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CN-122011487-A - Preparation process of supercritical foaming slippers

CN122011487ACN 122011487 ACN122011487 ACN 122011487ACN-122011487-A

Abstract

The invention relates to a preparation process of supercritical foaming slippers, which belongs to the technical field of foaming materials, and relates to a preparation process of supercritical foaming slippers, wherein a high-efficiency room-temperature self-repairing performance is given to materials by means of the cooperation of a hydrogen bond supermolecular network and a double dynamic structure of dynamic covalent bonds, a multistage hydrogen bond built in a polyurethane elastomer provides rapid and reversible intermolecular repairing power, a dynamic covalent bond introduced by a siloxane prepolymer realizes a stable broken bond reconnection effect, two types of dynamic bonds are uniformly dispersed and fully coupled by a high-temperature banburying process, the problems of agglomeration and phase separation are avoided, unexpected synergistic gain is formed by rapid response repairing of the hydrogen bond and long-acting stable repairing of the dynamic covalent bond, rapid healing of damage can be realized under the room-temperature condition without any external stimulus, and the retention rate of mechanical properties of repaired materials is greatly improved, and the service life of the slippers is remarkably prolonged.

Inventors

  • ZHANG CHENXI
  • ZHANG JINSONG

Assignees

  • 安徽拓驰鞋业股份有限公司

Dates

Publication Date
20260512
Application Date
20260409

Claims (10)

  1. 1. The preparation process of the supercritical foaming slipper is characterized by comprising the following steps: Step one, performing polycondensation reaction on phenylboronic acid and hydroxyl-terminated polydimethylsiloxane to obtain siloxane prepolymer; taking polycaprolactone triblock polyol as a soft segment, hexamethylene diisocyanate and ethylenediamine as hard segments, and polymerizing under the catalysis of a catalyst to obtain a polyurethane elastomer by end capping; and thirdly, carrying out high-temperature banburying and hot pressing on the polyurethane elastomer, the ethylene-vinyl acetate copolymer, the prepolymer containing siloxane, the carbon nano tube, the graphene and the zinc oxide to obtain a composite polyurethane material, carrying out supercritical foaming on the composite polyurethane material, and cooling and shaping to obtain the supercritical foaming slipper.
  2. 2. The process for preparing a pair of supercritical foaming slippers according to claim 1, wherein the specific preparation process of the siloxane prepolymer in the step one is as follows: Adding phenylboronic acid and absolute ethyl alcohol into a reaction kettle, stirring at 55-60 ℃ until the phenylboronic acid and the absolute ethyl alcohol are completely dissolved, adding hydroxyl-terminated polydimethylsiloxane, heating at 120-125 ℃ for 4-6 hours, and drying to obtain a prepolymer containing siloxane.
  3. 3. The process for preparing the supercritical foaming slipper according to claim 2, wherein the dosage ratio of the phenylboronic acid, the absolute ethyl alcohol and the hydroxyl-terminated polydimethylsiloxane is 50-60g:500-700mL:950-1150g.
  4. 4. The process for preparing supercritical foaming slippers according to claim 1, wherein the specific preparation process of the polyurethane elastomer in the second step is as follows: Adding polycaprolactone, hexamethylene diisocyanate, a catalyst and N, N-dimethylacetamide into a reaction kettle, reacting for 2-3 hours under the protection of nitrogen and at 75-80 ℃, reducing the temperature of a reaction system to 0 ℃ by using an ice water bath, slowly dripping ethylenediamine N, N-dimethylacetamide solution with the concentration of 0.20-0.38mol/L into the reaction kettle through a constant pressure dropping funnel, reacting for 6-8 hours at 0 ℃, finishing the reaction, adding anhydrous methanol under the condition of 75-77 ℃, blocking for 2-3 hours, precipitating in deionized water, filtering and drying to obtain the polyurethane elastomer.
  5. 5. The process for preparing supercritical foaming slipper according to claim 4, wherein the dosage ratio of polycaprolactone, hexamethylene diisocyanate, catalyst, N-dimethylacetamide, ethylenediamine N, N-dimethylacetamide solution and anhydrous methanol is 600-800g:112.1-152.1g:1.5-2.5mL:1.5-2.5L:2-3L:200-300mL.
  6. 6. The process for preparing supercritical foaming slipper according to claim 5, wherein the catalyst is any one of dibutyl tin dilaurate and bismuth isooctanoate.
  7. 7. The preparation process of the supercritical foaming slipper according to claim 1, wherein the specific preparation process of the composite polyurethane material in the third step is as follows: Adding polyurethane elastomer, ethylene-vinyl acetate copolymer and prepolymer containing siloxane into an internal mixer, setting the temperature at 185-190 ℃, mixing for 2-4min, adding carbon nano tube, continuing mixing for 2-4min, adding graphene and nano zinc oxide, mixing for 5-7min, placing the prepared sample at normal temperature for 24-26h, vulcanizing by a plate vulcanizing machine, setting the temperature at 190-200 ℃, preheating for 10-15min, hot-pressing for 3-5min, molding pressure at 10-12Mpa, placing the mold in a cold press for 5-7min, and cooling and shaping to obtain the composite polyurethane material.
  8. 8. The process for preparing supercritical foaming slipper according to claim 7, wherein the mass ratio of polyurethane elastomer, ethylene-vinyl acetate copolymer, siloxane-containing prepolymer, carbon nanotube, graphene and nano zinc oxide is 700-800:250-300:50-60:0-5:4-6:3-5.
  9. 9. The preparation process of the supercritical foaming slipper according to claim 1, wherein the specific preparation process of the supercritical foaming slipper in the third step is as follows: adding water and a composite polyurethane material into a high-pressure reaction kettle, sealing the kettle body, starting stirring, setting the rotating speed to 300-400r/min, introducing high-purity nitrogen, exhausting for 2-3 times, keeping the saturated time for 80-100min under the conditions of 138-140 ℃ and 12-14MPa to obtain a foaming embryo, rapidly transferring the foaming embryo into a special slipper foaming mold, rapidly closing the mold, rapidly releasing pressure to normal pressure within <1s, cooling and shaping to obtain the supercritical foaming slipper.
  10. 10. The process for preparing the supercritical foaming slipper according to claim 9, wherein the dosage ratio of the water to the composite polyurethane material is 3-5L:800-900g.

