A wet-slip wear-resistant thermoplastic polyurethane elastomer material and preparation method thereof

Abstract

The present invention discloses a wet-slip and 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) 0.1-1.5% acyclic heterooxygen atom chain extender; and E) 0.1-0.5% acyclic heteronitrogen atom chain extender. The present invention introduces a local hyperbranched structure with an acyclic heteroatom chain at the back end of the reaction, which combines with the multiple hydrogen bonds of the polyurethane to form a high-density hydrogen bond network. When the dynamic hydrogen bond network is destroyed on the damaged cross section, an activation layer is formed when it comes into contact with water. The "water bridge" promotes the rapid recombination and recovery of the hydrogen bond network between the cross sections, greatly improving the wet-slip and wear-resistant properties of the material. The material can be used in the fields of sole materials, blending modification, industrial products, etc.

Description

Technical Field

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

[0002] Thermoplastic polyurethane (TPU) is a linear polyurethane material that melts when heated, dissolves in solvents, and exhibits minimal or no crosslinking in its chemical structure. Its glass transition temperature lies between that of rubber and plastic. Due to its wide hardness range, ease of injection molding, and high mechanical properties, it is increasingly being used in footwear. However, while conventional TPU materials offer excellent mechanical and wear resistance, their slip resistance, particularly in wet conditions, is suboptimal, limiting their application. Therefore, further improvements in material performance are needed.

[0003] Patent CN112745657 A adds the anti-slip agent RGO-HCA as a graphene-based nanocomposite material to the preparation of thermoplastic polyurethane elastic material, achieving a certain anti-slip effect, but it will reduce the mechanical properties and affect the processing performance;

[0004] Patent CN112831175 A disperses vulcanized rubber particles of nitrile rubber in a polyurethane elastomer to obtain a modified thermoplastic polyurethane elastomer. This method not only maintains the mechanical properties and wear resistance of the thermoplastic polyurethane elastomer, but also improves the surface friction coefficient and loss factor of the material. However, its improvement in wet skid resistance is limited, and the process is irreversible.

[0005] Patent CN118003679 A obtains a prepolymer by reacting polytetramethylene glycol and isophorone diisocyanate. A cross-linked network is then formed under the action of a specific chain extender and triethanolamine, thereby improving the anti-slip performance of the material. However, this is a completely chemical cross-linking method, which is irreversible and affects the processing performance of the material.

[0006] Patent CN112724651 A introduces metal sulfide, fatty acid amide-modified nano-calcium carbonate, and MPMS-modified nano-silica to create a thermoplastic polyurethane elastomer material with both anti-slip and wear-resistant properties. However, this also affects processing performance, and the introduced metal sulfide is not environmentally friendly.

[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 insufficient wet anti-slip properties, poor processing performance, and reduced strength, which limit its wide application. Summary of the Invention

[0008] In view of the above-mentioned deficiencies in the prior art, the present invention provides a wet-slip and wear-resistant thermoplastic polyurethane elastomer material, while ensuring the mechanical properties and processing properties of the material.

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

[0010] A wet non-slip, wear-resistant thermoplastic polyurethane elastomer material is prepared from the following components in percentage by weight, based on the total mass of component AE being 100%:

[0011] A) polyol 45-85%; preferably 60-80%;

[0012] B) polyisocyanate 10-45%; preferably 15-35%;

[0013] C) 1-20% of a small molecule diol chain extender; preferably 3-15%;

[0014] D) 0.1-1.5% acyclic heterooxygen atom chain extender; preferably 0.3-1%;

[0015] E) Acyclic hetero nitrogen atom chain extender 0.1-0.5%; preferably 0.1-0.3%.

[0016] The number average molecular weight of the polyol of component A) is 800 to 4000 g / mol, preferably 1000 to 3000 g / mol.

[0017] The polyol of component A) is selected from polyester polyol, polyether polyol, polycaprolactone polyol, polycarbonate polyol or a combination thereof.

[0018] The polyester polyol is prepared from a dibasic acid and a diol through 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 polybutylene adipate.

[0019] 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. Preferably, the polyether polyol is polytetramethylene ether glycol.

[0020] 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.

[0021] 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.

[0022] The polyisocyanate of component B) 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.

[0023] 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, methylpropylene glycol, methylpentanediol, 1,4-cyclohexanediol, neopentyl glycol, and terephthalic acid methanol; preferably one or more of ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, and 1,6-hexanediol.

[0024] The general structural formula of the component D) acyclic heteroatom chain extender is as follows:

[0025]

[0026] Wherein, 1≤n≤10, and n is an integer;

[0027] Wherein, R1 and R2 are independently selected from any one of OH and NH2.

