WO2023240668A1 - 一种环保汽车脚垫材料及其制备方法 - Google Patents

一种环保汽车脚垫材料及其制备方法 Download PDF

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WO2023240668A1
WO2023240668A1 PCT/CN2022/100766 CN2022100766W WO2023240668A1 WO 2023240668 A1 WO2023240668 A1 WO 2023240668A1 CN 2022100766 W CN2022100766 W CN 2022100766W WO 2023240668 A1 WO2023240668 A1 WO 2023240668A1
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parts
polyether polyol
environmentally friendly
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floor mat
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PCT/CN2022/100766
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French (fr)
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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
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3271—Hydroxyamines
    • C08G18/3275—Hydroxyamines containing two hydroxy groups
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3271—Hydroxyamines
    • C08G18/3278—Hydroxyamines containing at least three hydroxy groups
    • C08G18/3281—Hydroxyamines containing at least three hydroxy groups containing three hydroxy groups
    • 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
    • C08G18/4812—Mixtures of polyetherdiols with polyetherpolyols having at least three hydroxy groups
    • 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
    • C08G18/7657—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
    • 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
    • C08G18/7657—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
    • 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
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/797—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing carbodiimide and/or uretone-imine groups
    • 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
    • C08G2101/00—Manufacture of cellular products
    • 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
    • C08G2110/00—Foam properties
    • C08G2110/0041—Foam properties having specified density
    • C08G2110/0066—≥ 150kg/m3
    • 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
    • C08G2110/00—Foam properties
    • C08G2110/0083—Foam properties prepared using water as the sole blowing agent

Definitions

  • the invention relates to the technical field of automobile floor mats, and in particular to an environmentally friendly automobile floor mat material and a preparation method thereof.
  • car floor mats have functions such as water absorption, dust collection, decontamination, and sound insulation.
  • Good floor mats can block chassis noise and tire noise and improve driving comfort.
  • the materials commonly used for car floor mats in the current market are: chemical fiber, plastic and rubber. Chemical fiber floor mats have good moth resistance and corrosion resistance, but their price is high. Plastic floor mats are cheap, but their shortcomings are also obvious. : Strong smell, slippery, and easy to harden in winter. Rubber mats are not so easy to deform when temperature changes are large, but the smell is strong.
  • polyurethane materials are rapidly expanding and promoting their production and application scope, and are playing an increasing role in various fields of the national economy.
  • many automobile manufacturers and accessories manufacturers have higher requirements for the comfort and especially the appearance of floor mats.
  • the performance of polyurethane car floor mats can be better than that of rubber type, and its cost is lower than that of rubber with the same performance.
  • the polyurethane type has a simple process and can be vulcanized at both high temperature and normal temperature. The vulcanization process can even be completed during transportation, greatly shortening the production cycle and improving production efficiency.
  • Another feature of polyurethane composite materials is that the color can be adjusted at will, which can meet the personalized needs of customers, so the current market potential is huge.
  • the purpose of the present invention is to propose an environmentally friendly automobile floor mat material and a preparation method thereof in order to solve the shortcomings existing in the prior art.
  • An environmentally friendly car floor mat material including component A and component B;
  • the raw materials of component A include: 100 parts of polymethylene polyphenyl isocyanate, 10-30 parts of carbodiimide-modified diphenylmethane diisocyanate, 5-15 parts of diphenylmethane diisocyanate;
  • the raw materials of component B include: 20-40 parts of polyether polyol I, 15-35 parts of polyether polyol II, 10-20 parts of polyether polyol III, 1-5 parts of microcrystalline cellulose, 40 parts of silicon carbide whiskers -60 parts, chain extender 1-5 parts, cross-linking agent 1-2 parts, surfactant 1-3 parts, foam stabilizer 1-2 parts, catalyst 1-2 parts, water 5-10 parts;
  • Polyether polyol I functionality is 2, hydroxyl value is 30-35 mg KOH/g;
  • Polyether polyol II functionality is 3, hydroxyl value is 200-240mg KOH/g;
  • Polyether polyol III has a functionality of 3 and a hydroxyl value of 300-350 mg KOH/g.
  • the catalyst is a tertiary amine catalyst or an organotin catalyst.
  • the chain extender is at least one of ethylene glycol, propylene glycol, 1,4-butanediol, and dipropylene glycol.
  • the cross-linking agent is at least one of glycerol, diethanolamine, triethanolamine, and trimethylolpropane.
  • the surfactant is at least one of fatty alcohol sulfate surfactants, fatty acid salt surfactants, and alkyl benzene sulfonic acid surfactants.
