CN108047421A - A kind of automotive trim superfine fiber chemical leather resin and preparation method thereof - Google Patents

A kind of automotive trim superfine fiber chemical leather resin and preparation method thereof Download PDF

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Publication number
CN108047421A
CN108047421A CN201711260861.3A CN201711260861A CN108047421A CN 108047421 A CN108047421 A CN 108047421A CN 201711260861 A CN201711260861 A CN 201711260861A CN 108047421 A CN108047421 A CN 108047421A
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automotive trim
superfine fiber
fiber chemical
chemical leather
mol
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CN108047421B (en
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钱建中
钱洪祥
胡大勇
钱迪
范汉清
仇菊平
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Fujian Rehui New Materials Co Ltd
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Fujian Rehui New Materials Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/48Polyethers
    • C08G18/4854Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08Processes
    • C08G18/10Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/42Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4236Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
    • C08G18/4238Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/42Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/44Polycarbonates
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/61Polysiloxanes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72Polyisocyanates or polyisothiocyanates
    • C08G18/74Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group

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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

The present invention relates to a kind of automotive trim superfine fiber chemical leather resin and preparation method thereof, the polyurethane resin includes the component of following weight percent content:Modified polytetrahydrofuran diol 4.0%~9.0%, makrolon caprolactone diol 6.5%~12.0%, polyadipate type polyester polyol 2.3%~4.0%, diphenyl methane 4,4 ‵ diisocyanate 8.0%~12.0%, ethylene glycol 0.7%~1.6%, hydroquinone double (β ethoxys) ether 1.2%~2.5%, dimethyl silicone polymer dihydric alcohol 0.5%~1.0%, N, N dimethylformamides 65%~70%.Superfine fiber synthetic leather base cloth is detected according to method specified in " 4,194 2011 automobile using Synthetic Leathers of QB/T " made of the resin, and the performances such as heat-resistant aging, cold resistance and folding fastness meet the requirement of automotive trim synthetic leather.

