WO2023240670A1 - Thermoplastic elastomer material for automotive foot mat and preparation method therefor - Google Patents

Thermoplastic elastomer material for automotive foot mat and preparation method therefor Download PDF

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Publication number
WO2023240670A1
WO2023240670A1 PCT/CN2022/100782 CN2022100782W WO2023240670A1 WO 2023240670 A1 WO2023240670 A1 WO 2023240670A1 CN 2022100782 W CN2022100782 W CN 2022100782W WO 2023240670 A1 WO2023240670 A1 WO 2023240670A1
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polyether polyol
component
pressure
molecular weight
thermoplastic elastomer
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PCT/CN2022/100782
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French (fr)
Chinese (zh)
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宋伟杰
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宋伟杰
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • C08J9/08—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing carbon dioxide
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    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K3/34—Silicon-containing compounds
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/02—CO2-releasing, e.g. NaHCO3 and citric acid
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/06—CO2, N2 or noble gases
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/08—Supercritical fluid
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    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/18—Binary blends of expanding agents
    • C08J2203/184—Binary blends of expanding agents of chemical foaming agent and physical blowing agent, e.g. azodicarbonamide and fluorocarbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C08J2375/08—Polyurethanes from polyethers
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
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    • C08K2003/265—Calcium, strontium or barium carbonate
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    • C08K2201/00—Specific properties of additives
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

Definitions

  • the present invention relates to the technical field of automobile decoration, and in particular to a thermoplastic elastomer material used for automobile floor mats and a preparation method thereof.
  • Car floor mats are car interior decorations and are used to keep the interior of the car clean.
  • Car floor mats are car interior parts that integrate the five main functions of water absorption, dust collection, decontamination, sound insulation, and host blanket protection. Car floor mats absorb water, vacuum and decontaminate, which can effectively prevent the residual moisture and dirt on the soles from sliding between the clutch, brake, accelerator, etc., effectively avoiding safety hazards and reducing the possibility of the interior being contaminated and damaged.
  • the car floor mats currently on the market are generally plastic floor mats.
  • the wear resistance of the plastic sheets is not good, the grade is not high, and the glue has an odor, which affects the breathing environment.
  • the production of rubber foot pads requires high pressure, cumbersome processes, and long cycle times.
  • its color is not easy to adjust. At the same time, it is easy to harden in winter, which greatly reduces the comfort of use.
  • thermoplastic elastomer material polyurethane has the characteristics of light weight, good low-temperature flexibility, safety and high vibration absorption, and its application in automobile floor mat materials has attracted attention. How to apply polyurethane to car floor mats and prepare a car floor mat with good wear resistance, high resilience and good thermal insulation effect has excellent application prospects.
  • the purpose of the present invention is to propose a thermoplastic elastomer material for automobile floor mats and a preparation method thereof in order to solve the shortcomings existing in the prior art.
  • thermoplastic elastomer material used for automobile floor mats including component A, component B, and component C;
  • Component A includes: 30-50 parts of toluene diisocyanate, 10-30 parts of diphenylmethane diisocyanate, 20-70 parts of polyether polyol I;
  • Polyether polyol I includes: a polyether polyol with a molecular weight of 4000 and a polyether polyol with a molecular weight of 6000.
  • the weight ratio of the polyether polyol with a molecular weight of 4000 and the polyether polyol with a molecular weight of 6000 is 10:1.
  • a polyether polyol with a molecular weight of 4000 has a functionality of 2
  • a polyether polyol with a molecular weight of 6000 has a functionality of 3;
  • Component B includes: 20-40 parts of polyether polyol II, 1-5 parts of chain extender, 1-3 parts of cross-linking agent, 5-15 parts of filler, 0.1-1 part of catalyst, and 1-2 parts of pigment;
  • the molecular weight of polyether polyol II is 1000 and its functionality is 3;
  • Component C includes: 10-15 parts of water-loaded silicon carbide skeleton.
  • the water-loaded silicon carbide skeleton is prepared by the following steps: polystyrene microspheres are used as the skeleton, silicon carbide nanowires are coated on the surface of the polystyrene microspheres, and the polystyrene microspheres are removed by calcining in an air atmosphere, and then Loaded with water.
  • the specific preparation steps of the water-loaded silicon carbide skeleton are as follows: disperse the silicon carbide nanowires in anhydrous ethanol, ultrasonic dispersion under stirring, the ultrasonic frequency is 10-20 kHz, add polystyrene microspheres and continue ultrasonic treatment. , vacuum filtration, drying at 100-120°C for 2-4h, calcining in air atmosphere at 450-550°C for 10-20min, crushing and sieving, adding water and stirring evenly to obtain a water-loaded silicon carbide skeleton.
  • the mass ratio of silicon carbide nanowires, polystyrene microspheres, and water is 5-10:5-10:1-4.
  • the polystyrene microspheres have an average diameter of 10-50 ⁇ m.
  • the density of silicon carbide nanowires is 3-3.5g/cm 3 , the diameter is 0.1-0.5 ⁇ m, and the length is 10-50 ⁇ m.
  • the chain extender is at least one of lysine, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, 1,4-butanediamine and ethylenediamine.
  • the cross-linking agent is at least one of glycerol, diethanolamine, triethanolamine, and trimethylolpropane.
  • the filler is nanometer calcium carbonate
  • the catalyst is an organic bismuth catalyst
  • thermoplastic elastomer material for automobile floor mats includes the following steps:
  • component A and component B are mixed and added into a high-pressure reaction kettle, and the pressure is maintained in a high-pressure state for 10-20 minutes before the pressure is released.
  • the nucleation speed is fast and the number of foams is large, and then the pressure is increased. Effectively control the uniformity of the foam, and then perform pressure relief to promote bubble growth.
  • the resulting foam pore size is 10-150 ⁇ m, and the foam pore size is evenly distributed, thereby reducing the thermal conductivity of the product, improving the thermal insulation performance, and having good stability.
  • substances such as foam stabilizers. ;
  • component C polystyrene microspheres are used as templates, and the polystyrene microspheres are removed by calcining in a high-temperature air atmosphere to obtain a three-dimensional silicon carbide skeleton with a honeycomb hole structure, which has high adsorption and loading strength for water.
  • the water slowly overflows under high pressure and reacts with toluene diisocyanate to form gas.
  • Cooperate with the subsequent pressure relief, pressure increase, and pressure relief process to effectively avoid bubbles.
  • the phenomenon of pore merger and cell collapse, and the silicon carbide skeleton is evenly dispersed in the system to form a skeleton structure, which not only has excellent wear resistance, but also cooperates with the porous structure to effectively improve the resilience performance.
  • the present invention uses toluene diisocyanate and diphenylmethane diisocyanate as main materials and polyether polyol I to synthesize a prepolymer with an NCO content of 3%, and then sequentially mixes it with polyether polyol II and loaded water.
  • the water-loaded silicon carbide skeleton has extremely high bonding strength and effectively forms a wear-resistant skeleton. While increasing the wear-resistant strength, it also has excellent rebound performance.
  • the foot pads have the advantages of plastic and rubber materials. , good mechanical properties, resistant to permanent compression deformation and long service life.
  • thermoplastic elastomer material used for automobile floor mats including component A, component B, and component C;
  • Component A includes: 30kg of toluene diisocyanate, 10kg of diphenylmethane diisocyanate, 20kg of polyether polyol I;
  • Polyether polyol I includes: a polyether polyol with a molecular weight of 4000 and a polyether polyol with a molecular weight of 6000.
  • the weight ratio of the polyether polyol with a molecular weight of 4000 and the polyether polyol with a molecular weight of 6000 is 10:1. ;
  • a polyether polyol with a molecular weight of 4000 has a functionality of 2, and a polyether polyol with a molecular weight of 6000 has a functionality of 3;
  • Component B includes: polyether polyol II 20kg, lysine 0.2kg, 1,6-hexanediol 0.8kg, glycerin 0.3kg, diethanolamine 0.7kg, nano calcium carbonate 5kg, bismuth laurate 0.1kg, pigment 1kg ;
  • the molecular weight of polyether polyol II is 1000 and its functionality is 3;
  • Component C includes: 10kg of water-loaded silicon carbide skeleton.
  • the water-loaded silicon carbide skeleton is prepared by the following steps: 5kg of silicon carbide nanowires with a density of 3-3.5g/cm 3 , a diameter of 0.1-0.5 ⁇ m, and a length of 10-50 ⁇ m are dispersed in 20kg of absolute ethanol, and stirred Under ultrasonic dispersion for 10 minutes, the stirring speed is 50r/min, the ultrasonic frequency is 10kHz, add 5kg polystyrene microspheres with an average diameter of 10-50 ⁇ m, continue ultrasonic treatment for 1h, vacuum filtration, dry at 100°C for 2h, and add to the horse In a furnace, calcined in an air atmosphere at 450°C for 10 minutes, crushed, passed through an 80-mesh sieve, and 1 kg of water was added and stirred evenly to obtain a water-loaded silicon carbide skeleton.
  • thermoplastic elastomer material for automobile floor mats includes the following steps:
  • thermoplastic elastomer material used for automobile floor mats including component A, component B, and component C;
  • Component A includes: 50kg of toluene diisocyanate, 30kg of diphenylmethane diisocyanate, 70kg of polyether polyol I;
  • Polyether polyol I includes: a polyether polyol with a molecular weight of 4000 and a polyether polyol with a molecular weight of 6000.
  • the weight ratio of the polyether polyol with a molecular weight of 4000 and the polyether polyol with a molecular weight of 6000 is 10:2. ;
  • a polyether polyol with a molecular weight of 4000 has a functionality of 2, and a polyether polyol with a molecular weight of 6000 has a functionality of 3;
  • Component B includes: polyether polyol II 40kg, diethylene glycol 4kg, 1,4-butanediamine 1kg, trimethylolpropane 3kg, nano calcium carbonate 15kg, bismuth laurate 1kg, pigment 2kg;
  • the molecular weight of polyether polyol II is 1000 and its functionality is 3;
  • Component C includes: 15kg of water-loaded silicon carbide skeleton.