  • the surfactant is an alkylbenzenesulfonic acid surfactant, preferably sodium lauryl sulfate.
  • the foam stabilizer is a silicone foam stabilizer.
  • the preparation method of the above-mentioned environmentally friendly car floor mat material includes the following steps:
  • step (3) add component A raw materials to the premix ⁇ and mix evenly at 80-90°C.
  • the present invention uses polymethylene polyphenyl isocyanate, carbodiimide-modified diphenylmethane diisocyanate, and diphenylmethane diisocyanate as main materials, and is combined with polyether polyol I and polyether polyol I.
  • the foot pads made of alcohol II and polyether polyol III not only have the advantages of plastic and rubber materials, but also do not produce three wastes and can achieve clean production. At the same time, the foot pads have good mechanical properties, are resistant to permanent compression deformation, and have a long service life. .
  • the present invention is a water-based foaming agent that does not damage the atmospheric ozone layer. It is not only safer and more environmentally friendly, but also has uniform foam, forming a large amount of closed-cell foam with good thermal insulation effect. It can effectively reduce product density and has good flexibility and strain.
  • microcrystalline cellulose By using microcrystalline cellulose to wrap the silicon carbide whiskers loaded with water, when material A and material B are mixed at 80-90°C, the moisture in the silicon carbide whiskers loaded with water inside slowly overflows and mixes with material A.
  • the gas formed by the component reaction combined with the action of the micro-bubble generator, forms micro-bubbles of 100-200 ⁇ m in the system. Not only can the foaming rate be accurately controlled, but the bubbles generated are uniform and extremely uniform, while silicon carbide whiskers are Dispersed in the system to form a three-dimensional network structure, it not only has good mechanical properties, but also has excellent wear resistance.
  • the raw materials used in the present invention are environmentally friendly, no three wastes are produced, and clean production is completely achieved.
  • the material for manufacturing automobile floor mats has the advantages of PVC and rubber materials while eliminating their shortcomings, with low cost, no odor, and fully achieves Automotive interior material standards.
  • An environmentally friendly car floor mat material including component A and component B;
  • the raw materials of component A include: 100kg of polymethylene polyphenyl isocyanate, 10kg of carbodiimide-modified diphenylmethane diisocyanate, and 5kg of diphenylmethane diisocyanate;
  • Component B raw materials include: polyether polyol I 20kg, polyether polyol II 15kg, polyether polyol III 10kg, microcrystalline cellulose 1kg, silicon carbide whiskers 40kg, ethylene glycol 1kg, glycerin 1kg, dodecyl fat Alcohol polyoxyethylene ether ammonium sulfate 1kg, polysiloxane-polyether foam stabilizer 1kg, dibutyltin dilaurate 1kg, water 5kg;
  • Polyether polyol I functionality is 2, hydroxyl value is 30 mg KOH/g;
  • Polyether polyol II functionality is 3, hydroxyl value is 200 mg KOH/g;
  • Polyether polyol III has a functionality of 3 and a hydroxyl value of 300 mg KOH/g.
  • the preparation method of the above-mentioned environmentally friendly car floor mat material includes the following steps:
  • An environmentally friendly car floor mat material including component A and component B;
  • the raw materials of component A include: 100kg of polymethylene polyphenyl isocyanate, 30kg of carbodiimide-modified diphenylmethane diisocyanate, and 15kg of diphenylmethane diisocyanate;
  • Component B raw materials include: polyether polyol I 40kg, polyether polyol II 35kg, polyether polyol III 20kg, microcrystalline cellulose 5kg, silicon carbide whiskers 60kg, propylene glycol 5kg, diethanolamine 2kg, fatty acid methyl ester sulfonate 3kg salt, 2kg polysiloxane-polyether foam stabilizer, 2kg N-methylmorpholine, 10kg water;
  • Polyether polyol I functionality is 2, hydroxyl value is 35 mg KOH/g;
  • Polyether polyol II functionality is 3, hydroxyl value is 240 mg KOH/g;
  • Polyether polyol III has a functionality of 3 and a hydroxyl value of 350 mg KOH/g.
  • the preparation method of the above-mentioned environmentally friendly car floor mat material includes the following steps:
  • An environmentally friendly car floor mat material including component A and component B;
  • Component A raw materials include: polymethylene polyphenyl isocyanate 100kg, carbodiimide modified diphenylmethane diisocyanate 15kg, diphenylmethane diisocyanate 12kg;
  • Component B raw materials include: polyether polyol I 25kg, polyether polyol II 30kg, polyether polyol III 12kg, microcrystalline cellulose 4kg, silicon carbide whiskers 45kg, 1,4-butanediol 4kg, triethanolamine 1.3kg, fatty alcohol ammonium sulfate 2.5kg, polysiloxane-polyether foam stabilizer 1.3kg, bis-(2-dimethylaminoethyl) ether 1.2kg, water 8kg;
  • Polyether polyol I has a functionality of 2 and a hydroxyl value of 34 mg KOH/g;
  • Polyether polyol II functionality is 3, hydroxyl value is 210 mg KOH/g;
  • Polyether polyol III has a functionality of 3 and a hydroxyl value of 345 mg KOH/g.