[0028] The general structural formula of the component E) acyclic nitrogen atom chain extender is as follows:

[0029]

[0030] Wherein, R3 and R4 are independently selected from any one of OH and NH2.

[0031] Optionally, one or a mixture of more than one of methyl titanate, ethyl titanate, propyl titanate, butyl titanate, stannous octoate, dibutyltin dilaurate, and triethylenediamine is added to the thermoplastic polyurethane elastomer material as a polymerization catalyst.

[0032] Optionally, processing auxiliary agents such as antioxidants, light stabilizers, ultraviolet absorbers, lubricants, etc. may be added to the thermoplastic polyurethane elastomer material.

[0033] On the other hand, the present invention also provides a method for preparing a thermoplastic polyurethane elastomer material, the method comprising the following steps:

[0034] The polyol, polyisocyanate and small molecule diol chain extender are mixed evenly, and then the mixed materials are fed into a reactive twin-screw extruder, and an acyclic heterooxygen atom chain extender and an acyclic heteronitrogen atom chain extender cross-linker are added. After reactive extrusion, underwater pelletizing and hopper drying, thermoplastic polyurethane elastomer particles are obtained.

[0035] 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-120min.

[0036] Finally, the present invention provides applications of the thermoplastic polyurethane elastomer material in the fields of sole materials, blending modification, and industrial supplies.

[0037] The beneficial effects of the present invention are:

[0038] This invention introduces acyclic heteroatom chains through the reaction backend to form a localized hyperbranched structure. These structures, combined with the polyurethane's multiple hydrogen bonds, form a high-density hydrogen bond network. When the dynamic hydrogen bond network is disrupted on a damaged surface, water forms an activation layer, which, through "water bridges," promotes rapid reorganization and recovery of the hydrogen bond network across the surface, significantly improving the material's wet-slip and wear-resistant properties. The material can be used in shoe sole materials, blending and modification, and industrial products. DETAILED DESCRIPTION

[0039] The principles and features of the present invention are described below with reference to examples. The examples are only used to explain the present invention and are not used to limit the scope of the present invention.

[0040] The raw materials used in the practice of the present invention are all commercially available conventional products.

[0041] Main sources of raw materials

[0042] A) Polyols:

[0043] PBA (polybutylene adipate), molecular weight 2000 g / mol, Wanhua Chemical Group Co., Ltd.

[0044] PEA (polyethylene adipate), molecular weight 1500 g / mol, Wanhua Chemical Group Co., Ltd.

[0045] PEBA (polyethylene glycol adipate), molecular weight 3000g / mol, Wanhua Chemical Group Co., Ltd.

[0046] PTMG (polytetramethylenetetramethylene ether), molecular weight 1000 g / mol, BASF Chemical Co., Ltd.;

[0047] NPG-PCL (neopentyl glycol initiated polycaprolactone), molecular weight 2000, Daicel (China) Investment Co., Ltd.;

[0048] PCDL (polycarbonate diol), molecular weight 2500 g / mol, Daicel (China) Investment Co., Ltd.;

[0049] B) Diisocyanate:

[0050] MDI (methylene diphenyl diisocyanate), HDI (hexamethylene diisocyanate), and TDI (toluene diisocyanate) were all from Wanhua Chemical Group Co., Ltd.;

[0051] C) Small molecule diol chain extender:

[0052] EG (ethylene glycol), PDO (1,3-propylene glycol), BDO (1,4-butanediol), and HDO (1,6-hexanediol) were purchased from Aladdin;

[0053] D) Non-cyclic heteroatom chain extender:

[0054] The structures of acyclic heteroatom chain extenders D-1 to D-5 are as follows:

[0055] D-1: n=1, R1 and R2 are both NH2, purchased from Aaron Chem, its structure is as follows

[0056]

[0057] D-2: n=2, R1 and R2 are both NH2, purchased from Aaron Chem, its structure is as follows

[0058]

[0059] D-3: n=2, R1 and R2 are both OH, purchased from TCI, its structure is as follows

[0060]

[0061] D-4: n=3, R1 is OH, R2 is NH2, purchased from Aaron Chem, its structure is as follows

[0062]

[0063] D-5: n=4, R1 is OH, R2 is NH2, purchased from Aurora, its structure is as follows

[0064]

[0065] E) Acyclic nitrogen atom chain extender crosslinker:

[0066] The structures of acyclic hetero nitrogen atom chain extender crosslinkers E-1 to E-3 are as follows:

[0067] E-1: R3 and R4 are both OH, purchased from Aaron Chem, and its structure is as follows:

[0068]

[0069] E-2: R3 and R4 are both NH2, purchased from Aaron Chem, and its structure is as follows:

[0070]

[0071] E-3: R3 is OH, R4 is NH2, purchased from Aaron Chem, its structure is as follows:

[0072]

[0073] Main test methods

[0074] Abrasion resistance is tested according to ISO 4649; wet and dry slip resistance is tested according to ASTM D1894.