  • the water-loaded silicon carbide skeleton is prepared by the following steps: 10kg of silicon carbide nanowires with a density of 3-3.5g/cm 3 , a diameter of 0.1-0.5 ⁇ m, and a length of 10-50 ⁇ m are dispersed in 40kg of absolute ethanol, and stirred Under ultrasonic dispersion for 20 minutes, the stirring speed is 100r/min, the ultrasonic frequency is 20kHz, add 10kg polystyrene microspheres with an average diameter of 10-50 ⁇ m, continue ultrasonic treatment for 2h, vacuum filtration, dry at 120°C for 4h, and add to the horse In a furnace, calcined in an air atmosphere at 550°C for 20 minutes, crushed, passed through a 100-mesh sieve, and 4kg of water was added and stirred evenly to obtain a water-loaded silicon carbide skeleton.
  • thermoplastic elastomer material for automobile floor mats includes the following steps:
  • thermoplastic elastomer material used for automobile floor mats including component A, component B, and component C;
  • Component A includes: 35kg of toluene diisocyanate, 25kg of diphenylmethane diisocyanate, 30kg of polyether polyol I;
  • Polyether polyol I includes: a polyether polyol with a molecular weight of 4000 and a polyether polyol with a molecular weight of 6000.
  • the weight ratio of the polyether polyol with a molecular weight of 4000 and the polyether polyol with a molecular weight of 6000 is 10:1.7 ;
  • a polyether polyol with a molecular weight of 4000 has a functionality of 2, and a polyether polyol with a molecular weight of 6000 has a functionality of 3;
  • Component B includes: polyether polyol II 25kg, 1,4-butanediol 3.5kg, ethylenediamine 0.5kg, triethanolamine 1.5kg, nano calcium carbonate 8kg, bismuth laurate 0.8kg, pigment 1.3kg;
  • the molecular weight of polyether polyol II is 1000 and its functionality is 3;
  • Component C includes: 12kg of water-loaded silicon carbide skeleton.
  • the water-loaded silicon carbide skeleton is prepared by the following steps: 8kg of silicon carbide nanowires with a density of 3-3.5g/cm 3 , a diameter of 0.1-0.5 ⁇ m, and a length of 10-50 ⁇ m are dispersed in 25kg of absolute ethanol, and stirred Under ultrasonic dispersion for 18 minutes, the stirring speed is 60r/min, the ultrasonic frequency is 18kHz, add 6kg polystyrene microspheres with an average diameter of 10-50 ⁇ m, continue ultrasonic treatment for 100min, vacuum filtration, dry at 105°C for 3.5h, add to In a muffle furnace, calcined in an air atmosphere at 480°C for 18 minutes, crushed, passed through an 85-mesh sieve, and 3kg of water was added and stirred evenly to obtain a water-loaded silicon carbide skeleton.
  • thermoplastic elastomer material for automobile floor mats includes the following steps:
  • thermoplastic elastomer material used for automobile floor mats including component A, component B, and component C;
  • Component A includes: 45kg of toluene diisocyanate, 15kg of diphenylmethane diisocyanate, 60kg of polyether polyol I;
  • Polyether polyol I includes: a polyether polyol with a molecular weight of 4000 and a polyether polyol with a molecular weight of 6000.
  • the weight ratio of the polyether polyol with a molecular weight of 4000 and the polyether polyol with a molecular weight of 6000 is 10:1.3 ;
  • a polyether polyol with a molecular weight of 4000 has a functionality of 2, and a polyether polyol with a molecular weight of 6000 has a functionality of 3;
  • Component B includes: polyether polyol II 35kg, lysine 1kg, 1,4-butanediol 1kg, glycerin 2.5kg, nano calcium carbonate 12kg, bismuth laurate 0.2kg, pigment 1.7kg;
  • the molecular weight of polyether polyol II is 1000 and its functionality is 3;
  • Component C includes: 14kg of water-loaded silicon carbide skeleton.
  • the water-loaded silicon carbide skeleton is prepared by the following steps: 6 kg of silicon carbide nanowires with a density of 3-3.5 g/cm 3 , a diameter of 0.1-0.5 ⁇ m, and a length of 10-50 ⁇ m are dispersed in 35 kg of absolute ethanol, and stirred Under ultrasonic dispersion for 12 minutes, the stirring speed is 80r/min, the ultrasonic frequency is 12kHz, add 8kg polystyrene microspheres with an average diameter of 10-50 ⁇ m, continue ultrasonic treatment for 80min, vacuum filtration, dry at 115°C for 2.5h, add to In a muffle furnace, calcined in an air atmosphere at 520°C for 12 minutes, crushed, passed through a 95-mesh sieve, and 2kg of water was added and stirred evenly to obtain a water-loaded silicon carbide skeleton.
  • thermoplastic elastomer material for automobile floor mats includes the following steps:
  • thermoplastic elastomer material used for automobile floor mats including component A, component B, and component C;
  • Component A includes: 40kg of toluene diisocyanate, 20kg of diphenylmethane diisocyanate, 45kg of polyether polyol I;
  • Polyether polyol I includes: a polyether polyol with a molecular weight of 4000 and a polyether polyol with a molecular weight of 6000.
  • the weight ratio of the polyether polyol with a molecular weight of 4000 and the polyether polyol with a molecular weight of 6000 is 10:1.5. ;
  • a polyether polyol with a molecular weight of 4000 has a functionality of 2, and a polyether polyol with a molecular weight of 6000 has a functionality of 3;
  • Component B includes: polyether polyol II 30kg, diethylene glycol 3kg, diethanolamine 2kg, nano calcium carbonate 10kg, bismuth laurate 0.5kg, pigment 1.5kg;
  • the molecular weight of polyether polyol II is 1000 and its functionality is 3;
  • Component C includes: 12kg of water-loaded silicon carbide skeleton.
  • the water-loaded silicon carbide skeleton is prepared by the following steps: 7kg of silicon carbide nanowires with a density of 3-3.5g/cm 3 , a diameter of 0.1-0.5 ⁇ m, and a length of 10-50 ⁇ m are dispersed in 30kg of absolute ethanol, and stirred Under ultrasonic dispersion for 15 minutes, the stirring speed is 70r/min, the ultrasonic frequency is 15kHz, add 7kg polystyrene microspheres with an average diameter of 10-50 ⁇ m, continue ultrasonic treatment for 90min, vacuum filtration, dry at 110°C for 3h, and add to horse In a furnace, calcined in an air atmosphere at 500°C for 15 minutes, crushed, passed through a 90-mesh sieve, and 2.5kg of water was added and stirred evenly to obtain a water-loaded silicon carbide skeleton.
  • thermoplastic elastomer material for automobile floor mats includes the following steps:
  • thermoplastic elastomer material used for automobile floor mats including component A, component B, and component C;
  • Component A includes: 40kg of toluene diisocyanate, 20kg of diphenylmethane diisocyanate, 45kg of polyether polyol I;
  • Polyether polyol I includes: a polyether polyol with a molecular weight of 4000 and a polyether polyol with a molecular weight of 6000.
  • the weight ratio of the polyether polyol with a molecular weight of 4000 and the polyether polyol with a molecular weight of 6000 is 10:1.5. ;
  • a polyether polyol with a molecular weight of 4000 has a functionality of 2, and a polyether polyol with a molecular weight of 6000 has a functionality of 3;
  • Component B includes: polyether polyol II 30kg, diethylene glycol 3kg, diethanolamine 2kg, nano calcium carbonate 10kg, bismuth laurate 0.5kg, pigment 1.5kg;
  • the molecular weight of polyether polyol II is 1000 and its functionality is 3;
  • Component C includes: water, where the added amount of water is the same as the water content in the water-loaded silicon carbide skeleton in Example 5.
  • thermoplastic elastomer material for automobile floor mats includes the following steps:
  • thermoplastic elastomer material used for automobile floor mats including component A, component B, and component C;
  • Component A includes: 40kg of toluene diisocyanate, 20kg of diphenylmethane diisocyanate, 45kg of polyether polyol I;
  • Polyether polyol I includes: a polyether polyol with a molecular weight of 4000 and a polyether polyol with a molecular weight of 6000.
  • the weight ratio of the polyether polyol with a molecular weight of 4000 and the polyether polyol with a molecular weight of 6000 is 10:1.5. ;
  • a polyether polyol with a molecular weight of 4000 has a functionality of 2, and a polyether polyol with a molecular weight of 6000 has a functionality of 3;
  • Component B includes: polyether polyol II 30kg, diethylene glycol 3kg, diethanolamine 2kg, nano calcium carbonate 10kg, bismuth laurate 0.5kg, pigment 1.5kg;
  • the molecular weight of polyether polyol II is 1000 and its functionality is 3;
  • Component C includes: water-loaded silicon carbide skeleton.
  • the water-loaded silicon carbide skeleton is prepared by the following steps: 7kg of silicon carbide nanowires with a density of 3-3.5g/cm 3 , a diameter of 0.1-0.5 ⁇ m, and a length of 10-50 ⁇ m are dispersed in 30kg of absolute ethanol, and stirred Under ultrasonic dispersion for 15 minutes, the stirring speed is 70r/min, the ultrasonic frequency is 15kHz, add 7kg polystyrene microspheres with an average diameter of 10-50 ⁇ m, continue ultrasonic treatment for 90min, vacuum filtration, dry at 110°C for 3h, and add to horse In a furnace, calcined in an air atmosphere at 500°C for 15 minutes, crushed, passed through a 90-mesh sieve, and 2.5kg of water was added and stirred evenly to obtain a water-loaded silicon carbide skeleton.