  • the preparation method of the above-mentioned environmentally friendly car floor mat material includes the following steps:
  • An environmentally friendly car floor mat material including component A and component B;
  • the raw materials of component A include: 100kg of polymethylene polyphenyl isocyanate, 25kg of carbodiimide-modified diphenylmethane diisocyanate, 8kg of diphenylmethane diisocyanate;
  • the raw materials of component B include: polyether polyol I 35kg, polyether polyol II 20kg, polyether polyol III 18kg, microcrystalline cellulose 2kg, silicon carbide whiskers 55kg, dipropylene glycol 2kg, glycerin 0.7kg, triglyceride 1kg ethanolamine, 1.5kg ethoxylated fatty acid methyl ester, 1.7kg polysiloxane-polyether foam stabilizer, 1.8kg pentamethyldipropylenediamine, 6kg water;
  • Polyether polyol I functionality is 2, hydroxyl value is 32 mg KOH/g;
  • Polyether polyol II functionality is 3, hydroxyl value is 230 mg KOH/g;
  • Polyether polyol III has a functionality of 3 and a hydroxyl value of 315 mg KOH/g.
  • the preparation method of the above-mentioned environmentally friendly car floor mat material includes the following steps:
  • An environmentally friendly car floor mat material including component A and component B;
  • the raw materials of component A include: 100kg of polymethylene polyphenyl isocyanate, 20kg of carbodiimide-modified diphenylmethane diisocyanate, and 10kg of diphenylmethane diisocyanate;
  • the raw materials of component B include: polyether polyol I 30kg, polyether polyol II 25kg, polyether polyol III 15kg, microcrystalline cellulose 3kg, silicon carbide whiskers 50kg, 1,4-butanediol 1kg, one shrinkage 2kg dipropylene glycol, 1.5kg trimethylolpropane, 2kg sodium lauryl sulfate, 1.5kg polysiloxane-polyether foam stabilizer, 0.5kg bis(dimethylaminoethyl) ether, triethylene glycol Amine 1kg, water 7kg;
  • Polyether polyol I functionality is 2, hydroxyl value is 33 mg KOH/g;
  • Polyether polyol II functionality is 3, hydroxyl value is 220 mg KOH/g;
  • Polyether polyol III has a functionality of 3 and a hydroxyl value of 333 mg KOH/g.
  • the preparation method of the above-mentioned environmentally friendly car floor mat material includes the following steps:
  • An environmentally friendly car floor mat material including component A and component B;
  • the raw materials of component A include: 100kg of polymethylene polyphenyl isocyanate, 20kg of carbodiimide-modified diphenylmethane diisocyanate, and 10kg of diphenylmethane diisocyanate;
  • the raw materials of component B include: polyether polyol I 30kg, polyether polyol II 25kg, polyether polyol III 15kg, microcrystalline cellulose 3kg, silicon carbide whiskers 50kg, 1,4-butanediol 1kg, one shrinkage 2kg dipropylene glycol, 1.5kg trimethylolpropane, 2kg sodium lauryl sulfate, 1.5kg polysiloxane-polyether foam stabilizer, 0.5kg bis(dimethylaminoethyl) ether, triethylene glycol Amine 1kg, water 7kg;
  • Polyether polyol I functionality is 2, hydroxyl value is 33 mg KOH/g;
  • Polyether polyol II functionality is 3, hydroxyl value is 220 mg KOH/g;
  • Polyether polyol III has a functionality of 3 and a hydroxyl value of 333 mg KOH/g.
  • the preparation method of the above-mentioned environmentally friendly car floor mat material includes the following steps:
  • An environmentally friendly car floor mat material including component A and component B;
  • the raw materials of component A include: 100kg of polymethylene polyphenyl isocyanate, 20kg of carbodiimide-modified diphenylmethane diisocyanate, and 10kg of diphenylmethane diisocyanate;
  • the raw materials of component B include: polyether polyol I 30kg, polyether polyol II 25kg, polyether polyol III 15kg, microcrystalline cellulose 3kg, silicon carbide whiskers 50kg, 1,4-butanediol 1kg, one shrinkage 2kg dipropylene glycol, 1.5kg trimethylolpropane, 2kg sodium lauryl sulfate, 1.5kg polysiloxane-polyether foam stabilizer, 0.5kg bis(dimethylaminoethyl) ether, triethylene glycol Amine 1kg, water 7kg;
  • Polyether polyol I functionality is 2, hydroxyl value is 33 mg KOH/g;
  • Polyether polyol II functionality is 3, hydroxyl value is 220 mg KOH/g;
  • Polyether polyol III has a functionality of 3 and a hydroxyl value of 333 mg KOH/g.