[0075] Examples 1-8

[0076] Example 1

[0077] A thermoplastic polyurethane elastomer comprises the following components, by weight: 60 parts of polybutylene adipate, 7 parts of 1,4-butanediol, and 32 parts of diphenylmethane diisocyanate, uniformly mixed in a blender, followed by uniform mixing of 0.9 parts of a D-1 chain extender and 0.1 parts of an E-1 chain extender crosslinker in zones 7-9. The mixture is then fed into a reactive twin-screw extruder, followed by reactive extrusion, underwater pelletizing, and hopper drying to produce thermoplastic polyurethane elastomer pellets. The twin-screw extruder temperature is between 120°C and 250°C, the screw speed is 800 RPM, the pelletizing water temperature is 45°C, the drying temperature is 60°C, and the drying time is 2 hours.

[0078] Example 2-10

[0079] The formulations of Examples 2-10 are shown in Table 1, and the preparation methods are the same as those of Example 1.

[0080] Comparative Examples 1-3

[0081] The formulations of Comparative Examples 1-3 are shown in Table 1, and the preparation methods are the same as those of Example 1.

[0082] Table 1 Composition of thermoplastic polyurethane elastomer

[0083]

[0084]

[0085] The thermoplastic polyurethane elastomers obtained in Examples 1-10 and Comparative Examples 1-3 were subjected to performance tests. The wear resistance was tested according to ISO 4649 standard; the dry and wet anti-slip test was tested according to ASTM D1894 standard. The test results are shown in Table 2.

[0086] Table 2 Performance test

[0087]

[0088]

[0089] It can be seen from the performance test data in Table 2 that, compared with comparative examples 1-3, the product embodiments 1-10 of the present invention have greatly improved in terms of wear resistance and wet anti-skid force.

[0090] 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 principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A wet-slip, wear-resistant thermoplastic polyurethane elastomer material, comprising the following components in percentage by weight, based on the total weight of components A) to E) being 100%: The general structural formula of the component D) acyclic heteroatom chain extender is as follows: in, 1≤n≤10, and n is an integer; R1 and R2 are independently selected from any one of OH and NH2; the component E) acyclic hetero nitrogen atom chain extender has the following general structure: wherein R3 and R4 are independently selected from any one of OH and NH2; The preparation method comprises the following steps: The polyol, polyisocyanate and small molecule diol chain extender are mixed evenly, and then the mixed materials are fed into a reactive twin-screw extruder, and an acyclic heterooxygen atom chain extender and an acyclic heteronitrogen atom chain extender are added. After reactive extrusion, underwater pelletizing and hopper drying, thermoplastic polyurethane elastomer particles are obtained.

2. The wet non-slip and wear-resistant thermoplastic polyurethane elastomer material according to claim 1, characterized in that: Based on the total mass of components A)-E) being 100%, the composition is prepared from the following components in percentage by weight:

3. The wet non-slip and wear-resistant thermoplastic polyurethane elastomer material according to claim 1, characterized in that: The number average molecular weight of the polyol in component A) is 800-4000 g / mol; and / or the polyol in component A) is selected from polyester polyol, polyether polyol or a combination thereof.

4. The wet non-slip and wear-resistant thermoplastic polyurethane elastomer material according to claim 1, characterized in that: The polyol of component A) is selected from polycaprolactone polyol, polycarbonate polyol or a combination thereof.

5. The wet non-slip and wear-resistant thermoplastic polyurethane elastomer material according to claim 1, characterized in that: The number average molecular weight of the polyol of component A) is 1000 to 3000 g / mol.

6. The wet non-slip and wear-resistant thermoplastic polyurethane elastomer material according to any one of claims 1 to 5, characterized in that: The polyisocyanate of component B) 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.

7. The wet non-slip and wear-resistant thermoplastic polyurethane elastomer material according to any one of claims 1 to 5, characterized in that: 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, methylpropylene glycol, methylpentanediol, 1,4-cyclohexanediol, neopentyl glycol, and terephthalic acid.

8. The wet non-slip and wear-resistant thermoplastic polyurethane elastomer material according to any one of claims 1 to 5, characterized in that: The temperature of the twin-screw extruder is between 120-250°C, the screw speed is 800-1200RPM, the pelletizing water temperature is 30-60°C, the drying temperature is 40-80°C, and the drying time is 30min-120min.

9. Use of the wet non-slip and wear-resistant thermoplastic polyurethane elastomer material according to any one of claims 1 to 8 in the fields of sole materials, blending modification, and industrial products.

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