  • thermoplastic elastomer material for automobile floor mats includes the following steps:
  • thermoplastic elastomer materials for automobile floor mats obtained in Example 5 and Comparative Examples 1-2 were subjected to comparative performance tests, as follows:
  • Example 5 Comparative example 1 Comparative example 2 Testing standards Density, g/cm 3 0.68 0.79 0.71 / Shore A hardness 52 66 57 GB/T 531-2008 Breaking strength, Mpa 5.5 4.0 4.9 GB/T 10654-2001 Elongation at break, % 793 603 684 GB/T 10654-2001
  • Example 5 Comparative example 1 Comparative example 2 Akron wear volume, cm 3 0.11 0.36 0.23 Impact rebound, % 57 44 51 Thermal conductivity, mW/(m ⁇ K) 15.8 18.8 17.9

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Abstract

Disclosed is a thermoplastic elastomer material for an automotive foot mat, which material comprises a component A, a component B and a component C, wherein the component A comprises, by weight, 30-50 of toluene diisocynate, 10-30 of diphenylmethane diisocyanate, and 20-70 of a polyether polyol I, which comprises a polyether polyol having a molecular weight of 4000 and a polyether polyol having a molecular weight of 6000, the weight ratio of the polyether polyol having a molecular weight of 4000 to the polyether polyol having a molecular weight of 6000 being 10 : 1-2, the degree of functionality of the polyether polyol having a molecular weight of 4000 being 2, and the degree of functionality of the polyether polyol having a molecular weight of 6000 being 3; the component B comprises, by weight, 20-40 of a polyether polyol II, 1-5 of a chain extender, 1-3 of a cross-linking agent, 5-15 of a filler, 0.1-1 of a catalyst, and 1-2 of a pigment, the degree of functionality of the polyether polyol II being 3; and the component C comprises, by weight, 10-15 of a water-loaded silicon carbide skeleton.

Description

用于汽车脚垫的热塑性弹性体材料及其制备方法Thermoplastic elastomer material for automobile floor mats and preparation method thereof 技术领域Technical field
本发明涉及汽车装饰技术领域，尤其涉及一种用于汽车脚垫的热塑性弹性体材料及其制备方法。The present invention relates to the technical field of automobile decoration, and in particular to a thermoplastic elastomer material used for automobile floor mats and a preparation method thereof.
背景技术Background technique
随着人民生活水平的提高，汽车逐渐走入各个家庭，人们对汽车的要求也越来越高。汽车脚垫属于汽车内部装饰品，用于保护车内洁净。With the improvement of people's living standards, cars have gradually entered every family, and people's requirements for cars are getting higher and higher. Car floor mats are car interior decorations and are used to keep the interior of the car clean.
汽车脚垫是集吸水、吸尘、去污、隔音、保护主机毯五大主要功能为一体的汽车内饰零部件。汽车脚垫吸水、吸尘、去污，可以有效防止鞋底残留的水分、脏物与离合器、制动器、油门等间的滑动，有效避免安全隐患，降低内饰被污染和损坏的可能性。Car floor mats are car interior parts that integrate the five main functions of water absorption, dust collection, decontamination, sound insulation, and host blanket protection. Car floor mats absorb water, vacuum and decontaminate, which can effectively prevent the residual moisture and dirt on the soles from sliding between the clutch, brake, accelerator, etc., effectively avoiding safety hazards and reducing the possibility of the interior being contaminated and damaged.
目前市场上出现的汽车脚垫一般为塑料脚垫，塑料片的耐磨性能不好，档次不高，胶水有气味，影响呼吸环境。而橡胶脚垫生产所需的压力大，工艺繁琐，周期长，而且其颜色不易调配，同时冬天容易变硬，使用舒适性大打折扣。The car floor mats currently on the market are generally plastic floor mats. The wear resistance of the plastic sheets is not good, the grade is not high, and the glue has an odor, which affects the breathing environment. However, the production of rubber foot pads requires high pressure, cumbersome processes, and long cycle times. Moreover, its color is not easy to adjust. At the same time, it is easy to harden in winter, which greatly reduces the comfort of use.
目前，随着汽车制造业的迅猛发展，汽车脚垫的需求量也迅速上涨，对其舒适性、耐磨性、回弹性、保温性的要求也越来越高。热塑性弹性体材料聚氨酯具有质量轻、低温柔韧性好、安全性及吸振性高等特点，在汽车脚垫材料中的应用受到关注。目前如何将聚氨酯应用于汽车脚垫，并制备一种耐磨性好、回弹性高、保温效果好的汽车脚垫，具有极好的应用前景。At present, with the rapid development of the automobile manufacturing industry, the demand for automobile floor mats is also rising rapidly, and the requirements for comfort, wear resistance, resilience, and heat preservation are also getting higher and higher. The thermoplastic elastomer material polyurethane has the characteristics of light weight, good low-temperature flexibility, safety and high vibration absorption, and its application in automobile floor mat materials has attracted attention. How to apply polyurethane to car floor mats and prepare a car floor mat with good wear resistance, high resilience and good thermal insulation effect has excellent application prospects.
发明内容Contents of the invention
本发明的目的是为了解决现有技术中存在的缺点，而提出的一种用于汽车脚垫的热塑性弹性体材料及其制备方法。The purpose of the present invention is to propose a thermoplastic elastomer material for automobile floor mats and a preparation method thereof in order to solve the shortcomings existing in the prior art.
一种用于汽车脚垫的热塑性弹性体材料，包括A组分、B组分、C组分；A thermoplastic elastomer material used for automobile floor mats, including component A, component B, and component C;
按重量份，By weight,
A组分包括：甲苯二异氰酸酯30-50份，二苯基甲烷二异氰酸酯10-30份，聚醚多元醇I20-70份；Component A includes: 30-50 parts of toluene diisocyanate, 10-30 parts of diphenylmethane diisocyanate, 20-70 parts of polyether polyol I;
聚醚多元醇I包括：分子量为4000的聚醚多元醇、分子量为6000的聚醚多元醇，其中分子量为4000的聚醚多元醇与分子量为6000的聚醚多元醇的重量比为10：1-2；分子量为4000的聚醚多元醇的官能度为2，分子量为6000的聚醚多元醇的官能度为3；Polyether polyol I includes: a polyether polyol with a molecular weight of 4000 and a polyether polyol with a molecular weight of 6000. The weight ratio of the polyether polyol with a molecular weight of 4000 and the polyether polyol with a molecular weight of 6000 is 10:1. -2; a polyether polyol with a molecular weight of 4000 has a functionality of 2, and a polyether polyol with a molecular weight of 6000 has a functionality of 3;
B组分包括：聚醚多元醇II20-40份，扩链剂1-5份，交联剂1-3份，填料5-15份，催化剂0.1-1份，颜料1-2份；Component B includes: 20-40 parts of polyether polyol II, 1-5 parts of chain extender, 1-3 parts of cross-linking agent, 5-15 parts of filler, 0.1-1 part of catalyst, and 1-2 parts of pigment;
聚醚多元醇II的分子量为1000，其官能度为3；The molecular weight of polyether polyol II is 1000 and its functionality is 3;
C组分包括：负载水的碳化硅骨架10-15份。Component C includes: 10-15 parts of water-loaded silicon carbide skeleton.
优选地，负载水的碳化硅骨架采用如下步骤制取：以聚苯乙烯微球为骨架，碳化硅纳米线包覆在聚苯乙烯微球表面，经空气氛煅烧除去聚苯乙烯微球，然后与水负载而成。Preferably, the water-loaded silicon carbide skeleton is prepared by the following steps: polystyrene microspheres are used as the skeleton, silicon carbide nanowires are coated on the surface of the polystyrene microspheres, and the polystyrene microspheres are removed by calcining in an air atmosphere, and then Loaded with water.
优选地，负载水的碳化硅骨架具体制取步骤如下：将碳化硅纳米线分散于无水乙醇中，搅拌状态下超声分散，超声频率为10-20kHz，加入聚苯乙烯微球后继续超声处理，真空抽滤，100-120℃干燥2-4h，450-550℃空气氛煅烧10-20min，粉碎过筛，加入水搅拌均匀得到负载水的碳化硅骨架。Preferably, the specific preparation steps of the water-loaded silicon carbide skeleton are as follows: disperse the silicon carbide nanowires in anhydrous ethanol, ultrasonic dispersion under stirring, the ultrasonic frequency is 10-20 kHz, add polystyrene microspheres and continue ultrasonic treatment. , vacuum filtration, drying at 100-120℃ for 2-4h, calcining in air atmosphere at 450-550℃ for 10-20min, crushing and sieving, adding water and stirring evenly to obtain a water-loaded silicon carbide skeleton.
优选地，碳化硅纳米线、聚苯乙烯微球、水的质量比为5-10：5-10：1-4。Preferably, the mass ratio of silicon carbide nanowires, polystyrene microspheres, and water is 5-10:5-10:1-4.
优选地，聚苯乙烯微球的平均直径为10-50μm。Preferably, the polystyrene microspheres have an average diameter of 10-50 μm.
优选地，碳化硅纳米线密度为3-3.5g/cm 3，直径为0.1-0.5μm，长度为10-50μm。 Preferably, the density of silicon carbide nanowires is 3-3.5g/cm 3 , the diameter is 0.1-0.5 μm, and the length is 10-50 μm.
优选地，扩链剂为赖氨酸、1,4-丁二醇、1,6-己二醇、二甘醇、1,4-丁二胺、 乙二胺中至少一种。Preferably, the chain extender is at least one of lysine, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, 1,4-butanediamine and ethylenediamine.
优选地，交联剂为甘油、二乙醇胺、三乙醇胺、三羟甲基丙烷中至少一种。Preferably, the cross-linking agent is at least one of glycerol, diethanolamine, triethanolamine, and trimethylolpropane.
优选地，填料为纳米碳酸钙，催化剂为有机铋催化剂。Preferably, the filler is nanometer calcium carbonate, and the catalyst is an organic bismuth catalyst.