  • the preparation method of the above-mentioned environmentally friendly car floor mat material includes the following steps:
  • Example 5 The environmentally friendly car floor mat materials obtained in Example 5 and Comparative Examples 1-2 were tested for comparative performance, as follows:
  • Example 5 Comparative example 1 Comparative example 2 Testing standards Density, g/cm 3 0.65 0.77 0.73 / Shore A hardness 54 63 58 GB/T531-2008 Breaking strength, Mpa 6.0 4.3 5.2 GB/T10654-2001 Elongation at break, % 845 573 659 GB/T10654-2001 Compression set,% twenty one 34 30 GB/T10653-2001
  • DIN abrasion test Test Shaopol (DIN) abrasion according to GB/T9867-2008. Using an electronic specific gravity balance, first measure the mass M 1 of the standard model in the air, and then measure the model density ⁇ . Then place the sample on the DIN abrasion tester for abrasion testing, and place the sample after the experiment on the electronic specific gravity balance. Measure weight M 2 .

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

一种环保汽车脚垫材料，包括A组分与B组分；按重量份，A组分原料包括：多亚甲基多苯基异氰酸酯100，碳化二亚胺改性二苯基甲烷二异氰酸酯10-30，二苯基甲烷二异氰酸酯5-15；B组分原料包括：聚醚多元醇I 20-40，聚醚多元醇II 15-35，聚醚多元醇III 10-20，微晶纤维素1-5，碳化硅晶须40-60，扩链剂1-5，交联剂1-2，表面活性剂1-3，泡沫稳定剂1-2，催化剂1-2；聚醚多元醇I，官能度为2，羟值为30-35mg KOH/g；聚醚多元醇II，官能度为3，羟值为200-240mg KOH/g；聚醚多元醇III，官能度为3，羟值为300-350mg KOH/g。

Description

一种环保汽车脚垫材料及其制备方法 技术领域
本发明涉及汽车脚垫技术领域，尤其涉及一种环保汽车脚垫材料及其制备方法。
背景技术
随着经济建设的发展，人们的生活水平的提高，汽车已经成为一种不可替代的交通工具，人们在汽车内度过的时间也越来越长，对于汽车内饰的美观性及乘坐的舒适性要求也越来越高，在汽车内铺设脚垫已是必备配饰，其具有美化整部汽车内部结构及增加乘坐舒适性的效果。
汽车脚垫作为汽车内饰部件之一，具有集吸水、吸尘、去污、隔音等功能。好的脚垫可以阻止底盘噪音和轮胎噪音，提高驾驶舒适性。目前市场汽车脚垫通常用的材料为：化纤、塑料及橡胶，其中化纤脚垫有良好的耐蛀、耐腐蚀性能，但是其价格高昂，而塑料脚垫的价格便宜，但是其缺点也同样明显：味道重，会滑动，冬天容易变硬，橡胶脚垫在温度变化比较大的情况下不那么容易变形，但是味道较重。