Description

Preparation process of supercritical foaming slippers Technical Field The invention belongs to the technical field of foaming materials, and relates to a preparation process of supercritical foaming slippers. Background As a necessary article for multiple scenes, the market demand is continuously increased along with the upgrade of consumption, and the performance requirements of consumers on environmental protection, comfort, durability and the like are increasingly improved, so that the iteration of the preparation process is promoted. The conventional chemical foaming process mainly used at present takes EVA, PVC and the like as raw materials and is matched with a chemical foaming agent for molding, but has the advantages of low cost and simple flow, but has various defects such as harmful byproducts, peculiar smell and environmental pollution during foaming, poor product performance caused by poor control of foam cells, high energy consumption, and difficult meeting of the requirements of energy conservation and emission reduction, and the market demand is difficult to meet. To solve the above problems, supercritical fluid foaming technology has become a central development direction. The technology takes supercritical carbon dioxide or nitrogen as a physical foaming agent, has no harmful byproducts, is free from zero emission of VOCs, can accurately regulate and control the cell structure, and remarkably improves the rebound resilience, the cushioning property and the durability of the slippers. The Chinese patent application with publication number of CN119859342A discloses a graphene modified EVA supercritical foaming sole or slipper and a preparation method thereof, wherein the foaming material comprises the following raw materials of ethylene-vinyl acetate copolymer, modified graphene, stearic acid, zinc stearate and a cross-linking agent, the prepared foaming sole or slipper is higher in strength and lighter in material, and the foaming material is endowed with more excellent flexibility and slow rebound resilience by compounding the modified graphene, the thermoplastic elastomer and EVA, and after the foaming material is made into a sole material, the sole has good rebound resilience and is softer and can obviously relieve plantar pressure under the condition of long-time use. According to the EVA supercritical foaming sole, an irreversible chemical crosslinking network is adopted, dynamic reversible bonds and self-repairing functional components are not introduced, physical enhancement is realized only by means of EVA and graphene, supercritical foaming is only a physical forming process, molecular rearrangement and bonding reconstruction capability required by self-repairing cannot be provided for materials, and the EVA supercritical foaming sole has no self-repairing performance as a whole. Disclosure of Invention The invention aims to provide a preparation process of supercritical foaming slippers, which constructs a reconfigurable cross-linked network by introducing dynamic reversible bonds and self-repairing components, realizes molecular rearrangement and bonding reconstruction by combining supercritical foaming, and solves the problems of no self-repairing, easy damage and short service life of the traditional scheme. The aim of the invention can be achieved by the following technical scheme: a preparation process of supercritical foaming slippers comprises the following steps: And step one, performing polycondensation reaction on phenylboronic acid and hydroxyl-terminated polydimethylsiloxane to obtain a siloxane prepolymer. And step two, polymerizing under the catalysis of a catalyst by taking polycaprolactone triblock polyol as a soft segment and hexamethylene diisocyanate and ethylenediamine as hard segments, and blocking to obtain the polyurethane elastomer. And thirdly, carrying out high-temperature banburying and hot pressing on the polyurethane elastomer, the ethylene-vinyl acetate copolymer, the prepolymer containing siloxane, the carbon nano tube, the graphene and the zinc oxide to obtain a composite polyurethane material, carrying out supercritical foaming on the composite polyurethane material, and cooling and shaping to obtain the supercritical foaming slipper. Further, the specific preparation process of the siloxane prepolymer is as follows: Adding phenylboronic acid and absolute ethyl alcohol into a reaction kettle, stirring at 55-60 ℃ until the phenylboronic acid and the absolute ethyl alcohol are completely dissolved, adding hydroxyl-terminated polydimethylsiloxane, heating at 120-125 ℃ for 4-6 hours, and drying to obtain a prepolymer containing siloxane. The ethanol is used as a cosolvent to promote the uniform dissolution of the phenylboronic acid, the raw material volatilization is avoided by low-temperature dissolution, the efficient polycondensation is realized by heating at 120-125 ℃, meanwhile, the ethanol and water molecules are removed, the small molecule residu