上述用于汽车脚垫的热塑性弹性体材料的制备方法，包括如下步骤：The preparation method of the above-mentioned thermoplastic elastomer material for automobile floor mats includes the following steps:
S1、将聚醚多元醇I抽真空脱水1-2h，抽真空脱水过程中维持温度为100-120℃，降至45-55℃后加入甲苯二异氰酸酯、二苯基甲烷二异氰酸酯，70-80℃合成异氰酸酯基含量为3％的预聚体；S1. Vacuum and dehydrate polyether polyol I for 1-2 hours. During the vacuum and dehydration process, maintain the temperature at 100-120°C. After lowering to 45-55°C, add toluene diisocyanate and diphenylmethane diisocyanate, 70-80 ℃ to synthesize a prepolymer with an isocyanate group content of 3%;
S2、将B组分混合均匀，再加入S1所得预聚体，然后向其中加入C组分混合均匀，加入至高压反应釜中，充入二氧化碳至超临界状态，控制高压反应釜内压强为9-10MPa，保压10-20min，然后泄压至5.2-5.8MPa，保压20-40s，继续升压至8-8.5MPa，保压1-2min，然后以1-2MPa/min的速度泄压至常压状态，倒入温度为40-50℃模具中熟化0.5-2h，得到用于汽车脚垫的热塑性弹性体材料。S2. Mix component B evenly, then add the prepolymer obtained in S1, then add component C and mix evenly, add it to the high-pressure reactor, fill it with carbon dioxide to a supercritical state, and control the pressure in the high-pressure reactor to 9 -10MPa, maintain the pressure for 10-20min, then release the pressure to 5.2-5.8MPa, maintain the pressure for 20-40s, continue to increase the pressure to 8-8.5MPa, maintain the pressure for 1-2min, and then release the pressure at a speed of 1-2MPa/min To the normal pressure state, pour into a mold with a temperature of 40-50°C and mature for 0.5-2 hours to obtain a thermoplastic elastomer material for automobile floor mats.
本发明的技术效果如下所示：The technical effects of the present invention are as follows:
(1)本发明将A组分与B组分混匀加入至高压反应釜中，在高压状态保压10-20min后再进行泄压，成核速度快，泡沫数量多，再进行升压，有效控制泡沫均一度，再进行泄压促使气泡生长，所得泡沫孔径为10-150μm，泡沫孔径分布均匀，从而降低产品的导热系数，提高保温性能，稳定性好，同时无需添加稳泡剂等物质；(1) In the present invention, component A and component B are mixed and added into a high-pressure reaction kettle, and the pressure is maintained in a high-pressure state for 10-20 minutes before the pressure is released. The nucleation speed is fast and the number of foams is large, and then the pressure is increased. Effectively control the uniformity of the foam, and then perform pressure relief to promote bubble growth. The resulting foam pore size is 10-150 μm, and the foam pore size is evenly distributed, thereby reducing the thermal conductivity of the product, improving the thermal insulation performance, and having good stability. At the same time, there is no need to add substances such as foam stabilizers. ;
(2)在C组分中，采用聚苯乙烯微球为模板，经过高温空气氛煅烧去除聚苯乙烯微球，得到具有蜂窝状孔洞结构的三维碳化硅骨架，对水的吸附与负载强度高，与A组分、B组分混合均匀后，在高压反应釜中，高压状态下水分缓慢溢出，与甲苯二异氰酸酯反应形成气体，配合后续泄压、升压、再次泄压过程，有效避免泡孔合并、泡孔坍塌现象，而其中的碳化硅骨架均匀分散在体系 中形成骨架结构，不仅耐磨性能极佳，而且与多孔结构配合，有效提高回弹性能。(2) In component C, polystyrene microspheres are used as templates, and the polystyrene microspheres are removed by calcining in a high-temperature air atmosphere to obtain a three-dimensional silicon carbide skeleton with a honeycomb hole structure, which has high adsorption and loading strength for water. , after mixing evenly with component A and component B, in the high-pressure reaction kettle, the water slowly overflows under high pressure and reacts with toluene diisocyanate to form gas. Cooperate with the subsequent pressure relief, pressure increase, and pressure relief process to effectively avoid bubbles. The phenomenon of pore merger and cell collapse, and the silicon carbide skeleton is evenly dispersed in the system to form a skeleton structure, which not only has excellent wear resistance, but also cooperates with the porous structure to effectively improve the resilience performance.
(3)本发明采用甲苯二异氰酸酯、二苯基甲烷二异氰酸酯复配为主料与聚醚多元醇I合成NCO含量为3％的预聚体，然后再依次与聚醚多元醇II、负载水的碳化硅骨架作用，负载水的碳化硅骨架在其中结合强度极高，有效构筑形成耐磨骨架，在增加耐磨强度的同时，回弹性能优异，同时脚垫兼具塑料、橡胶材料的优点，力学性能好，耐永久压缩变形，使用寿命长。(3) The present invention uses toluene diisocyanate and diphenylmethane diisocyanate as main materials and polyether polyol I to synthesize a prepolymer with an NCO content of 3%, and then sequentially mixes it with polyether polyol II and loaded water. The water-loaded silicon carbide skeleton has extremely high bonding strength and effectively forms a wear-resistant skeleton. While increasing the wear-resistant strength, it also has excellent rebound performance. At the same time, the foot pads have the advantages of plastic and rubber materials. , good mechanical properties, resistant to permanent compression deformation and long service life.
具体实施方式Detailed ways
下面结合具体实施例对本发明作进一步解说。The present invention will be further explained below in conjunction with specific embodiments.
实施例1Example 1
一种用于汽车脚垫的热塑性弹性体材料，包括A组分、B组分、C组分；A thermoplastic elastomer material used for automobile floor mats, including component A, component B, and component C;
A组分包括：甲苯二异氰酸酯30kg，二苯基甲烷二异氰酸酯10kg，聚醚多元醇I 20kg；Component A includes: 30kg of toluene diisocyanate, 10kg of diphenylmethane diisocyanate, 20kg of polyether polyol I;
聚醚多元醇I包括：分子量为4000的聚醚多元醇、分子量为6000的聚醚多元醇，其中分子量为4000的聚醚多元醇与分子量为6000的聚醚多元醇的重量比为10：1；Polyether polyol I includes: a polyether polyol with a molecular weight of 4000 and a polyether polyol with a molecular weight of 6000. The weight ratio of the polyether polyol with a molecular weight of 4000 and the polyether polyol with a molecular weight of 6000 is 10:1. ;
分子量为4000的聚醚多元醇的官能度为2，分子量为6000的聚醚多元醇的官能度为3；A polyether polyol with a molecular weight of 4000 has a functionality of 2, and a polyether polyol with a molecular weight of 6000 has a functionality of 3;
B组分包括：聚醚多元醇II 20kg，赖氨酸0.2kg，1,6-己二醇0.8kg，甘油0.3kg，二乙醇胺0.7kg，纳米碳酸钙5kg，月桂酸铋0.1kg，颜料1kg；Component B includes: polyether polyol II 20kg, lysine 0.2kg, 1,6-hexanediol 0.8kg, glycerin 0.3kg, diethanolamine 0.7kg, nano calcium carbonate 5kg, bismuth laurate 0.1kg, pigment 1kg ;
聚醚多元醇II的分子量为1000，其官能度为3；The molecular weight of polyether polyol II is 1000 and its functionality is 3;
C组分包括：负载水的碳化硅骨架10kg。Component C includes: 10kg of water-loaded silicon carbide skeleton.
负载水的碳化硅骨架采用如下步骤制取：将5kg密度为3-3.5g/cm 3、直径为 0.1-0.5μm、长度为10-50μm的碳化硅纳米线分散于20kg无水乙醇中，搅拌状态下超声分散10min，搅拌速度为50r/min，超声频率为10kHz，加入5kg平均直径为10-50μm的聚苯乙烯微球后继续超声处理1h，真空抽滤，100℃干燥2h，加入至马弗炉中，450℃空气氛煅烧10min，粉碎，过80目筛，加入1kg水搅拌均匀得到负载水的碳化硅骨架。 The water-loaded silicon carbide skeleton is prepared by the following steps: 5kg of silicon carbide nanowires with a density of 3-3.5g/cm 3 , a diameter of 0.1-0.5μm, and a length of 10-50μm are dispersed in 20kg of absolute ethanol, and stirred Under ultrasonic dispersion for 10 minutes, the stirring speed is 50r/min, the ultrasonic frequency is 10kHz, add 5kg polystyrene microspheres with an average diameter of 10-50μm, continue ultrasonic treatment for 1h, vacuum filtration, dry at 100°C for 2h, and add to the horse In a furnace, calcined in an air atmosphere at 450°C for 10 minutes, crushed, passed through an 80-mesh sieve, and 1 kg of water was added and stirred evenly to obtain a water-loaded silicon carbide skeleton.
上述用于汽车脚垫的热塑性弹性体材料的制备方法，包括如下步骤：The preparation method of the above-mentioned thermoplastic elastomer material for automobile floor mats includes the following steps:
S1、将聚醚多元醇I抽真空脱水1h，抽真空脱水过程中维持温度为100℃，降至45℃后加入甲苯二异氰酸酯、二苯基甲烷二异氰酸酯，70℃合成异氰酸酯基含量为3％的预聚体；S1. Dehydrate polyether polyol I under vacuum for 1 hour. During the vacuum dehydration process, maintain the temperature at 100°C. After lowering to 45°C, add toluene diisocyanate and diphenylmethane diisocyanate. The isocyanate group content is synthesized at 70°C to 3%. prepolymer;
S2、将B组分混合均匀，再加入S1所得预聚体，然后向其中加入C组分混合均匀，加入至高压反应釜中，充入二氧化碳至超临界状态，控制高压反应釜内压强为9MPa，保压10min，然后泄压至5.2MPa，保压20s，继续升压至8MPa，保压1min，然后以1MPa/min的速度泄压至常压状态，倒入温度为40℃模具中熟化0.5h，得到用于汽车脚垫的热塑性弹性体材料。S2. Mix component B evenly, then add the prepolymer obtained in S1, then add component C and mix evenly, add it to the high-pressure reactor, fill it with carbon dioxide to a supercritical state, and control the pressure in the high-pressure reactor to 9MPa , maintain the pressure for 10 minutes, then release the pressure to 5.2MPa, maintain the pressure for 20s, continue to increase the pressure to 8MPa, maintain the pressure for 1min, then release the pressure to normal pressure at a speed of 1MPa/min, pour it into a mold with a temperature of 40°C and mature for 0.5 h, obtain thermoplastic elastomer materials for automobile floor mats.