目前聚氨酯材料凭借其优越的性能，其生产和应用范围正在迅速扩大和推广，已在国民经济的各个领域中发挥着越来越大的作用。近年来，许多汽车生产及配件厂家对脚垫的舒适性尤其外观有了更高的要求，聚氨酯型汽车脚垫性能可以比橡胶型做得更好，而其成本比相同性能橡胶更低，同时聚氨酯型工艺简单，既可高温硫化又可以常温硫化，甚至在运输过程中即可完成硫化过程，大大缩短生产周期，提高生产效率。聚氨酯型组合料还有一个特点就是可以随意调节颜色，能够满足客户个性化的需求，因此目前市场潜力巨大。
但目前聚氨酯用作汽车脚垫材料时，其耐磨性欠佳，保温效果差，而且耐 永久压缩变形差，导致使用寿命受限，成为目前制约其发展的技术问题。
发明内容
本发明的目的是为了解决现有技术中存在的缺点，而提出的一种环保汽车脚垫材料及其制备方法。
一种环保汽车脚垫材料，包括A组分与B组分；
按重量份，
A组分原料包括：多亚甲基多苯基异氰酸酯100份，碳化二亚胺改性二苯基甲烷二异氰酸酯10-30份，二苯基甲烷二异氰酸酯5-15份；
B组分原料包括：聚醚多元醇I 20-40份，聚醚多元醇II 15-35份，聚醚多元醇III 10-20份，微晶纤维素1-5份，碳化硅晶须40-60份，扩链剂1-5份，交联剂1-2份，表面活性剂1-3份，泡沫稳定剂1-2份，催化剂1-2份，水5-10份；
聚醚多元醇I，官能度为2，羟值为30-35mg KOH/g；
聚醚多元醇II，官能度为3，羟值为200-240mg KOH/g；
聚醚多元醇III，官能度为3，羟值为300-350mg KOH/g。
优选地，催化剂为叔胺类催化剂或有机锡类催化剂。
优选地，扩链剂为乙二醇、丙二醇、1,4-丁二醇、一缩二丙二醇中至少一种。
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。
优选地，表面活性剂为脂肪醇硫酸盐类表面活性剂、脂肪酸盐类表面活性剂、烷基苯磺酸表面活性剂中至少一种。
更优选地，表面活性剂为烷基苯磺酸表面活性剂，优选为十二烷基硫酸钠。
优选地，泡沫稳定剂为有机硅泡沫稳定剂。
上述环保汽车脚垫材料的制备方法，包括如下步骤：
(1)将微晶纤维素溶胀于氢氧化钠溶液中得到预处理微晶纤维素；将水加 入至碳化硅晶须中搅拌均匀，再加入至流化床中，采用预处理微晶纤维素包裹，得到预混料α；
(2)将预混料α与剩余B组分原料混合均匀得到预混料γ；
(3)向预混料γ中加入A组分原料混合均匀，开动微细气泡发生器产生100-200μm的微细气泡，加入模具中定型得到环保汽车脚垫材料。
优选地，步骤(3)中，向预混料γ中加入A组分原料，80-90℃混合均匀。
本发明的技术效果如下所示：
(1)本发明采用多亚甲基多苯基异氰酸酯、碳化二亚胺改性二苯基甲烷二异氰酸酯、二苯基甲烷二异氰酸酯复配为主料，配合聚醚多元醇I、聚醚多元醇II、聚醚多元醇III制备的脚垫，不仅兼具塑料、橡胶材料的优点，而且没有三废产生，可做到清洁化生产，同时脚垫力学性能好，耐永久压缩变形，使用寿命长。
(2)本发明为水基发泡剂，不破坏大气臭氧层，不仅更为安全环保，而且泡沫均匀，形成大量闭孔泡沫，保温效果好，同时可有效降低产品密度，并且具有良好的柔性应变特性，用作汽车脚垫，可大面积柔顺贴合在汽车内，使用舒适度佳。
(3)通过采用微晶纤维素对负载有水的碳化硅晶须包裹，当A物料与B物料在80-90℃混合时，内部负载有水的碳化硅晶须的水分缓慢溢出，与A组分反应形成的气体，配合微细气泡发生器作用，在体系中形成100-200μm的微细气泡，不仅可准确控制发泡速率，同时产生的气泡均匀，均一度极高，而碳化硅晶须则分散在体系中形成三维网络结构，不仅力学性能好，同时耐磨性能极佳。
本发明所采用的原料环保，没有三废产生，完全做到清洁化生产，并且制 造汽车脚垫材料在兼具PVC、橡胶材料的优点的同时，摒除了其缺点，成本低，无异味，完全达到汽车内饰材料标准。
具体实施方式
下面结合具体实施例对本发明作进一步解说。
实施例1
一种环保汽车脚垫材料，包括A组分与B组分；
A组分原料包括：多亚甲基多苯基异氰酸酯100kg，碳化二亚胺改性二苯基甲烷二异氰酸酯10kg，二苯基甲烷二异氰酸酯5kg；
