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CN-122011330-A - Micro-crosslinking polyurea polyurethane, application method and product thereof

CN122011330ACN 122011330 ACN122011330 ACN 122011330ACN-122011330-A

Abstract

The invention provides micro-crosslinking polyurea polyurethane, an application method thereof and a product thereof, wherein the micro-crosslinking polyurea polyurethane comprises a first component and a second component, the first component is polyurea polyurethane base material prepared by polymerization reaction of diisocyanate, prepolymer dihydric alcohol, dihydric alcohol chain extender and diamine chain extender, the second component is polyisocyanate compounds comprising at least one of HDI trimer, TDI trimer, IPDI trimer and triphenylmethane triisocyanate, the first component and the second component are uniformly mixed in an organic solvent and then spontaneously undergo micro-crosslinking/self-curing reaction to form the micro-crosslinking polyurea polyurethane, and the mass ratio of the second component is 0.5-5% of the mass of the first component. And (3) uniformly mixing the first component and the second component, coating the mixture on the surface-treated midsole within 2 hours, and drying the midsole to obtain the outsole after the surface coating is solidified. The sports shoe outsole made of the micro-crosslinked polyurea polyurethane can show light weight, high wear resistance and high anti-slip property.

Inventors

  • WANG XU
  • CUI KEJIAN
  • YI XIAOLIN
  • SHI FEI
  • XU ZONGCHAO
  • XU JIANGUANG

Assignees

  • 李宁体育科技(北京)有限公司

Dates

Publication Date
20260512
Application Date
20260309

Claims (10)

  1. 1. The micro-crosslinking polyurea polyurethane is characterized by comprising a first component and a second component, wherein the first component is a polyurea polyurethane base material prepared by polymerization of diisocyanate, prepolymer dihydric alcohol, dihydric alcohol chain extender and diamine chain extender; the first component and the second component are uniformly mixed in an organic solvent to form a mixed solution, and the mixed solution spontaneously undergoes micro-crosslinking/self-curing reaction to form micro-crosslinking polyurea polyurethane, wherein the mass ratio of the second component is 0.5-5% of the mass of the first component.
  2. 2. The micro-crosslinked polyurea urethane of claim 1, wherein the organic solvent is at least one of N, N-dimethylformamide, N-dimethylacetamide, tetrahydrofuran, pyridine, and carbon tetrachloride.
  3. 3. The micro-crosslinked polyurea-polyurethane according to claim 1, wherein the solid content of the mixed solution is controlled within 5-30% so as to facilitate the curing of the coating on the carrier to form the micro-crosslinked polyurea-polyurethane.
  4. 4. The micro-crosslinked polyurea urethane of claim 1, wherein the diisocyanate is an aromatic diisocyanate or an aliphatic diisocyanate, the aromatic diisocyanate comprises at least one of methylene diphenyl diisocyanate, toluene diisocyanate, p-phenylene diisocyanate, and xylylene diisocyanate, and the aliphatic diisocyanate comprises at least one of hexamethylene diisocyanate, methylene dicyclohexyl diisocyanate, isophorone diisocyanate, and cyclohexane dimethylene diisocyanate.
  5. 5. The micro-crosslinked polyurea polyurethane of claim 1, wherein the glycol prepolymer is at least one of polyethylene adipate, polypropylene adipate, polybutylene adipate, polyepsilon caprolactone diol, polycarbonate diol, polyethylene oxide homo polyether diol, polypropylene oxide homo polyether diol, polytetrahydrofuran ether diol.
  6. 6. The micro-crosslinked polyurea polyurethane of claim 1, wherein the glycol chain extender is at least one of ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol.
  7. 7. The micro-crosslinked polyurea urethane of claim 1, wherein the diamine chain extender is at least one of ethylenediamine, butanediamine, hexamethylenediamine, isophoronediamine, 3, 5-dimethylthiotoluenediamine, diethyltoluenediamine, 1, 3-propanediol bis (4-aminobenzoate), 4' -methylenebis (2-ethyl) aniline, bis-sec-butylamino-diphenylmethane.
  8. 8. The micro cross-linked polyurea-polyurethane according to any one of claims 1 to 7, wherein the molar ratio of diisocyanate, diol prepolymer and diol/amine chain extender is further 10:2 to 8: 8~2, i.e. the molar amount of diisocyanate is the sum of the molar amounts of diol prepolymer and diol/amine chain extender, wherein the molar ratio of diol prepolymer and diol/amine chain extender is between 1:4 and 4:1, and the molar ratio of diol chain extender to diamine chain extender is between 3:1 and 1:3.
  9. 9. A method of using the micro-crosslinked polyurea-polyurethane of claim 8, comprising the steps of: S1, weighing diisocyanate, prepolymer dihydric alcohol, dihydric alcohol chain extender and diamine chain extender according to a proportion, preparing a first component through polymerization reaction, and drying and then preserving for later use; S2, sequentially treating the surface of the midsole by using a cleaning agent and a surfactant, and ensuring that the next operation is performed within 12 hours; s3, dissolving the first component in an organic solvent, adding the second component after the first component is completely dissolved, further uniformly mixing, and coating the second component on the midsole after the surface treatment in the step S2 within 2 hours; And S4, placing the coated midsole in an oven, and transferring to a ventilation place until the solvent is completely volatilized after the surface coating is solidified, so as to finish the manufacture of the outsole.
  10. 10. An article of footwear characterized in that the sole is made by the method of application of the micro-crosslinked polyurea polyurethane described above.