Description

A kind of automotive trim superfine fiber chemical leather resin and preparation method thereof
Technical field
The present invention relates to polyurethane resin preparing technical field, more specifically, being related to a kind of automotive trim with ultra-fine fibre Tie up synthetic leather resin and preparation method thereof.
Background technology
Superfine fiber chemical leather is surpassed using the pencil similar to the 26S Proteasome Structure and Function of pencil collagenous fibres in natural leather The high density non-woven cloth with three-dimensional net structure is made in fine fibre, fills with the polyurethane tree of high-quality open type microcellular structure The high-grade emulated artificial leather for exactly liking natural leather is made with reference to composite cover processing technology for fat.No matter is superfine fiber chemical leather From internal microstructure, or appearance tactile impression and physical characteristic etc., it can compare favourably with advanced natural leather, almost have Natural leather all characteristic and advantage, and in mechanical strength, chemical-resistance, sucting wet air permeability, mass uniformity, guarantor's type Property, automation cut out flexibility (adaptability) of operation and waterproof, anti-mildew etc. better than natural leather.
With the improvement of living standards and living-pattern preservation, the chance of people by bus is more and more, to automotive trim The quality of leather proposes new, higher requirement, and since natural leather resource is limited, environment damage ratio is tighter in process Weight, content of beary metal is easily exceeded, and utilization rate is low in process, so its cost is generally costly, therefore foreign enterprise through the country Industry tries to explore the manufacturing that synthetic leather is applied to automotive trim.Automotive trim synthetic leather is low temperature resistant in high temperature resistant, fire-retardant, Wear-resisting, corrosion-resistant, environmentally friendly, comfort level etc. has very high requirement, all very excellent superfine fibre synthesis of various aspects of performance Leather is just increasingly used in automotive trim.
Under the irradiation of summer sunlight strong, the temperature in automobile can be very high, and high temperature can cause the performance of synthetic leather drastically to decline, The aging for causing leather piece product is even damaged, therefore requirement of the automotive trim leather to heat resistance is higher.In the cold winter Season, low temperature can cause synthetic leather leather surface to be hardened, and the elastic recovery and comfort level of leather are all deteriorated therewith.Therefore develop a kind of resistance to High temperature, all relatively good automobile leather of resistance to low temperature have become the demand in market with superfine fiber chemical leather.
The content of the invention
One of problem to be solved by this invention is to provide a kind of high temperature resistant, and all preferable automotive trim of resistance to low temperature is used Superfine fiber chemical leather resin.
The second technical problem to be solved by the present invention is to provide a kind of above-mentioned automotive trim superfine fiber chemical leather The preparation method of resin.
The technical problems to be solved by the invention can be achieved through the following technical solutions:
A kind of automotive trim superfine fiber chemical leather resin, is made of the raw material of following mass percent:
In the preferred embodiment of the present invention, the modification polytetrahydrofuran diol is taken by tetrahydrofuran and side group The modification polytetrahydrofuran diol being copolymerized for tetrahydrofuran.
In the preferred embodiment of the present invention, the modified polytetrahydrofuran diol be number-average molecular weight for 2000~ The mixture of one or both of the modification polytetrahydrofuran diol of 4000g/mol.
In the preferred embodiment of the present invention, the makrolon-caprolactone diol is carbonic ester and caprolactone diol Polyol, the mass ratio of wherein carbonic ester and caprolactone diol is:80/20, molecular weight 2000g/mol.
In the preferred embodiment of the present invention, the molar ratio of ethylene glycol and hydroquinone-bis- (beta-hydroxyethyls) ether is 1/1 ~4/1.
In the preferred embodiment of the present invention, dimethyl silicone polymer dihydric alcohol is a kind of number-average molecular weight 2000- 5000g/mol, the polydimethylsiloxanediols diols containing 2 degrees of functionality.
In the preferred embodiment of the present invention, the polyadipate type polyester polyol is that number-average molecular weight is The polybutylene glyool adipate of 2000g/mol or number-average molecular weight 2000g/mol -3 methyl-1 of polyadipate, 5 penta The mixture of one or both of glycol esterdiol.
Wherein polyadipate type polyester polyol accounts for the ratio control of polyalcohol total amount in formula between 10-20%.
A kind of preparation method of automotive trim superfine fiber chemical leather resin as second aspect of the present invention, including with Lower step:
(1) makrolon-caprolactone diol, polyadipate type polyester polyol, poly dimethyl silicon are put into a kettle Oxygen alkane dihydric alcohol and n,N-Dimethylformamide, input part diphenyl methane -4 after stirring 30 minutes, 4 '-diisocyanate, It is 0.95 to control isocyanate group and the molar ratio of hydroxyl in reaction system:1~0.98:1, reaction temperature is controlled 75~85 DEG C, the control of reaction system solid content is 50%~65%, when reaction system viscosity reaches 50Pa.s~200Pas/50 DEG C, the Single step reaction terminates;
(2) a certain amount of solvent n,N-Dimethylformamide, modified polytetrahydrofuran diol, second two are put into a kettle Alcohol, hydroquinone-bis- (beta-hydroxyethyls) ether put into diphenyl methane -4 of metering, 4 '-diisocyanate, control after stirring evenly Isocyanate group and the molar ratio of hydroxyl are 0.94 in reaction system processed:1~0.97:1, the solid content of reaction system is controlled 40 ~50%, after reacting 1~2h, diphenyl methane -4 of surplus are added portionwise at 75~85 DEG C in reaction temperature control control, 4 '-diisocyanate and remaining n,N-Dimethylformamide until final viscosity reaches 50~100Pas/25 DEG C, terminate Reaction.
A kind of interior leather for automobiles of the present invention has selected makrolon-caprolactone diol to make with superfine fiber chemical leather resin It is because this copolymerization esterdiol is remaining the excellent hydrolytic resistance of polycarbonate glycol for one kind of soft segment polyalcohol Its low temperature resistant the shortcomings that deflecting poor performance is improved while the advantages that energy, thermal stability, weatherability and wearability, and uses this The feel ratio of resin is directly with polycarbonate glycol more soft comfortable made from kind copolymerization esterdiol.Being modified erythritan is What the tetrahydrofuran substituted by tetrahydrofuran and side group was copolymerized, due to the introducing of side group, crystallinity compares PolyTHF Glycol is weak, makes it on the premise of unique physical property with erythritan, and with better low temperature resistant flexural property. The advantages that polymethyl siloxane has good weatherability, and low-temperature flexibility is good, and heat-resistant stability is good, being introduced in polyurethane molecular has Machine silicon segment can not only increase the resistance to low temperature of resin, while can also further improve the feel of resin.The present invention uses Polyadipate type polyester polyol for the preferable adipic acid type polyester polyol of hydrolytic resistance, use it as raw material be in order to The difference of resin surface and internal setting rate is adjusted on the premise of resin anti-hydrolytic performance is ensured, and then adjusts resin Foam structure, using microfiber synthetic leather made from the resin feel closer to corium feel.
Polyurethane resin is a kind of block copolymerization type high-molecular compound, by soft segment (polyalcohol) and rigid chain segment (chain extender and isocyanates) forms.Soft segment and rigid chain segment have thermodynamics incompatibility matter cause to generate it is special Micro phase separation structure, wherein with the variation of microphase separation degree, mechanical property and resilience can all change.Chain extender Hydroquinone-bis- (beta-hydroxyethyl) ether is symmetry aromatic diol chain extender, and crystallinity is strong, and temperature tolerance is high.Meanwhile introduce it It makees chain extender and also improves the microphase separation degree of polyurethane resin, and then improve the low temperature resistant flexibility of polyurethane finished product Energy.
It is to make more regular same of the arrangement of hard section and soft segment in addition, the present invention uses the synthesis technology of pre-polymerization method When in turn avoid the undue concentration of hard section, polyurethane resin obtained is enable to form ideal micro phase separation structure, so The feel and physical property of resin can be embodied preferably.
Specific embodiment
With reference to specific embodiment, the present invention is described in more detail.
Embodiment 1
1st, it is formulated
2nd, preparation method
Makrolon-caprolactone diol (number-average molecular weight 2000g/mol) 76kg, polyadipate type are put into a kettle Polyester polyol (number-average molecular weight 2000g/mol) 38kg, -3 methyl-1 of polyadipate, 5 pentadiol ester glycol (number-average molecular weights 2000g/mol) 11kg, n,N-Dimethylformamide 94kg put into diphenyl methane -4,4 '-diisocyanate after stirring evenly 15.6kg, reaction temperature are controlled at 75~85 DEG C, after reacting 4~6h, when reaction system viscosity reaches 80~90Pas/50 DEG C, Modified polytetrahydrofuran diol (number-average molecular weight 2000g/mol) 76kg, ethylene glycol 13.9kg are put into a kettle, to benzene two Phenol-bis- (beta-hydroxyethyl) ether 14.8kg and n,N-Dimethylformamide 308kg, input diphenyl methane -4 after stirring evenly, 4 ' - Diisocyanate 79.3kg, reaction temperature are controlled at 75~85 DEG C, and after reacting 1~2h, the diphenylmethyl of surplus is added portionwise Alkane -4,4 '-diisocyanate and remaining n,N-Dimethylformamide, until final viscosity reaches 50~100Pas/25 DEG C, Reaction was completed.
Embodiment 2
1st, it is formulated
2nd, preparation method
