 parts of PBA, 6 parts of 1,3-propylene glycol, 0.5 parts of D-1 chain extender, 33.5 parts of diphenylmethane diisocyanate, a total of 100 parts. The components are uniformly mixed in a stirrer, and then the uniformly mixed materials are fed into a reactive twin-screw extruder, and the particles of the thermoplastic polyurethane elastomer are obtained after reactive extrusion, underwater pelletizing, and hopper drying. The temperature of the twin-screw extruder is between 120-250°C, the screw speed is 800RPM, the granulation water temperature is 45°C, the drying temperature is 60°C, and the drying time is 2h.

[0062] Embodiment 2-7

[0063] The formulations of Examples 2-7 are shown in Table 1, and the preparation methods are the same as those of Example 1.

[0064] Comparative Example 1-2

[0065] The formula of Comparative Example 1-2 is shown in Table 1, and the preparation method is the same as Example 1.

[0066] Table 1 Composition of thermoplastic polyurethane elastomer

[0067]

[0068] The thermoplastic polyurethane elastomers obtained in Examples 1-8 and Comparative Examples 1-2 were subjected to performance tests. The wear resistance was tested according to ISO 4649 standard; the transparency was tested according to ASTM D2132 standard. The test results are shown in Table 2.

[0069] Table 2 Performance test

[0070]

[0071] It can be seen from the performance test data in Table 2 that, compared with Comparative Examples 1 and 2, the product Examples 1-8 of the present invention have greatly improved wear resistance and transparency.

[0072] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A highly transparent, wear-resistant thermoplastic polyurethane elastomer, characterized in that: Taking the total mass of component AD as 100%, the following raw materials are included in weight percentage: Component D) polypyrrole chain extender crosslinking agent general structure formula is as follows: Wherein, R1 and R2 are selected from any one of H, OH, and CH2OH, respectively. Wherein, n is a natural number from 0 to 10.

2. The thermoplastic polyurethane elastomer according to claim 1, characterized in that Taking the total mass of component AD as 100%, the following raw materials are included in weight percentage:

3. The thermoplastic polyurethane elastomer according to claim 1, characterized in that n is a natural number from 0 to 4.

4. The thermoplastic polyurethane elastomer according to claim 1, characterized in that The number average molecular weight of the polyol of component A) is 800 to 4000 g / mol.

5. The thermoplastic polyurethane elastomer according to claim 4, characterized in that: The number average molecular weight of the polyol of component A) is 1000 to 2500 g / mol.

6. The thermoplastic polyurethane elastomer according to any one of claims 1 to 5, characterized in that: The polyol of component A) is selected from polyester polyols.

7. The thermoplastic polyurethane elastomer according to any one of claims 1 to 5, characterized in that: The component A) polyol is at least one selected from polyether polyol, polycaprolactone polyol and polycarbonate polyol.

8. The thermoplastic polyurethane elastomer according to claim 6, characterized in that The polyester polyol is prepared from a dibasic acid and a diol; wherein the dibasic acid is one or more of succinic acid, adipic acid, and sebacic acid, and the diol is one or more of ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, 1,6-hexanediol, diethylene glycol, dipropylene glycol, and neopentyl glycol.

9. The thermoplastic polyurethane elastomer according to claim 8, characterized in that: The polyester polyol is one or more of polybutylene adipate, polyhexylene adipate, and polyethylene adipate.

10. The thermoplastic polyurethane elastomer according to claim 7, characterized in that: The polyether polyol is prepared by ring-opening polymerization of an epoxy compound containing an active hydrogen compound as an initiator; wherein the epoxy compound is one or more of propylene oxide, tetrahydrofuran and ethylene oxide.

11. The thermoplastic polyurethane elastomer according to claim 10, characterized in that: The polyether polyol is polytetramethylene ether glycol.

12. The thermoplastic polyurethane elastomer according to claim 7, characterized in that: The polycaprolactone polyol is prepared by ring-opening polymerization of ε-caprolactone monomer and an initiator, wherein the initiator is one or more of 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, diethylene glycol, and ethylene glycol.

13. The thermoplastic polyurethane elastomer according to claim 7, characterized in that: The polycarbonate polyol is prepared by ester exchange reaction between a small molecule diol and a small molecule carbonate; the small molecule diol is one or more of 1,6-hexanediol, 1,4-butanediol, 1,4-cyclohexanedimethanol, 1,5-pentanediol, and 3-methylpentanediol; the small molecule carbonate is one or more of dimethyl carbonate, diethyl carbonate, dipropyl carbonate, diphenyl carbonate, ethylene carbonate, or propylene carbonate.

14. The thermoplastic polyurethane elastomer according to any one of claims 1 to 3, characterized in that: The component B) polyisocyanate is one or more of toluene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, p-phenylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, 3,3-dimethyl-4,4-biphenyl diisocyanate, cyclohexane dimethylene diisocyanate, 4,4-dicyclohexylmethane diisocyanate and 3,3-dimethyl-4,4-diphenylmethane diisocyanate.

15. The thermoplastic polyurethane elastomer according to any one of claims 1 to 3, characterized in that: The component C) small molecule diol is selected from one or more of ethylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, 1,2-propylene glycol, methylpropylene glycol, methylpentanediol, 1,4-cyclohexanediol, neopentyl glycol, and terephthalic acid.

16. The thermoplastic polyurethane elastomer according to any one of claims 1 to 3, characterized in that: One or more of methyl titanate, ethyl titanate, propyl titanate, butyl titanate, stannous octoate, dibutyltin dilaurate and triethylenediamine are optionally added to the elastomer as a catalyst for the polymerization reaction.

17. The thermoplastic polyurethane elastomer according to any one of claims 1 to 3, characterized in that: Antioxidants, light stabilizers, ultraviolet absorbers and lubricants can be optionally added to the elastomer.

18. The thermoplastic polyurethane elastomer according to any one of claims 1 to 3, characterized in that: The preparation method comprises the following preparation steps: The polyol, polyisocyanate, small molecule diol chain extender and polypyrrole chain extender crosslinker are uniformly mixed and then fed into a reactive twin-screw extruder to obtain thermoplastic polyurethane elastomer particles after reactive extrusion, underwater pelletizing and hopper drying.

19. The thermoplastic polyurethane elastomer according to claim 18, wherein the temperature of the twin-screw extruder is between 120-250°C, the screw speed is 800-1200RPM, the granulation water temperature is 30-60°C, the drying temperature is 40-80°C, and the drying time is 30min-2h.

20. Use of the thermoplastic polyurethane elastomer according to any one of claims 1 to 19, in fields including sole materials, consumer electronics and industrial products.

Images