Description

Micro-crosslinking polyurea polyurethane, application method and product thereof Technical Field The invention relates to the technical field of polyurethane, in particular to micro-crosslinking polyurea polyurethane, an application method thereof and a product thereof. Background Polyurethane (PU) is a polymer material which is produced by polymerization reaction of polyol, isocyanate and chain extender and takes urethane bond as core repeated functional group. PU has the characteristics of high strength, high toughness, wear resistance, oil resistance, ozone resistance and the like, and is widely applied to the outsole of sports shoes, thereby providing excellent slip resistance and wear resistance for the outsole. Thermoplastic polyurea polyurethanes refer to thermoplastic polyurethanes containing allophanate linkages in the molecular chain, which have higher mechanical strength, abrasion resistance, and chemical resistance than typical thermoplastic polyurethanes. Wear resistance is one of the key parameters for evaluating whether the outsole function and the quality of the outsole are excellent, determines the life cycle and consumption public praise of the sports shoes, and is the hot spot direction of the research and development of various brands of sports shoes. In the face of the same wear-resisting requirement, the wear resistance of the outsole is greatly improved, and the thickness of the outsole can be thinned, so that the weight of the sports shoes is reduced, and further the sports experience of consumers and the sports performance of professional runners are improved. In addition, during relatively strenuous activities such as long distance running, basketball, table tennis and badminton, etc., or during hot summer hours, the friction between the sole and the ground may cause the outsole to heat and heat up, even up to 60 ℃ and above, which also creates a high thermal wear resistance requirement for the outsole material. Patent US 2020/015489 A1 discloses a coated article comprising an intumescent thermoplastic polyurethane, the polyurethaneurea solution of which is prepared and applied to a substrate by brushing, spraying, rolling, slot coating, dipping and/or printing to form a protective coating. The polyurethane urea of the technology comprises a polycarbonate structural unit (polycarbonate diol is used as a polyol), can improve the adhesiveness between a polyurethane urea coating and the surface of the expansion TPU, has enough flexibility, and can still maintain high bonding strength when the expansion TPU is bent. While this technique indicates that it can be applied to soles, it is functionally more decorative and does not focus on the wear resistance of the coating, let alone the thermal wear resistance. The patent application CN 111356713A discloses a method for forming an elastomer polyurethane product, wherein the wear resistance of the product is better, the isocyanate component and the isocyanate reactive component are respectively prepared in the preparation process, and a thixotropic agent is added to directly generate the polyurethane product through exothermic reaction/self-curing reaction (the coating on a carrier is required to be completed before the complete curing), the exothermic reaction is more severe, the generated heat is higher, the interval temperature is higher than 100 ℃, and if the product is coated on a low-density insole in a proper viscosity range (namely, when the carrier matrix is a low-density foaming shoe material), the higher reaction temperature can cause the defects of wrinkling, local shrinkage and the like on the surface of the low-density shoe material, so that the use of the product on the low-density sole is limited, and the weight reduction of the whole shoe is not facilitated. In addition, the direct and severe reaction of the isocyanate component and the isocyanate-reactive component is also unfavorable for the control of the degree of crosslinking, and the finally obtained product tends to have higher degree of crosslinking, better wear resistance, poorer damping and poor slip resistance. Therefore, the coatable thermoplastic polyurethane material with wear resistance and slip resistance is provided, and is suitable for coating the middle sole of the low-density shoe, and the sole has better thermal wear resistance (the loss of the sole under the condition of severe sports is reduced, the service life is prolonged) and slip resistance, has more practical significance, and is beneficial to improving the sports experience of the ultra-light sports shoe. Disclosure of Invention The invention provides micro-crosslinked polyurea polyurethane, an application method and a product thereof, and aims to solve the problems that the coating polyurethane sole in the prior art is poor in thermal wear resistance and difficult to have wear resistance and slip resistance, and the like. The technical scheme of the invention is as follows: The micro-crosslin