实施例2Example 2
一种用于汽车脚垫的热塑性弹性体材料，包括A组分、B组分、C组分；A thermoplastic elastomer material used for automobile floor mats, including component A, component B, and component C;
A组分包括：甲苯二异氰酸酯50kg，二苯基甲烷二异氰酸酯30kg，聚醚多元醇I 70kg；Component A includes: 50kg of toluene diisocyanate, 30kg of diphenylmethane diisocyanate, 70kg of polyether polyol I;
聚醚多元醇I包括：分子量为4000的聚醚多元醇、分子量为6000的聚醚多元醇，其中分子量为4000的聚醚多元醇与分子量为6000的聚醚多元醇的重量比为10：2；Polyether polyol I includes: a polyether polyol with a molecular weight of 4000 and a polyether polyol with a molecular weight of 6000. The weight ratio of the polyether polyol with a molecular weight of 4000 and the polyether polyol with a molecular weight of 6000 is 10:2. ;
分子量为4000的聚醚多元醇的官能度为2，分子量为6000的聚醚多元醇的官能度为3；A polyether polyol with a molecular weight of 4000 has a functionality of 2, and a polyether polyol with a molecular weight of 6000 has a functionality of 3;
B组分包括：聚醚多元醇II 40kg，二甘醇4kg，1,4-丁二胺1kg，三羟甲基丙烷3kg，纳米碳酸钙15kg，月桂酸铋1kg，颜料2kg；Component B includes: polyether polyol II 40kg, diethylene glycol 4kg, 1,4-butanediamine 1kg, trimethylolpropane 3kg, nano calcium carbonate 15kg, bismuth laurate 1kg, pigment 2kg;
聚醚多元醇II的分子量为1000，其官能度为3；The molecular weight of polyether polyol II is 1000 and its functionality is 3;
C组分包括：负载水的碳化硅骨架15kg。Component C includes: 15kg of water-loaded silicon carbide skeleton.
负载水的碳化硅骨架采用如下步骤制取：将10kg密度为3-3.5g/cm 3、直径为0.1-0.5μm、长度为10-50μm的碳化硅纳米线分散于40kg无水乙醇中，搅拌状态下超声分散20min，搅拌速度为100r/min，超声频率为20kHz，加入10kg平均直径为10-50μm的聚苯乙烯微球后继续超声处理2h，真空抽滤，120℃干燥4h，加入至马弗炉中，550℃空气氛煅烧20min，粉碎，过100目筛，加入4kg水搅拌均匀得到负载水的碳化硅骨架。 The water-loaded silicon carbide skeleton is prepared by the following steps: 10kg of silicon carbide nanowires with a density of 3-3.5g/cm 3 , a diameter of 0.1-0.5μm, and a length of 10-50μm are dispersed in 40kg of absolute ethanol, and stirred Under ultrasonic dispersion for 20 minutes, the stirring speed is 100r/min, the ultrasonic frequency is 20kHz, add 10kg polystyrene microspheres with an average diameter of 10-50μm, continue ultrasonic treatment for 2h, vacuum filtration, dry at 120°C for 4h, and add to the horse In a furnace, calcined in an air atmosphere at 550°C for 20 minutes, crushed, passed through a 100-mesh sieve, and 4kg of water was added and stirred evenly to obtain a water-loaded silicon carbide skeleton.
上述用于汽车脚垫的热塑性弹性体材料的制备方法，包括如下步骤：The preparation method of the above-mentioned thermoplastic elastomer material for automobile floor mats includes the following steps:
S1、将聚醚多元醇I抽真空脱水2h，抽真空脱水过程中维持温度为120℃，降至55℃后加入甲苯二异氰酸酯、二苯基甲烷二异氰酸酯，80℃合成异氰酸酯基含量为3％的预聚体；S1. Vacuum and dehydrate polyether polyol I for 2 hours. During the vacuum dehydration process, maintain the temperature at 120°C. After lowering to 55°C, add toluene diisocyanate and diphenylmethane diisocyanate. The isocyanate group content is synthesized at 80°C to 3%. prepolymer;
S2、将B组分混合均匀，再加入S1所得预聚体，然后向其中加入C组分混合均匀，加入至高压反应釜中，充入二氧化碳至超临界状态，控制高压反应釜内压强为10MPa，保压20min，然后泄压至5.8MPa，保压40s，继续升压至8.5MPa，保压2min，然后以2MPa/min的速度泄压至常压状态，倒入温度为50℃模具中熟化2h，得到用于汽车脚垫的热塑性弹性体材料。S2. Mix component B evenly, then add the prepolymer obtained in S1, then add component C and mix evenly, add it to the high-pressure reactor, fill it with carbon dioxide to a supercritical state, and control the pressure in the high-pressure reactor to 10MPa , maintain the pressure for 20min, then release the pressure to 5.8MPa, maintain the pressure for 40s, continue to increase the pressure to 8.5MPa, maintain the pressure for 2min, then release the pressure to normal pressure at a speed of 2MPa/min, pour it into a mold with a temperature of 50°C for maturation In 2 hours, the thermoplastic elastomer material used for automobile floor mats was obtained.
实施例3Example 3
一种用于汽车脚垫的热塑性弹性体材料，包括A组分、B组分、C组分；A thermoplastic elastomer material used for automobile floor mats, including component A, component B, and component C;
A组分包括：甲苯二异氰酸酯35kg，二苯基甲烷二异氰酸酯25kg，聚醚多元醇I 30kg；Component A includes: 35kg of toluene diisocyanate, 25kg of diphenylmethane diisocyanate, 30kg of polyether polyol I;
聚醚多元醇I包括：分子量为4000的聚醚多元醇、分子量为6000的聚醚多元醇，其中分子量为4000的聚醚多元醇与分子量为6000的聚醚多元醇的重量比为10：1.7；Polyether polyol I includes: a polyether polyol with a molecular weight of 4000 and a polyether polyol with a molecular weight of 6000. The weight ratio of the polyether polyol with a molecular weight of 4000 and the polyether polyol with a molecular weight of 6000 is 10:1.7 ;
分子量为4000的聚醚多元醇的官能度为2，分子量为6000的聚醚多元醇的官能度为3；A polyether polyol with a molecular weight of 4000 has a functionality of 2, and a polyether polyol with a molecular weight of 6000 has a functionality of 3;
B组分包括：聚醚多元醇II 25kg，1,4-丁二醇3.5kg，乙二胺0.5kg，三乙醇胺1.5kg，纳米碳酸钙8kg，月桂酸铋0.8kg，颜料1.3kg；Component B includes: polyether polyol II 25kg, 1,4-butanediol 3.5kg, ethylenediamine 0.5kg, triethanolamine 1.5kg, nano calcium carbonate 8kg, bismuth laurate 0.8kg, pigment 1.3kg;
聚醚多元醇II的分子量为1000，其官能度为3；The molecular weight of polyether polyol II is 1000 and its functionality is 3;
C组分包括：负载水的碳化硅骨架12kg。Component C includes: 12kg of water-loaded silicon carbide skeleton.
负载水的碳化硅骨架采用如下步骤制取：将8kg密度为3-3.5g/cm 3、直径为0.1-0.5μm、长度为10-50μm的碳化硅纳米线分散于25kg无水乙醇中，搅拌状态下超声分散18min，搅拌速度为60r/min，超声频率为18kHz，加入6kg平均直径为10-50μm的聚苯乙烯微球后继续超声处理100min，真空抽滤，105℃干燥3.5h，加入至马弗炉中，480℃空气氛煅烧18min，粉碎，过85目筛，加入3kg水搅拌均匀得到负载水的碳化硅骨架。 The water-loaded silicon carbide skeleton is prepared by the following steps: 8kg of silicon carbide nanowires with a density of 3-3.5g/cm 3 , a diameter of 0.1-0.5μm, and a length of 10-50μm are dispersed in 25kg of absolute ethanol, and stirred Under ultrasonic dispersion for 18 minutes, the stirring speed is 60r/min, the ultrasonic frequency is 18kHz, add 6kg polystyrene microspheres with an average diameter of 10-50μm, continue ultrasonic treatment for 100min, vacuum filtration, dry at 105°C for 3.5h, add to In a muffle furnace, calcined in an air atmosphere at 480°C for 18 minutes, crushed, passed through an 85-mesh sieve, and 3kg of water was added and stirred evenly to obtain a water-loaded silicon carbide skeleton.
上述用于汽车脚垫的热塑性弹性体材料的制备方法，包括如下步骤：The preparation method of the above-mentioned thermoplastic elastomer material for automobile floor mats includes the following steps:
S1、将聚醚多元醇I抽真空脱水1.2h，抽真空脱水过程中维持温度为115℃，降至48℃后加入甲苯二异氰酸酯、二苯基甲烷二异氰酸酯，77℃合成异氰酸酯基含量为3％的预聚体；S1. Dehydrate polyether polyol I under vacuum for 1.2 hours. During the vacuum dehydration process, the temperature is maintained at 115°C. After lowering to 48°C, toluene diisocyanate and diphenylmethane diisocyanate are added. The isocyanate group content is synthesized at 77°C to 3 % prepolymer;
S2、将B组分混合均匀，再加入S1所得预聚体，然后向其中加入C组分混合均匀，加入至高压反应釜中，充入二氧化碳至超临界状态，控制高压反应釜内压强为9.3MPa，保压18min，然后泄压至5.4MPa，保压35s，继续升压至8.1MPa，保压1.8min，然后以1.3MPa/min的速度泄压至常压状态，倒入温度为 47℃模具中熟化1h，得到用于汽车脚垫的热塑性弹性体材料。S2. Mix component B evenly, then add the prepolymer obtained in S1, then add component C and mix evenly, add it to the high-pressure reactor, fill it with carbon dioxide to a supercritical state, and control the pressure in the high-pressure reactor to 9.3 MPa, maintain the pressure for 18 minutes, then release the pressure to 5.4MPa, maintain the pressure for 35s, continue to increase the pressure to 8.1MPa, maintain the pressure for 1.8min, then release the pressure to normal pressure at a speed of 1.3MPa/min, and the pouring temperature is 47°C After aging in the mold for 1 hour, a thermoplastic elastomer material for automobile floor mats is obtained.