B组分原料包括：聚醚多元醇I 20kg，聚醚多元醇II 15kg，聚醚多元醇III 10kg，微晶纤维素1kg，碳化硅晶须40kg，乙二醇1kg，甘油1kg，十二脂肪醇聚氧乙烯醚硫酸铵1kg，聚硅氧烷-聚醚稳泡剂1kg，二月桂酸二丁基锡1kg，水5kg；
聚醚多元醇I，官能度为2，羟值为30mg KOH/g；
聚醚多元醇II，官能度为3，羟值为200mg KOH/g；
聚醚多元醇III，官能度为3，羟值为300mg KOH/g。
上述环保汽车脚垫材料的制备方法，包括如下步骤：
(1)将微晶纤维素溶胀于氢氧化钠溶液中得到预处理微晶纤维素；将水加入至碳化硅晶须中搅拌均匀，再加入至流化床中，采用预处理微晶纤维素包裹，得到预混料α；
(2)将预混料α与剩余B组分原料混合均匀得到预混料γ；
(3)向预混料γ中加入A组分原料，80℃混合均匀，开动微细气泡发生器产生100-200μm的微细气泡，加入模具中定型得到环保汽车脚垫材料。
实施例2
一种环保汽车脚垫材料，包括A组分与B组分；
A组分原料包括：多亚甲基多苯基异氰酸酯100kg，碳化二亚胺改性二苯基甲烷二异氰酸酯30kg，二苯基甲烷二异氰酸酯15kg；
B组分原料包括：聚醚多元醇I 40kg，聚醚多元醇II 35kg，聚醚多元醇III 20kg，微晶纤维素5kg，碳化硅晶须60kg，丙二醇5kg，二乙醇胺2kg，脂肪酸甲酯磺酸盐3kg，聚硅氧烷-聚醚稳泡剂2kg，N-甲基吗啉2kg，水10kg；
聚醚多元醇I，官能度为2，羟值为35mg KOH/g；
聚醚多元醇II，官能度为3，羟值为240mg KOH/g；
聚醚多元醇III，官能度为3，羟值为350mg KOH/g。
上述环保汽车脚垫材料的制备方法，包括如下步骤：
(1)将微晶纤维素溶胀于氢氧化钠溶液中得到预处理微晶纤维素；将水加入至碳化硅晶须中搅拌均匀，再加入至流化床中，采用预处理微晶纤维素包裹，得到预混料α；
(2)将预混料α与剩余B组分原料混合均匀得到预混料γ；
(3)向预混料γ中加入A组分原料，90℃混合均匀，开动微细气泡发生器产生100-200μm的微细气泡，加入模具中定型得到环保汽车脚垫材料。
实施例3
一种环保汽车脚垫材料，包括A组分与B组分；
A组分原料包括：多亚甲基多苯基异氰酸酯100kg，碳化二亚胺改性二苯基甲烷二异氰酸酯15kg，二苯基甲烷二异氰酸酯12kg；
B组分原料包括：聚醚多元醇I 25kg，聚醚多元醇II 30kg，聚醚多元醇III 12kg，微晶纤维素4kg，碳化硅晶须45kg，1,4-丁二醇4kg，三乙醇胺1.3kg，脂肪醇硫酸铵2.5kg，聚硅氧烷-聚醚稳泡剂1.3kg，双-(2-二甲氨基乙基)醚1.2kg， 水8kg；
聚醚多元醇I，官能度为2，羟值为34mg KOH/g；
聚醚多元醇II，官能度为3，羟值为210mg KOH/g；
聚醚多元醇III，官能度为3，羟值为345mg KOH/g。
上述环保汽车脚垫材料的制备方法，包括如下步骤：
(1)将微晶纤维素溶胀于氢氧化钠溶液中得到预处理微晶纤维素；将水加入至碳化硅晶须中搅拌均匀，再加入至流化床中，采用预处理微晶纤维素包裹，得到预混料α；
(2)将预混料α与剩余B组分原料混合均匀得到预混料γ；
(3)向预混料γ中加入A组分原料，82℃混合均匀，开动微细气泡发生器产生100-200μm的微细气泡，加入模具中定型得到环保汽车脚垫材料。
实施例4
一种环保汽车脚垫材料，包括A组分与B组分；
A组分原料包括：多亚甲基多苯基异氰酸酯100kg，碳化二亚胺改性二苯基甲烷二异氰酸酯25kg，二苯基甲烷二异氰酸酯8kg；
B组分原料包括：聚醚多元醇I 35kg，聚醚多元醇II 20kg，聚醚多元醇III 18kg，微晶纤维素2kg，碳化硅晶须55kg，一缩二丙二醇2kg，甘油0.7kg，三乙醇胺1kg，乙氧基化脂肪酸甲酯1.5kg，聚硅氧烷-聚醚稳泡剂1.7kg，五甲基二亚丙基二胺1.8kg，水6kg；
聚醚多元醇I，官能度为2，羟值为32mg KOH/g；
聚醚多元醇II，官能度为3，羟值为230mg KOH/g；
聚醚多元醇III，官能度为3，羟值为315mg KOH/g。
上述环保汽车脚垫材料的制备方法，包括如下步骤：
