Wet non-slip wear-resistant thermoplastic polyurethane elastomer material and preparation method thereof

Abstract

The invention discloses a wet non-slip wear-resistant thermoplastic polyurethane elastomer material and a preparation method thereof. The polyester resin is prepared from the following raw materials: A) 45-85% of polyhydric alcohol; b) 10 to 45 percent of polyisocyanate; c) 1-20% of a micromolecular dihydric alcohol chain extender; d) 0.1 to 1.5 percent of an acyclic heterocyclic oxygen atom chain extender; and E) 0.1 to 0.5 percent of an acyclic nitrogen atom chain extender. According to the invention, an acyclic heteroatom chain is introduced at the reaction rear end to form a local hyperbranched structure, and the local hyperbranched structure is combined with multiple hydrogen bonds of polyurethane to form a high-density hydrogen bond network. When the dynamic hydrogen bond network is damaged on a damaged section, an activation layer is formed when the dynamic hydrogen bond network encounters water, rapid recombination and recovery of the hydrogen bond network between the sections are promoted through a water bridge, and the wet non-slip property and the wear resistance of the material are greatly improved. The method can be used in the fields of sole materials, blending modification, industrial products and the like.

Description

Technical Field

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

[0002] Thermoplastic polyurethane elastomer (TPU) is a type of linear polyurethane material that can be melted by heating, dissolved by solvents, has no or little crosslinking in its chemical structure, and has a glass transition temperature between rubber and plastic. Due to its wide hardness range, easy injection molding, high mechanical properties and other performance advantages, it is increasingly widely used in the field of footwear. However, although traditional TPU materials have good mechanical and wear resistance, their anti-slip properties, especially wet slip properties, are not ideal, which limits their application. Therefore, it is necessary to further upgrade the material performance.

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

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

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

[0006] Patent CN112724651 A obtains a thermoplastic polyurethane elastomer material with both anti-slip and wear-resistant properties by introducing metal sulfide, fatty acid amide-modified nano-calcium carbonate and MPMS-modified nano-silicon dioxide, but it also affects the 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 properties, 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 non-slip and wear-resistant thermoplastic polyurethane elastomer material, while ensuring the mechanical properties and processing properties of the material.

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

[0010] A wet non-slip and 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 small molecule diol chain extender; preferably 3-15%;

[0014] D) 0.1-1.5% acyclic heteroatom 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 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.

[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 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.

[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, methyl propanediol, methyl pentanediol, 1,4-cyclohexanediol, neopentyl glycol, and terephthalic acid; preferably one or more of ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, and 1,6-hexanediol.

[0024] The component D) acyclic heteroatom chain extender has the following general structure:

[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 component E) acyclic nitrogen atom chain extender has the following general structure:

[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 catalyst for the polymerization reaction.

[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 acyclic heterooxygen atom chain extender and 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 products.

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

[0038] The present invention introduces acyclic heteroatom chains to form a local hyperbranched structure through the reaction back end, which is combined with multiple hydrogen bonds of polyurethane to form a high-density hydrogen bond network. When the dynamic hydrogen bond network is destroyed on the damaged section, an activation layer will be formed when it encounters water, and the "water bridge" will promote the rapid reorganization and recovery of the hydrogen bond network between the sections, greatly improving the wet anti-slip and wear resistance of the material. It can be used in the fields of sole materials, blending modification, industrial products, etc. DETAILED DESCRIPTION

[0039] 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.

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

[0041] Main raw material sources

[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 butanediol), molecular weight 3000g / mol, Wanhua Chemical Group Co., Ltd.

[0046] PTMG (polytetramethylene glycol), 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) all come 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 all 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 extension crosslinking agent:

[0066] The structures of acyclic hetero nitrogen atom chain extension crosslinking agents 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, and its structure is as follows:

[0072]

[0073] Main test methods

[0074] The wear resistance is tested according to ISO 4649 standard; the dry and wet anti-slip test is tested according to ASTM D1894 standard

[0075] Examples 1-8

[0076] Example 1

[0077] A thermoplastic polyurethane elastomer, the components of which are measured by weight: 60 parts of polybutylene adipate, 7 parts of 1,4-butanediol, and 32 parts of diphenylmethane diisocyanate are uniformly mixed in a stirrer for reaction, and then 0.9 parts of D-1 chain extender and 0.1 parts of E-1 chain extender crosslinker are uniformly mixed in zones 7-9 and 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 pelletizing water temperature is 45°C, the drying temperature is 60°C, and the drying time is 2h.

[0078] Embodiment 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, product embodiments 1-10 of the present invention have greatly improved 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 principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A wet non-slip, wear-resistant thermoplastic polyurethane elastomer material, which is prepared from the following components in percentage by weight, based on the total mass of component AE being 100%: A) polyol 45-85%, preferably 60-80%; B) polyisocyanate 10-45%; preferably 15-35%; C) 1-20% of small molecule diol chain extender; preferably 3-15%; D) 0.1-1.5% acyclic heteroatom chain extender; preferably 0.3-1%; E) Acyclic hetero nitrogen atom chain extender 0.1-0.5%; preferably 0.1-0.3%.

2. 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 800-4000 g / mol, preferably 1000-3000 g / mol; and / or the polyol of component A) is selected from polyester polyol, polyether polyol, polycaprolactone polyol, polycarbonate polyol or a combination thereof.

3. The wet non-slip and wear-resistant thermoplastic polyurethane elastomer material according to claim 1 or 2, 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; 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.

4. The wet non-slip and wear-resistant thermoplastic polyurethane elastomer material according to any one of claims 1 to 3, 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, methyl propanediol, methyl pentanediol, 1,4-cyclohexanediol, neopentyl glycol, and terephthalic acid; preferably one or more of ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, and 1,6-hexanediol.

5. The wet non-slip and wear-resistant thermoplastic polyurethane elastomer material according to any one of claims 1 to 4, characterized in that: The component D) acyclic heteroatom chain extender has the following general structure: Wherein, 1≤n≤10, and n is an integer; R1 and R2 are independently selected from any one of OH and NH2.

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 component E) acyclic nitrogen atom chain extender has the following general structure: Wherein, R3 and R4 are independently selected from any one of OH and NH2.

7. The method for preparing the wet non-slip and wear-resistant thermoplastic polyurethane elastomer material according to any one of claims 1 to 6, characterized in that: The 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 acyclic heterooxygen atom chain extender and acyclic heteronitrogen atom chain extender cross-linker are added. After reactive extrusion, underwater pelletizing and hopper drying, thermoplastic polyurethane elastomer particles are obtained.

8. The preparation method according to claim 7, characterized in that: 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.

9. Application of the wet anti-skid and wear-resistant thermoplastic polyurethane elastomer material according to any one of claims 1 to 6 or the wet anti-skid and wear-resistant thermoplastic polyurethane elastomer material prepared by the preparation method according to claim 7 or 8 in the fields of sole materials, blending modification, and industrial products.

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