实施例4Example 4
一种用于汽车脚垫的热塑性弹性体材料，包括A组分、B组分、C组分；A thermoplastic elastomer material used for automobile floor mats, including component A, component B, and component C;
A组分包括：甲苯二异氰酸酯45kg，二苯基甲烷二异氰酸酯15kg，聚醚多元醇I 60kg；Component A includes: 45kg of toluene diisocyanate, 15kg of diphenylmethane diisocyanate, 60kg of polyether polyol I;
聚醚多元醇I包括：分子量为4000的聚醚多元醇、分子量为6000的聚醚多元醇，其中分子量为4000的聚醚多元醇与分子量为6000的聚醚多元醇的重量比为10：1.3；Polyether polyol I includes: a polyether polyol with a molecular weight of 4000 and a polyether polyol with a molecular weight of 6000. The weight ratio of the polyether polyol with a molecular weight of 4000 and the polyether polyol with a molecular weight of 6000 is 10:1.3 ;
分子量为4000的聚醚多元醇的官能度为2，分子量为6000的聚醚多元醇的官能度为3；A polyether polyol with a molecular weight of 4000 has a functionality of 2, and a polyether polyol with a molecular weight of 6000 has a functionality of 3;
B组分包括：聚醚多元醇II 35kg，赖氨酸1kg，1,4-丁二醇1kg，甘油2.5kg，纳米碳酸钙12kg，月桂酸铋0.2kg，颜料1.7kg；Component B includes: polyether polyol II 35kg, lysine 1kg, 1,4-butanediol 1kg, glycerin 2.5kg, nano calcium carbonate 12kg, bismuth laurate 0.2kg, pigment 1.7kg;
聚醚多元醇II的分子量为1000，其官能度为3；The molecular weight of polyether polyol II is 1000 and its functionality is 3;
C组分包括：负载水的碳化硅骨架14kg。Component C includes: 14kg of water-loaded silicon carbide skeleton.
负载水的碳化硅骨架采用如下步骤制取：将6kg密度为3-3.5g/cm 3、直径为0.1-0.5μm、长度为10-50μm的碳化硅纳米线分散于35kg无水乙醇中，搅拌状态下超声分散12min，搅拌速度为80r/min，超声频率为12kHz，加入8kg平均直径为10-50μm的聚苯乙烯微球后继续超声处理80min，真空抽滤，115℃干燥2.5h，加入至马弗炉中，520℃空气氛煅烧12min，粉碎，过95目筛，加入2kg水搅拌均匀得到负载水的碳化硅骨架。 The water-loaded silicon carbide skeleton is prepared by the following steps: 6 kg of silicon carbide nanowires with a density of 3-3.5 g/cm 3 , a diameter of 0.1-0.5 μm, and a length of 10-50 μm are dispersed in 35 kg of absolute ethanol, and stirred Under ultrasonic dispersion for 12 minutes, the stirring speed is 80r/min, the ultrasonic frequency is 12kHz, add 8kg polystyrene microspheres with an average diameter of 10-50μm, continue ultrasonic treatment for 80min, vacuum filtration, dry at 115°C for 2.5h, add to In a muffle furnace, calcined in an air atmosphere at 520°C for 12 minutes, crushed, passed through a 95-mesh sieve, and 2kg of water was added and stirred evenly to obtain a water-loaded silicon carbide skeleton.
上述用于汽车脚垫的热塑性弹性体材料的制备方法，包括如下步骤：The preparation method of the above-mentioned thermoplastic elastomer material for automobile floor mats includes the following steps:
S1、将聚醚多元醇I抽真空脱水1.8h，抽真空脱水过程中维持温度为105℃，降至52℃后加入甲苯二异氰酸酯、二苯基甲烷二异氰酸酯，73℃合成异氰酸酯 基含量为3％的预聚体；S1. Dehydrate polyether polyol I under vacuum for 1.8 hours. During the vacuum dehydration process, the temperature is maintained at 105°C. After lowering to 52°C, toluene diisocyanate and diphenylmethane diisocyanate are added. The isocyanate group content is synthesized at 73°C to 3 % prepolymer;
S2、将B组分混合均匀，再加入S1所得预聚体，然后向其中加入C组分混合均匀，加入至高压反应釜中，充入二氧化碳至超临界状态，控制高压反应釜内压强为9.7MPa，保压12min，然后泄压至5.6MPa，保压25s，继续升压至8.3MPa，保压1.2min，然后以1.7MPa/min的速度泄压至常压状态，倒入温度为43℃模具中熟化1.5h，得到用于汽车脚垫的热塑性弹性体材料。S2. Mix component B evenly, then add the prepolymer obtained in S1, then add component C and mix evenly, add it to the high-pressure reactor, fill it with carbon dioxide to a supercritical state, and control the pressure in the high-pressure reactor to 9.7 MPa, maintain the pressure for 12 minutes, then release the pressure to 5.6MPa, maintain the pressure for 25s, continue to increase the pressure to 8.3MPa, maintain the pressure for 1.2min, then release the pressure to normal pressure at a speed of 1.7MPa/min, and the pouring temperature is 43°C After aging in the mold for 1.5 hours, a thermoplastic elastomer material for automobile floor mats was obtained.
实施例5Example 5
一种用于汽车脚垫的热塑性弹性体材料，包括A组分、B组分、C组分；A thermoplastic elastomer material used for automobile floor mats, including component A, component B, and component C;
A组分包括：甲苯二异氰酸酯40kg，二苯基甲烷二异氰酸酯20kg，聚醚多元醇I 45kg；Component A includes: 40kg of toluene diisocyanate, 20kg of diphenylmethane diisocyanate, 45kg of polyether polyol I;
聚醚多元醇I包括：分子量为4000的聚醚多元醇、分子量为6000的聚醚多元醇，其中分子量为4000的聚醚多元醇与分子量为6000的聚醚多元醇的重量比为10：1.5；Polyether polyol I includes: a polyether polyol with a molecular weight of 4000 and a polyether polyol with a molecular weight of 6000. The weight ratio of the polyether polyol with a molecular weight of 4000 and the polyether polyol with a molecular weight of 6000 is 10:1.5. ;
分子量为4000的聚醚多元醇的官能度为2，分子量为6000的聚醚多元醇的官能度为3；A polyether polyol with a molecular weight of 4000 has a functionality of 2, and a polyether polyol with a molecular weight of 6000 has a functionality of 3;
B组分包括：聚醚多元醇II 30kg，二甘醇3kg，二乙醇胺2kg，纳米碳酸钙10kg，月桂酸铋0.5kg，颜料1.5kg；Component B includes: polyether polyol II 30kg, diethylene glycol 3kg, diethanolamine 2kg, nano calcium carbonate 10kg, bismuth laurate 0.5kg, pigment 1.5kg;
聚醚多元醇II的分子量为1000，其官能度为3；The molecular weight of polyether polyol II is 1000 and its functionality is 3;
C组分包括：负载水的碳化硅骨架12kg。Component C includes: 12kg of water-loaded silicon carbide skeleton.
负载水的碳化硅骨架采用如下步骤制取：将7kg密度为3-3.5g/cm 3、直径为0.1-0.5μm、长度为10-50μm的碳化硅纳米线分散于30kg无水乙醇中，搅拌状态下超声分散15min，搅拌速度为70r/min，超声频率为15kHz，加入7kg平均直径为10-50μm的聚苯乙烯微球后继续超声处理90min，真空抽滤，110℃干燥3h， 加入至马弗炉中，500℃空气氛煅烧15min，粉碎，过90目筛，加入2.5kg水搅拌均匀得到负载水的碳化硅骨架。 The water-loaded silicon carbide skeleton is prepared by the following steps: 7kg of silicon carbide nanowires with a density of 3-3.5g/cm 3 , a diameter of 0.1-0.5μm, and a length of 10-50μm are dispersed in 30kg of absolute ethanol, and stirred Under ultrasonic dispersion for 15 minutes, the stirring speed is 70r/min, the ultrasonic frequency is 15kHz, add 7kg polystyrene microspheres with an average diameter of 10-50μm, continue ultrasonic treatment for 90min, vacuum filtration, dry at 110°C for 3h, and add to horse In a furnace, calcined in an air atmosphere at 500°C for 15 minutes, crushed, passed through a 90-mesh sieve, and 2.5kg of water was added and stirred evenly to obtain a water-loaded silicon carbide skeleton.
上述用于汽车脚垫的热塑性弹性体材料的制备方法，包括如下步骤：The preparation method of the above-mentioned thermoplastic elastomer material for automobile floor mats includes the following steps:
S1、将聚醚多元醇I抽真空脱水1.5h，抽真空脱水过程中维持温度为110℃，降至50℃后加入甲苯二异氰酸酯、二苯基甲烷二异氰酸酯，75℃合成异氰酸酯基含量为3％的预聚体；S1. Dehydrate polyether polyol I under vacuum for 1.5 hours. During the vacuum dehydration process, the temperature is maintained at 110°C. After lowering to 50°C, toluene diisocyanate and diphenylmethane diisocyanate are added. The isocyanate group content is synthesized at 75°C to 3 % prepolymer;
S2、将B组分混合均匀，再加入S1所得预聚体，然后向其中加入C组分混合均匀，加入至高压反应釜中，充入二氧化碳至超临界状态，控制高压反应釜内压强为9.5MPa，保压15min，然后泄压至5.5MPa，保压30s，继续升压至8.2MPa，保压1.5min，然后以1.5MPa/min的速度泄压至常压状态，倒入温度为45℃模具中熟化1.2h，得到用于汽车脚垫的热塑性弹性体材料。S2. Mix component B evenly, then add the prepolymer obtained in S1, then add component C and mix evenly, add it to the high-pressure reactor, fill it with carbon dioxide to a supercritical state, and control the pressure in the high-pressure reactor to 9.5 MPa, maintain the pressure for 15 minutes, then release the pressure to 5.5MPa, maintain the pressure for 30s, continue to increase the pressure to 8.2MPa, maintain the pressure for 1.5min, then release the pressure to normal pressure at a rate of 1.5MPa/min, and the pouring temperature is 45°C After aging in the mold for 1.2 hours, a thermoplastic elastomer material for automobile floor mats was obtained.