(1)将微晶纤维素溶胀于氢氧化钠溶液中得到预处理微晶纤维素；将水加入至碳化硅晶须中搅拌均匀，再加入至流化床中，采用预处理微晶纤维素包裹，得到预混料α；
(2)将预混料α与剩余B组分原料混合均匀得到预混料γ；
(3)向预混料γ中加入A组分原料，88℃混合均匀，开动微细气泡发生器产生100-200μm的微细气泡，加入模具中定型得到环保汽车脚垫材料。
实施例5
一种环保汽车脚垫材料，包括A组分与B组分；
A组分原料包括：多亚甲基多苯基异氰酸酯100kg，碳化二亚胺改性二苯基甲烷二异氰酸酯20kg，二苯基甲烷二异氰酸酯10kg；
B组分原料包括：聚醚多元醇I 30kg，聚醚多元醇II 25kg，聚醚多元醇III 15kg，微晶纤维素3kg，碳化硅晶须50kg，1,4-丁二醇1kg，一缩二丙二醇2kg，三羟甲基丙烷1.5kg，十二烷基硫酸钠2kg，聚硅氧烷-聚醚稳泡剂1.5kg，双(二甲胺基乙基)醚0.5kg，三亚乙基二胺1kg，水7kg；
聚醚多元醇I，官能度为2，羟值为33mg KOH/g；
聚醚多元醇II，官能度为3，羟值为220mg KOH/g；
聚醚多元醇III，官能度为3，羟值为333mg KOH/g。
上述环保汽车脚垫材料的制备方法，包括如下步骤：
(1)将微晶纤维素溶胀于氢氧化钠溶液中得到预处理微晶纤维素；将水加入至碳化硅晶须中搅拌均匀，再加入至流化床中，采用预处理微晶纤维素包裹，得到预混料α；
(2)将预混料α与剩余B组分原料混合均匀得到预混料γ；
(3)向预混料γ中加入A组分原料，85℃混合均匀，开动微细气泡发生器 产生100-200μm的微细气泡，加入模具中定型得到环保汽车脚垫材料。
对比例1
一种环保汽车脚垫材料，包括A组分与B组分；
A组分原料包括：多亚甲基多苯基异氰酸酯100kg，碳化二亚胺改性二苯基甲烷二异氰酸酯20kg，二苯基甲烷二异氰酸酯10kg；
B组分原料包括：聚醚多元醇I 30kg，聚醚多元醇II 25kg，聚醚多元醇III 15kg，微晶纤维素3kg，碳化硅晶须50kg，1,4-丁二醇1kg，一缩二丙二醇2kg，三羟甲基丙烷1.5kg，十二烷基硫酸钠2kg，聚硅氧烷-聚醚稳泡剂1.5kg，双(二甲胺基乙基)醚0.5kg，三亚乙基二胺1kg，水7kg；
聚醚多元醇I，官能度为2，羟值为33mg KOH/g；
聚醚多元醇II，官能度为3，羟值为220mg KOH/g；
聚醚多元醇III，官能度为3，羟值为333mg KOH/g。
上述环保汽车脚垫材料的制备方法，包括如下步骤：
(1)将B组分原料混合均匀得到预混料γ；
(2)向预混料γ中加入A组分原料，85℃混合均匀，开动微细气泡发生器产生100-200μm的微细气泡，加入模具中定型得到环保汽车脚垫材料。
对比例2
一种环保汽车脚垫材料，包括A组分与B组分；
A组分原料包括：多亚甲基多苯基异氰酸酯100kg，碳化二亚胺改性二苯基甲烷二异氰酸酯20kg，二苯基甲烷二异氰酸酯10kg；
B组分原料包括：聚醚多元醇I 30kg，聚醚多元醇II 25kg，聚醚多元醇III 15kg，微晶纤维素3kg，碳化硅晶须50kg，1,4-丁二醇1kg，一缩二丙二醇2kg，三羟甲基丙烷1.5kg，十二烷基硫酸钠2kg，聚硅氧烷-聚醚稳泡剂1.5kg，双(二 甲胺基乙基)醚0.5kg，三亚乙基二胺1kg，水7kg；
聚醚多元醇I，官能度为2，羟值为33mg KOH/g；
聚醚多元醇II，官能度为3，羟值为220mg KOH/g；
聚醚多元醇III，官能度为3，羟值为333mg KOH/g。
上述环保汽车脚垫材料的制备方法，包括如下步骤：
(1)将微晶纤维素溶胀于氢氧化钠溶液中得到预处理微晶纤维素；将水加入至碳化硅晶须中搅拌均匀，再加入至流化床中，采用预处理微晶纤维素包裹，得到预混料α；
(2)将预混料α与剩余B组分原料混合均匀得到预混料γ；
(3)向预混料γ中加入A组分原料，85℃混合均匀，加入模具中定型得到环保汽车脚垫材料。
将实施例5和对比例1-2所得环保汽车脚垫材料进行对比性能测试，具体如下：
1、机械性能测试
  实施例5 对比例1 对比例2 检测标准
密度，g/cm 3 0.65 0.77 0.73 /
邵A硬度 54 63 58 GB/T531-2008