Makrolon-caprolactone diol (number-average molecular weight 2000g/mol) 120kg, polyadipate are put into a kettle Type polyester polyol (number-average molecular weight 3000g/mol) 40kg, dimethyl silicone polymer dihydric alcohol (number-average molecular weight 2000g/ Mol) 10kg, n,N-Dimethylformamide 102kg, input diphenyl methane -4 after stirring evenly, 4 '-diisocyanate 19kg, Reaction temperature is controlled at 75~85 DEG C, after reacting 4~6h, when reaction system viscosity reaches 90~110Pas/50 DEG C, is being reacted Modified polytetrahydrofuran diol (number-average molecular weight 3000g/mol) 40kg, ethylene glycol 7.1kg, hydroquinone-bis- are put into kettle (beta-hydroxyethyl) ether 22.6kg and n,N-Dimethylformamide 290kg puts into diphenyl methane -4 after stirring evenly, 4 '-two is different Cyanate 58kg, reaction temperature are controlled at 75~85 DEG C, and after reacting 1~2h, diphenyl methane -4 of surplus are added portionwise, 4 '-diisocyanate and remaining n,N-Dimethylformamide until final viscosity reaches 50~100Pas/25 DEG C, terminate Reaction.
Embodiment 3
1st, it is formulated
2nd, preparation method
Makrolon-caprolactone diol (number-average molecular weight 2000g/mol) 66kg, polyadipate -3 are put into a kettle Methyl-1,5 pentadiol ester glycol (number-average molecular weight 3000g/mol) 28kg, dimethyl silicone polymer dihydric alcohol (number-average molecular weight 2000g/mol) 8kg, n,N-Dimethylformamide 114kg put into diphenyl methane -4,4 '-diisocyanate after stirring evenly 11.5kg, reaction temperature are controlled at 75~85 DEG C, and after reacting 4~6h, reaction system viscosity reaches 100~110Pas/50 DEG C When, put into modified polytetrahydrofuran diol (number-average molecular weight 2000g/mol) 94kg in a kettle, ethylene glycol 16.4kg is right Benzenediol-bis- (beta-hydroxyethyl) ether 26.2kg and n,N-Dimethylformamide 305kg, after stirring evenly put into diphenyl methane- 4,4 '-diisocyanate 106kg, reaction temperature are controlled at 75~85 DEG C, and after reacting 1~2h, the hexichol of surplus is added portionwise Methylmethane -4,4 '-diisocyanate and remaining n,N-Dimethylformamide, until final viscosity reaches 50~100Pas/ 25 DEG C, reaction was completed.
Embodiment 4
1st, it is formulated
2nd, preparation method
In a kettle put into makrolon-caprolactone diol (number-average molecular weight 2000g/mol) 100kg, polyadipate- 3 methyl-1s, 5 pentadiol ester glycol (number-average molecular weight 2000g/mol) 20kg, polybutylene glyool adipate (the equal molecule of number Measure 2000g/mol), dimethyl silicone polymer dihydric alcohol (number-average molecular weight 2000g/mol) 5.5kg, n,N-Dimethylformamide 113kg puts into diphenyl methane -4,4 '-diisocyanate 24kg after stirring evenly, reaction temperature is controlled at 75~85 DEG C, instead After answering 4~6h, when reaction system viscosity reaches 80~90Pas/50 DEG C, modified polytetrahydrofuran diol is put into a kettle (number-average molecular weight 2000g/mol) 60kg, ethylene glycol 12.4kg, hydroquinone-bis- (beta-hydroxyethyl) ether 13.2kg and N, N- bis- Methylformamide 282kg, puts into diphenyl methane -4,4 '-diisocyanate 65kg after stirring evenly, reaction temperature is controlled 75 ~85 DEG C, after reacting 1~2h, diphenyl methane -4 of surplus, 4 '-diisocyanate and remaining N, N- diformazan is added portionwise Base formamide, until final viscosity reaches 50~100Pas/25 DEG C, reaction was completed.
Embodiment 5
1st, it is formulated
2nd, preparation method
Makrolon-caprolactone diol (number-average molecular weight 2000g/mol) 95kg, polyadipate -3 are put into a kettle Methyl-1,5 pentadiol ester glycol (number-average molecular weight 3000g/mol) 25kg, dimethyl silicone polymer dihydric alcohol (number-average molecular weight 5000g/mol) 11kg, n,N-Dimethylformamide 145kg put into diphenyl methane -4,4 '-diisocyanate after stirring evenly 14kg, reaction temperature are controlled at 75~85 DEG C, after reacting 4~6h, when reaction system viscosity reaches 80~90Pas/50 DEG C, Modified polytetrahydrofuran diol (number-average molecular weight 2000g/mol) 80kg, ethylene glycol 12.2kg are put into reaction kettle, to benzene two Phenol-bis- (beta-hydroxyethyl) ether 13kg and n,N-Dimethylformamide 243kg, input diphenyl methane -4 after stirring evenly, 4 '-two Isocyanates 73kg, reaction temperature are controlled at 75~85 DEG C, and after reacting 1~2h, diphenyl methane -4 of surplus are added portionwise, 4 '-diisocyanate and remaining n,N-Dimethylformamide until final viscosity reaches 50~100Pas/25 DEG C, terminate Reaction.
The island woven fabric non-woven fabrics of Wuxi Shuangxiang Superfibers Co., Ltd.'s production is chosen in advance, by above-described embodiment In obtained polyurethane resin is impregnated, solidification, washing, superfine fiber synthetic leather base cloth is made after decrement.
Using the Polyurethane resin slurry obtained by above-described embodiment 1-5, addition auxiliary agent is deployed into impregnation work slurry, is used for Impregnation process in superfine fiber synthetic leather base cloth production, obtained base fabric is according to " QB/T4194-2011 automobile usings polyurethane closes Method specified in finished leather " detects, and what heat-resistant aging and the performances such as cold resisting type and folding fastness met A classes in the standard will It asks, the requirement of automotive trim synthetic leather can be met completely.