对比例1Comparative example 1
一种用于汽车脚垫的热塑性弹性体材料，包括A组分、B组分、C组分；A thermoplastic elastomer material used for automobile floor mats, including component A, component B, and component C;
A组分包括：甲苯二异氰酸酯40kg，二苯基甲烷二异氰酸酯20kg，聚醚多元醇I 45kg；Component A includes: 40kg of toluene diisocyanate, 20kg of diphenylmethane diisocyanate, 45kg of polyether polyol I;
聚醚多元醇I包括：分子量为4000的聚醚多元醇、分子量为6000的聚醚多元醇，其中分子量为4000的聚醚多元醇与分子量为6000的聚醚多元醇的重量比为10：1.5；Polyether polyol I includes: a polyether polyol with a molecular weight of 4000 and a polyether polyol with a molecular weight of 6000. The weight ratio of the polyether polyol with a molecular weight of 4000 and the polyether polyol with a molecular weight of 6000 is 10:1.5. ;
分子量为4000的聚醚多元醇的官能度为2，分子量为6000的聚醚多元醇的官能度为3；A polyether polyol with a molecular weight of 4000 has a functionality of 2, and a polyether polyol with a molecular weight of 6000 has a functionality of 3;
B组分包括：聚醚多元醇II 30kg，二甘醇3kg，二乙醇胺2kg，纳米碳酸钙10kg，月桂酸铋0.5kg，颜料1.5kg；Component B includes: polyether polyol II 30kg, diethylene glycol 3kg, diethanolamine 2kg, nano calcium carbonate 10kg, bismuth laurate 0.5kg, pigment 1.5kg;
聚醚多元醇II的分子量为1000，其官能度为3；The molecular weight of polyether polyol II is 1000 and its functionality is 3;
C组分包括：水，其中水的添加量与实施例5中负载水的碳化硅骨架中水的含量相同。Component C includes: water, where the added amount of water is the same as the water content in the water-loaded silicon carbide skeleton in Example 5.
上述用于汽车脚垫的热塑性弹性体材料的制备方法，包括如下步骤：The preparation method of the above-mentioned thermoplastic elastomer material for automobile floor mats includes the following steps:
S1、将聚醚多元醇I抽真空脱水1.5h，抽真空脱水过程中维持温度为110℃，降至50℃后加入甲苯二异氰酸酯、二苯基甲烷二异氰酸酯，75℃合成异氰酸酯基含量为3％的预聚体；S1. Dehydrate polyether polyol I under vacuum for 1.5 hours. During the vacuum dehydration process, the temperature is maintained at 110°C. After lowering to 50°C, toluene diisocyanate and diphenylmethane diisocyanate are added. The isocyanate group content is synthesized at 75°C to 3 % prepolymer;
S2、将B组分混合均匀，再加入S1所得预聚体，然后向其中加入C组分混合均匀，加入至高压反应釜中，充入二氧化碳至超临界状态，控制高压反应釜内压强为9.5MPa，保压15min，然后泄压至5.5MPa，保压30s，继续升压至8.2MPa，保压1.5min，然后以1.5MPa/min的速度泄压至常压状态，倒入温度为45℃模具中熟化1.2h，得到用于汽车脚垫的热塑性弹性体材料。S2. Mix component B evenly, then add the prepolymer obtained in S1, then add component C and mix evenly, add it to the high-pressure reactor, fill it with carbon dioxide to a supercritical state, and control the pressure in the high-pressure reactor to 9.5 MPa, maintain the pressure for 15 minutes, then release the pressure to 5.5MPa, maintain the pressure for 30s, continue to increase the pressure to 8.2MPa, maintain the pressure for 1.5min, then release the pressure to normal pressure at a rate of 1.5MPa/min, and the pouring temperature is 45°C After aging in the mold for 1.2 hours, a thermoplastic elastomer material for automobile floor mats was obtained.
对比例2Comparative example 2
一种用于汽车脚垫的热塑性弹性体材料，包括A组分、B组分、C组分；A thermoplastic elastomer material used for automobile floor mats, including component A, component B, and component C;
A组分包括：甲苯二异氰酸酯40kg，二苯基甲烷二异氰酸酯20kg，聚醚多元醇I 45kg；Component A includes: 40kg of toluene diisocyanate, 20kg of diphenylmethane diisocyanate, 45kg of polyether polyol I;
聚醚多元醇I包括：分子量为4000的聚醚多元醇、分子量为6000的聚醚多元醇，其中分子量为4000的聚醚多元醇与分子量为6000的聚醚多元醇的重量比为10：1.5；Polyether polyol I includes: a polyether polyol with a molecular weight of 4000 and a polyether polyol with a molecular weight of 6000. The weight ratio of the polyether polyol with a molecular weight of 4000 and the polyether polyol with a molecular weight of 6000 is 10:1.5. ;
分子量为4000的聚醚多元醇的官能度为2，分子量为6000的聚醚多元醇的官能度为3；A polyether polyol with a molecular weight of 4000 has a functionality of 2, and a polyether polyol with a molecular weight of 6000 has a functionality of 3;
B组分包括：聚醚多元醇II 30kg，二甘醇3kg，二乙醇胺2kg，纳米碳酸钙10kg，月桂酸铋0.5kg，颜料1.5kg；Component B includes: polyether polyol II 30kg, diethylene glycol 3kg, diethanolamine 2kg, nano calcium carbonate 10kg, bismuth laurate 0.5kg, pigment 1.5kg;
聚醚多元醇II的分子量为1000，其官能度为3；The molecular weight of polyether polyol II is 1000 and its functionality is 3;
C组分包括：负载水的碳化硅骨架。Component C includes: water-loaded silicon carbide skeleton.
负载水的碳化硅骨架采用如下步骤制取：将7kg密度为3-3.5g/cm 3、直径为0.1-0.5μm、长度为10-50μm的碳化硅纳米线分散于30kg无水乙醇中，搅拌状态下超声分散15min，搅拌速度为70r/min，超声频率为15kHz，加入7kg平均直径为10-50μm的聚苯乙烯微球后继续超声处理90min，真空抽滤，110℃干燥3h，加入至马弗炉中，500℃空气氛煅烧15min，粉碎，过90目筛，加入2.5kg水搅拌均匀得到负载水的碳化硅骨架。 The water-loaded silicon carbide skeleton is prepared by the following steps: 7kg of silicon carbide nanowires with a density of 3-3.5g/cm 3 , a diameter of 0.1-0.5μm, and a length of 10-50μm are dispersed in 30kg of absolute ethanol, and stirred Under ultrasonic dispersion for 15 minutes, the stirring speed is 70r/min, the ultrasonic frequency is 15kHz, add 7kg polystyrene microspheres with an average diameter of 10-50μm, continue ultrasonic treatment for 90min, vacuum filtration, dry at 110°C for 3h, and add to horse In a furnace, calcined in an air atmosphere at 500°C for 15 minutes, crushed, passed through a 90-mesh sieve, and 2.5kg of water was added and stirred evenly to obtain a water-loaded silicon carbide skeleton.
上述用于汽车脚垫的热塑性弹性体材料的制备方法，包括如下步骤：The preparation method of the above-mentioned thermoplastic elastomer material for automobile floor mats includes the following steps:
S1、将聚醚多元醇I抽真空脱水1.5h，抽真空脱水过程中维持温度为110℃，降至50℃后加入甲苯二异氰酸酯、二苯基甲烷二异氰酸酯，75℃合成异氰酸酯基含量为3％的预聚体；S1. Dehydrate polyether polyol I under vacuum for 1.5 hours. During the vacuum dehydration process, the temperature is maintained at 110°C. After lowering to 50°C, toluene diisocyanate and diphenylmethane diisocyanate are added. The isocyanate group content is synthesized at 75°C to 3 % prepolymer;
S2、将B组分混合均匀，再加入S1所得预聚体，然后向其中加入C组分混合均匀，加入至高压反应釜中，充入二氧化碳至超临界状态，控制高压反应釜内压强为9.5MPa，保压15min，然后以1.5MPa/min的速度泄压至常压状态，倒入温度为45℃模具中熟化1.2h，得到用于汽车脚垫的热塑性弹性体材料。S2. Mix component B evenly, then add the prepolymer obtained in S1, then add component C and mix evenly, add it to the high-pressure reactor, fill it with carbon dioxide to a supercritical state, and control the pressure in the high-pressure reactor to 9.5 MPa, maintain the pressure for 15 minutes, then release the pressure to normal pressure at a speed of 1.5 MPa/min, pour it into a mold at a temperature of 45°C and mature for 1.2 hours to obtain a thermoplastic elastomer material for automobile floor mats.
将实施例5和对比例1-2所得用于汽车脚垫的热塑性弹性体材料进行对比性能测试，具体如下：The thermoplastic elastomer materials for automobile floor mats obtained in Example 5 and Comparative Examples 1-2 were subjected to comparative performance tests, as follows:
1、机械性能测试1. Mechanical performance test
 ​ 实施例5Example 5 对比例1Comparative example 1 对比例2Comparative example 2 检测标准Testing standards
密度，g/cm 3 Density, g/cm 3 0.680.68 0.790.79 0.710.71 //
邵A硬度Shore A hardness 5252 6666 5757 GB/T 531-2008GB/T 531-2008
拉断强度，MpaBreaking strength, Mpa 5.55.5 4.04.0 4.94.9 GB/T 10654-2001GB/T 10654-2001
拉断伸长率，％Elongation at break, % 793793 603603 684684 GB/T 10654-2001GB/T 10654-2001
压缩永久变形，％Compression set,% 22twenty two 3232 2828 GB/T 10653-2001GB/T 10653-2001
2、耐磨、回弹和导热系数测试2. Wear resistance, rebound and thermal conductivity tests
2.1阿克隆磨耗测试：参照GB/T 1689-2014测试耐磨性能，各组试样固定在胶轮轴上，启动电机，使试样按顺时针方向旋转，预磨15-20min后取下，刷净胶屑，称其质量为M 1。然后用预磨后的试样进行试验。试样行驶1.61km后，关闭电机，取下试样，刷去胶屑，在1h内称量质量M 2。 2.1 Akron wear test: Refer to GB/T 1689-2014 to test the wear resistance. Each group of samples is fixed on the rubber wheel shaft, start the motor, rotate the sample clockwise, pre-grind for 15-20 minutes, remove it, and brush The mass of net rubber scraps is M 1 . The pre-ground specimens were then used for testing. After the sample travels 1.61km, turn off the motor, remove the sample, brush off the glue chips, and weigh the mass M 2 within 1 hour.