拉断强度，Mpa 6.0 4.3 5.2 GB/T10654-2001
拉断伸长率，％ 845 573 659 GB/T10654-2001
压缩永久变形，％ 21 34 30 GB/T10653-2001
2、耐磨、回弹和导热系数测试
2.1 DIN磨耗测试：按GB/T9867-2008测试邵坡尔(DIN)磨耗。利用电子比重天平，先测出标准式样在空气中的质量M 1，再测出式样密度ρ，然后将试样置于DIN磨耗测试仪上进行磨耗测试，将实验后试样至于电子比重天平上测 重M 2。
2.2利用模压的标准回弹试样在回弹测试仪上进行测试。
2.3选择某品牌汽车，汽车驾驶位地面选择一点，将分贝仪固定在该位置，关闭车门，启动发动机，使发动机转速为3000rpm，读取分贝仪数值为A1；然后在汽车驾驶位铺设各组脚垫试样，在脚垫上选择上述相同位置，将分贝仪固定在该位置，关闭车门，启动发动机，使发动机转速为3000rpm，读取分贝仪数值为An，A1与An的差值即为隔音分贝差。
  实施例5 对比例1 对比例2
DIN相对磨耗体积，mm 3 22 30 27
冲击回弹，％ 54 42 50
隔音分贝差，dB 11 6 8
导热系数，mW/(m·K) 16.3 19.2 18.5
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。

Claims (9)

  1. 一种环保汽车脚垫材料，其特征在于，包括A组分与B组分；
    按重量份，
    A组分原料包括：多亚甲基多苯基异氰酸酯100份，碳化二亚胺改性二苯基甲烷二异氰酸酯10-30份，二苯基甲烷二异氰酸酯5-15份；
    B组分原料包括：聚醚多元醇I 20-40份，聚醚多元醇II 15-35份，聚醚多元醇III 10-20份，微晶纤维素1-5份，碳化硅晶须40-60份，扩链剂1-5份，交联剂1-2份，表面活性剂1-3份，泡沫稳定剂1-2份，催化剂1-2份，水5-10份；
    聚醚多元醇I，官能度为2，羟值为30-35mg KOH/g；
    聚醚多元醇II，官能度为3，羟值为200-240mg KOH/g；
    聚醚多元醇III，官能度为3，羟值为300-350mg KOH/g。
  2. 根据权利要求1所述环保汽车脚垫材料，其特征在于，催化剂为叔胺类催化剂或有机锡类催化剂。
  3. 根据权利要求1所述环保汽车脚垫材料，其特征在于，扩链剂为乙二醇、丙二醇、1,4-丁二醇、一缩二丙二醇中至少一种。
  4. 根据权利要求1所述环保汽车脚垫材料，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。
  5. 根据权利要求1所述环保汽车脚垫材料，其特征在于，表面活性剂为脂肪醇硫酸盐类表面活性剂、脂肪酸盐类表面活性剂、烷基苯磺酸表面活性剂中至少一种。
  6. 根据权利要求1所述环保汽车脚垫材料，其特征在于，表面活性剂为烷基苯磺酸表面活性剂，优选为十二烷基硫酸钠。
  7. 根据权利要求1所述环保汽车脚垫材料，其特征在于，泡沫稳定剂为有机硅泡沫稳定剂。
  8. 一种如权利要求1-7任一项所述环保汽车脚垫材料的制备方法，其特征在于，包括如下步骤：
    (1)将微晶纤维素溶胀于氢氧化钠溶液中得到预处理微晶纤维素；将水加入至碳化硅晶须中搅拌均匀，再加入至流化床中，采用预处理微晶纤维素包裹，得到预混料α；
    (2)将预混料α与剩余B组分原料混合均匀得到预混料γ；
    (3)向预混料γ中加入A组分原料混合均匀，开动微细气泡发生器产生100-200μm的微细气泡，加入模具中定型得到环保汽车脚垫材料。
  9. 根据权利要求8所述环保汽车脚垫材料的制备方法，其特征在于，步骤(3)中，向预混料γ中加入A组分原料，80-90℃混合均匀。
PCT/CN2022/100766 2022-06-17 2022-06-23 一种环保汽车脚垫材料及其制备方法 WO2023240668A1 (zh)

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