Claims (9)

1. a kind of automotive trim superfine fiber chemical leather resin, it is characterised in that prepared by the raw material of following weight percentage It forms:
2. a kind of automotive trim superfine fiber chemical leather resin according to claim 1, which is characterized in that described changes Property polytetrahydrofuran diol is the modification polytetrahydrofuran diol being copolymerized by tetrahydrofuran and side group substituted tetrahydrofuran.
A kind of 3. automotive trim superfine fiber chemical leather resin according to claim 2, which is characterized in that the modification Polytetrahydrofuran diol is one or both of modification polytetrahydrofuran diol that number-average molecular weight is 2000~4000g/mol Mixture.
A kind of 4. automotive trim superfine fiber chemical leather resin according to claim 1, which is characterized in that the poly- carbon Acid esters-caprolactone diol is the quality of the polyol, wherein carbonic ester and caprolactone diol of carbonic ester and caprolactone diol Than for:80/20, number-average molecular weight 2000g/mol.
A kind of 5. automotive trim superfine fiber chemical leather resin according to claim 1, which is characterized in that the second The molar ratio of glycol and hydroquinone-bis- (beta-hydroxyethyls) ether is 1/1~4/1.
6. a kind of automotive trim superfine fiber chemical leather resin according to claim 1, which is characterized in that described is poly- Dimethyl siloxane dihydric alcohol is that a kind of number-average molecular weight is 2000~5000g/mol, and degree of functionality is 2 dimethyl silicone polymer Glycol.
7. a kind of automotive trim superfine fiber chemical leather resin according to claim 1, which is characterized in that described is poly- Adipic acid type polyester polyol is the polybutylene glyool adipate that number-average molecular weight is 2000g/mol or number-average molecular weight is The mixture of one or both of -3 methyl-1 of polyadipate of 2000g/mol, 5 pentadiol ester glycol.
8. a kind of automotive trim superfine fiber chemical leather resin according to claim 7, which is characterized in that described is poly- The ratio that adipic acid type polyester polyol accounts for polyalcohol total amount in formula is controlled between 10-20%.
9. a kind of preparation of automotive trim superfine fiber chemical leather resin described in any one of claim 1 to 8 claim Method, which is characterized in that comprise the steps of:
(1) makrolon-caprolactone diol, polyadipate type polyester polyol, dimethyl silicone polymer are put into a kettle Dihydric alcohol and n,N-Dimethylformamide, stirring put into part diphenyl methane -4,4 '-diisocyanate, control after 30 minutes Isocyanate group and the molar ratio of hydroxyl are 0.95 in reaction system:1~0.98:1, reaction temperature is controlled at 75~85 DEG C, Gu Content control is 50%~65%, and when reaction system viscosity reaches 50~200Pas/50 DEG C, first step reaction terminates;
(2) put into a kettle a certain amount of solvent n,N-Dimethylformamide, modified polytetrahydrofuran diol, ethylene glycol, Hydroquinone-bis- (beta-hydroxyethyl) ether puts into diphenyl methane -4 of metering after stirring evenly, 4 '-diisocyanate, control is instead It is 0.94 to answer isocyanate group and the molar ratio of hydroxyl in system:1~0.97:1, the control of the solid content of reaction system 40%~ 50%, reaction temperature control control is at 75~85 DEG C, after reacting 1~2h, is added portionwise diphenyl methane -4 of surplus, 4 ' - Diisocyanate and remaining n,N-Dimethylformamide until final viscosity reaches 80~120Pas/25 DEG C, terminate anti- It should.
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CN110105525A (en) * 2019-05-21 2019-08-09 株洲时代新材料科技股份有限公司 A kind of wet and heat ageing resistant NDI base polyurethane micropore elastomer and preparation method thereof
CN110951030A (en) * 2019-12-11 2020-04-03 上海华峰超纤科技股份有限公司 Low-temperature-resistant and wear-resistant non-yellowing polyurethane resin and superfine fiber synthetic leather prepared from same
CN112280283A (en) * 2020-10-17 2021-01-29 浙江禾欣科技有限公司 Double-component polyurethane resin for automobile leather and preparation method thereof
CN114149560A (en) * 2021-12-14 2022-03-08 福建汇得新材料有限公司 Wet-process polyurethane resin and preparation method and application thereof

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