2.2利用模压的标准回弹试样在回弹测试仪上进行测试。2.2 Use the molded standard rebound specimen to test on the rebound tester.
 ​ 实施例5Example 5 对比例1Comparative example 1 对比例2Comparative example 2
阿克隆磨耗体积，cm 3 Akron wear volume, cm 3 0.110.11 0.360.36 0.230.23
冲击回弹，％Impact rebound, % 5757 4444 5151
导热系数，mW/(m·K)Thermal conductivity, mW/(m·K) 15.815.8 18.818.8 17.917.9
以上所述，仅为本发明较佳的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，根据本发明的技术方案及其发明构思加以等同替换或改变，都应涵盖在本发明的保护范围之内。The above are only preferred specific embodiments of the present invention, but the protection scope of the present invention is not limited thereto. Any person familiar with the technical field can, within the technical scope disclosed in the present invention, implement the technical solutions of the present invention. Equivalent substitutions or changes of the inventive concept thereof shall be included in the protection scope of the present invention.

Claims (10)

  1. 一种用于汽车脚垫的热塑性弹性体材料，其特征在于，包括A组分、B组分、C组分；A thermoplastic elastomer material used for automobile floor mats, which is characterized in that it includes component A, component B, and component C;
    按重量份，By weight,
    A组分包括：甲苯二异氰酸酯30-50份，二苯基甲烷二异氰酸酯10-30份，聚醚多元醇I 20-70份；Component A includes: 30-50 parts of toluene diisocyanate, 10-30 parts of diphenylmethane diisocyanate, 20-70 parts of polyether polyol I;
    聚醚多元醇I包括：分子量为4000的聚醚多元醇、分子量为6000的聚醚多元醇，其中分子量为4000的聚醚多元醇与分子量为6000的聚醚多元醇的重量比为10：1-2；分子量为4000的聚醚多元醇的官能度为2，分子量为6000的聚醚多元醇的官能度为3；Polyether polyol I includes: a polyether polyol with a molecular weight of 4000 and a polyether polyol with a molecular weight of 6000. The weight ratio of the polyether polyol with a molecular weight of 4000 and the polyether polyol with a molecular weight of 6000 is 10:1. -2; a polyether polyol with a molecular weight of 4000 has a functionality of 2, and a polyether polyol with a molecular weight of 6000 has a functionality of 3;
    B组分包括：聚醚多元醇II 20-40份，扩链剂1-5份，交联剂1-3份，填料5-15份，催化剂0.1-1份，颜料1-2份；Component B includes: 20-40 parts of polyether polyol II, 1-5 parts of chain extender, 1-3 parts of cross-linking agent, 5-15 parts of filler, 0.1-1 part of catalyst, and 1-2 parts of pigment;
    聚醚多元醇II的分子量为1000，其官能度为3；The molecular weight of polyether polyol II is 1000 and its functionality is 3;
    C组分包括：负载水的碳化硅骨架10-15份。Component C includes: 10-15 parts of water-loaded silicon carbide skeleton.
  2. 根据权利要求1所述用于汽车脚垫的热塑性弹性体材料，其特征在于，负载水的碳化硅骨架采用如下步骤制取：以聚苯乙烯微球为骨架，碳化硅纳米线包覆在聚苯乙烯微球表面，经空气氛煅烧除去聚苯乙烯微球，然后与水负载而成。The thermoplastic elastomer material for automobile floor mats according to claim 1, characterized in that the water-loaded silicon carbide skeleton is prepared by the following steps: polystyrene microspheres are used as the skeleton, and the silicon carbide nanowires are coated in the polystyrene microspheres. The surface of styrene microspheres is calcined in an air atmosphere to remove polystyrene microspheres, and then loaded with water.
  3. 根据权利要求1所述用于汽车脚垫的热塑性弹性体材料，其特征在于，负载水的碳化硅骨架具体制取步骤如下：将碳化硅纳米线分散于无水乙醇中，搅拌状态下超声分散，超声频率为10-20kHz，加入聚苯乙烯微球后继续超声处理，真空抽滤，100-120℃干燥2-4h，450-550℃空气氛煅烧10-20min，粉碎过筛，加入水搅拌均匀得到负载水的碳化硅骨架。The thermoplastic elastomer material for automobile floor mats according to claim 1, characterized in that the specific preparation steps of the water-loaded silicon carbide skeleton are as follows: dispersing the silicon carbide nanowires in absolute ethanol, and ultrasonic dispersion under stirring , the ultrasonic frequency is 10-20kHz, add polystyrene microspheres and continue ultrasonic treatment, vacuum filtration, dry at 100-120℃ for 2-4h, calcine at 450-550℃ in air atmosphere for 10-20min, crush and sieve, add water and stir A water-loaded silicon carbide skeleton is uniformly obtained.
  4. 根据权利要求2或3所述用于汽车脚垫的热塑性弹性体材料，其特征在 于，碳化硅纳米线、聚苯乙烯微球、水的质量比为5-10：5-10：1-4。The thermoplastic elastomer material for automobile floor mats according to claim 2 or 3, characterized in that the mass ratio of silicon carbide nanowires, polystyrene microspheres and water is 5-10:5-10:1-4 .
  5. 根据权利要求2或3所述用于汽车脚垫的热塑性弹性体材料，其特征在于，聚苯乙烯微球的平均直径为10-50μm。The thermoplastic elastomer material for automobile floor mats according to claim 2 or 3, characterized in that the average diameter of the polystyrene microspheres is 10-50 μm.
  6. 根据权利要求2或3所述用于汽车脚垫的热塑性弹性体材料，其特征在于，碳化硅纳米线密度为3-3.5g/cm 3，直径为0.1-0.5μm，长度为10-50μm。 The thermoplastic elastomer material for automobile floor mats according to claim 2 or 3, characterized in that the silicon carbide nanowire density is 3-3.5g/cm 3 , the diameter is 0.1-0.5 μm, and the length is 10-50 μm.
  7. 根据权利要求1所述用于汽车脚垫的热塑性弹性体材料，其特征在于，扩链剂为赖氨酸、1,4-丁二醇、1,6-己二醇、二甘醇、1,4-丁二胺、乙二胺中至少一种。The thermoplastic elastomer material for automobile floor mats according to claim 1, wherein the chain extender is lysine, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, 1 , at least one of 4-butanediamine and ethylenediamine.
  8. 根据权利要求1所述用于汽车脚垫的热塑性弹性体材料，其特征在于，交联剂为甘油、二乙醇胺、三乙醇胺、三羟甲基丙烷中至少一种。The thermoplastic elastomer material for automobile floor mats according to claim 1, wherein the cross-linking agent is at least one of glycerin, diethanolamine, triethanolamine, and trimethylolpropane.
  9. 根据权利要求1所述用于汽车脚垫的热塑性弹性体材料，其特征在于，填料为纳米碳酸钙，催化剂为有机铋催化剂。The thermoplastic elastomer material for automobile floor mats according to claim 1, wherein the filler is nano-calcium carbonate and the catalyst is an organic bismuth catalyst.
  10. 一种如权利要求1-9任一项所述用于汽车脚垫的热塑性弹性体材料的制备方法，其特征在于，包括如下步骤：A method for preparing a thermoplastic elastomer material for automobile floor mats according to any one of claims 1 to 9, characterized in that it includes the following steps:
    S1、将聚醚多元醇I抽真空脱水1-2h，抽真空脱水过程中维持温度为100-120℃，降至45-55℃后加入甲苯二异氰酸酯、二苯基甲烷二异氰酸酯，70-80℃合成异氰酸酯基含量为3％的预聚体；S1. Vacuum and dehydrate polyether polyol I for 1-2 hours. During the vacuum and dehydration process, maintain the temperature at 100-120°C. After lowering to 45-55°C, add toluene diisocyanate and diphenylmethane diisocyanate, 70-80 ℃ to synthesize a prepolymer with an isocyanate group content of 3%;
    S2、将B组分混合均匀，再加入S1所得预聚体，然后向其中加入C组分混合均匀，加入至高压反应釜中，充入二氧化碳至超临界状态，控制高压反应釜内压强为9-10MPa，保压10-20min，然后泄压至5.2-5.8MPa，保压20-40s，继续升压至8-8.5MPa，保压1-2min，然后以1-2MPa/min的速度泄压至常压状态，倒入温度为40-50℃模具中熟化0.5-2h，得到用于汽车脚垫的热塑性弹性体材料。S2. Mix component B evenly, then add the prepolymer obtained in S1, then add component C and mix evenly, add it to the high-pressure reactor, fill it with carbon dioxide to a supercritical state, and control the pressure in the high-pressure reactor to 9 -10MPa, maintain the pressure for 10-20min, then release the pressure to 5.2-5.8MPa, maintain the pressure for 20-40s, continue to increase the pressure to 8-8.5MPa, maintain the pressure for 1-2min, and then release the pressure at a speed of 1-2MPa/min To the normal pressure state, pour into a mold with a temperature of 40-50°C and mature for 0.5-2 hours to obtain a thermoplastic elastomer material for automobile floor mats.
PCT/CN2022/100782 2022-06-17 2022-06-23 Thermoplastic elastomer material for automotive foot mat and preparation method therefor WO2023240670A1 (en)

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