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 PDFInfo
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- 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
- Authority
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- China
- Prior art keywords
- automotive trim
- superfine fiber
- fiber chemical
- chemical leather
- mol
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- Granted
Links
- 239000010985 leather Substances 0.000 title claims abstract description 35
- 229920005989 resin Polymers 0.000 title claims abstract description 27
- 239000011347 resin Substances 0.000 title claims abstract description 27
- 239000000835 fiber Substances 0.000 title claims abstract description 26
- 239000000126 substance Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical class CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 59
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 46
- 150000002009 diols Chemical class 0.000 claims abstract description 17
- 229920000909 polytetrahydrofuran Polymers 0.000 claims abstract description 17
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229920005906 polyester polyol Polymers 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 8
- 229920005573 silicon-containing polymer Polymers 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 7
- VDHWOHDSOHPGPC-UHFFFAOYSA-N 3,3-dihydroxyoxepan-2-one Chemical compound OC1(O)CCCCOC1=O VDHWOHDSOHPGPC-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 36
- 238000003756 stirring Methods 0.000 claims description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 11
- 150000002148 esters Chemical class 0.000 claims description 9
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 7
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 6
- 230000004048 modification Effects 0.000 claims description 6
- 238000012986 modification Methods 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 5
- -1 polybutylene Polymers 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 150000005846 sugar alcohols Polymers 0.000 claims description 4
- WTPYFJNYAMXZJG-UHFFFAOYSA-N 2-[4-(2-hydroxyethoxy)phenoxy]ethanol Chemical compound OCCOC1=CC=C(OCCO)C=C1 WTPYFJNYAMXZJG-UHFFFAOYSA-N 0.000 claims description 3
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 claims description 3
- 235000011037 adipic acid Nutrition 0.000 claims description 3
- 239000001361 adipic acid Substances 0.000 claims description 3
- 229920001748 polybutylene Polymers 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 229920005862 polyol Polymers 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims 1
- 239000004205 dimethyl polysiloxane Substances 0.000 claims 1
- 150000003077 polyols Chemical class 0.000 claims 1
- 239000002649 leather substitute Substances 0.000 abstract description 12
- 229920005749 polyurethane resin Polymers 0.000 abstract description 7
- 239000004744 fabric Substances 0.000 abstract description 5
- 230000032683 aging Effects 0.000 abstract description 3
- 229920000515 polycarbonate Polymers 0.000 abstract description 3
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 abstract 2
- 239000004425 Makrolon Substances 0.000 abstract 1
- 125000005442 diisocyanate group Chemical group 0.000 abstract 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 abstract 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 25
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000004970 Chain extender Substances 0.000 description 4
- 229920002635 polyurethane Polymers 0.000 description 4
- 239000004814 polyurethane Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- SSYDTHANSGMJTP-ZXZARUISSA-N (3s,4r)-oxolane-3,4-diol Chemical class O[C@H]1COC[C@H]1O SSYDTHANSGMJTP-ZXZARUISSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 description 1
- JWTDCPGVNRBTKT-UHFFFAOYSA-N 2-[2-(2-hydroxyethoxy)phenoxy]ethanol Chemical compound OCCOC1=CC=CC=C1OCCO JWTDCPGVNRBTKT-UHFFFAOYSA-N 0.000 description 1
- 108010022579 ATP dependent 26S protease Proteins 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 229920001410 Microfiber Polymers 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000012661 block copolymerization Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- JZZIHCLFHIXETF-UHFFFAOYSA-N dimethylsilicon Chemical compound C[Si]C JZZIHCLFHIXETF-UHFFFAOYSA-N 0.000 description 1
- 125000005982 diphenylmethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003658 microfiber Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Classifications
-
- 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
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene 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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer 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
-
- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
-
- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
-
- 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
- C08G18/61—Polysiloxanes
-
- 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
Landscapes
- 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
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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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN118600742A (en) * | 2024-06-24 | 2024-09-06 | 东莞市科迪实业有限公司 | A tear-resistant microfiber fabric for new energy vehicle interior and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102212183A (en) * | 2011-05-03 | 2011-10-12 | 烟台华大化学工业有限公司 | Polyurethane resin used for skin-imitated superfine fiber synthetic leather, and preparation method thereof |
| CN102532461A (en) * | 2011-12-23 | 2012-07-04 | 上海汇得化工有限公司 | Wet process polyurethane resin used for highly elastic water absorption basketball leather and preparation method |
| CN103665267A (en) * | 2013-12-16 | 2014-03-26 | 上海汇得化工有限公司 | Polyurethane leather resin for automobile seat trim and preparation method thereof |
| CN104530382A (en) * | 2014-12-23 | 2015-04-22 | 上海汇得化工有限公司 | Wet polyurethane resin for imitated micro-fiber synthetic leather and preparation method of wet polyurethane resin |
| CN106188480A (en) * | 2016-08-01 | 2016-12-07 | 旭川化学（苏州）有限公司 | A kind of soft waterborne polyurethane resin of high abrasion one pack system and preparation method thereof |
-
2017
- 2017-12-04 CN CN201711260861.3A patent/CN108047421B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102212183A (en) * | 2011-05-03 | 2011-10-12 | 烟台华大化学工业有限公司 | Polyurethane resin used for skin-imitated superfine fiber synthetic leather, and preparation method thereof |
| CN102532461A (en) * | 2011-12-23 | 2012-07-04 | 上海汇得化工有限公司 | Wet process polyurethane resin used for highly elastic water absorption basketball leather and preparation method |
| CN103665267A (en) * | 2013-12-16 | 2014-03-26 | 上海汇得化工有限公司 | Polyurethane leather resin for automobile seat trim and preparation method thereof |
| CN104530382A (en) * | 2014-12-23 | 2015-04-22 | 上海汇得化工有限公司 | Wet polyurethane resin for imitated micro-fiber synthetic leather and preparation method of wet polyurethane resin |
| CN106188480A (en) * | 2016-08-01 | 2016-12-07 | 旭川化学（苏州）有限公司 | A kind of soft waterborne polyurethane resin of high abrasion one pack system and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 刘益君: "《聚氨酯原料及助剂手册》", 30 April 2005, 化学工业出版社 * |
| 马兴元等: "《合成革化学与工艺学》", 30 November 2015, 中国轻工业出版社 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN110105525B (en) * | 2019-05-21 | 2021-11-16 | 株洲时代新材料科技股份有限公司 | NDI-based polyurethane microporous elastomer resistant to damp-heat aging 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 |
| CN110951030B (en) * | 2019-12-11 | 2021-11-05 | 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 |
| CN118600742A (en) * | 2024-06-24 | 2024-09-06 | 东莞市科迪实业有限公司 | A tear-resistant microfiber fabric for new energy vehicle interior and preparation method thereof |
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