CN107227138A - A kind of leather Aqueous Adhesives and preparation method thereof - Google Patents
A kind of leather Aqueous Adhesives and preparation method thereof Download PDFInfo
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- CN107227138A CN107227138A CN201710462229.0A CN201710462229A CN107227138A CN 107227138 A CN107227138 A CN 107227138A CN 201710462229 A CN201710462229 A CN 201710462229A CN 107227138 A CN107227138 A CN 107227138A
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- aqueous adhesives
- leather
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- soybean oil
- diisocyanate
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/36—Hydroxylated esters of higher fatty acids
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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
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
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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
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
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- 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
- C08G18/4833—Polyethers containing oxyethylene units
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—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
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- 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
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- 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
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
- C08G18/6644—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
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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
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
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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
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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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
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
- C08G18/6677—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
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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
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- 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
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/69—Polymers of conjugated dienes
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- 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
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/69—Polymers of conjugated dienes
- C08G18/698—Mixtures with compounds of group C08G18/40
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
Abstract
The invention provides a kind of leather Aqueous Adhesives and preparation method thereof.It is synthesis material that the leather employs epoxidized soybean oil with the preparation method of Aqueous Adhesives, epoxy soybean oil base polyol is made, polyurethane prepolymer is further prepared, further mixed with super branched polyurethane, silane coupler etc., emulsified and prepare leather Aqueous Adhesives；Epoxy soybean oil base polyol is made by synthesis material of epoxidized soybean oil, is conducive to environmental protection and economic sustainable development；Obtained adhesive has very high Bio-based content, with good viscoplasticity；In addition synthetic adhesive is used for using super branched polyurethane, can both strengthens chemical crosslinking and the physical crosslinking degree of leather Aqueous Adhesives, cementability of the leather Aqueous Adhesives to leather can be improved again；Leather of the present invention is moderate with aqueous gluing surface drying time, gluing superior performance, with very high practicality.
Description
Technical field
The present invention relates to leather processing preparation technique field, and in particular to a kind of leather Aqueous Adhesives and its preparation side
Method.
Background technology
The composition of traditional Aqueous Adhesives is generally：Polyester or PPG react the pre-polymerization to be formed with isocyanates
Body, then adds organic solvent, emulsifying agent and is distributed in water and forms polyaminoester emulsion.But it is due to use in the Aqueous Adhesives
Substantial amounts of organic solvent, organic solvent is poisonous and harmful to human body, and serious harmfulness is caused to human body, and its general volatile has
Machine thing content (VOC) is higher, and common product is in 10-100g/L.And when it removes consumption energy consumption, cost of manufacture is accordingly higher and imitates
Rate is low.And easily cohesive force occur in leather bonding process poor for the existing common adhesive of glue, and hardening occurs
Etc. phenomenon, performance is influenceed, situation about coming off easily occurs.Aqueous polyurethane is using water as decentralized medium, compared to solvent-borne type
Polyurethane, its characteristic such as have environment-friendly, construction safety convenient.Research as coating in recent years Yu adhesive industry
Focus.But so far, the raw material of production aqueous polyurethane is petroleum chemicals, and with the increasingly depleted of petroleum resources, it can
Sustainable development is tested.Renewable resource such as vegetable fat using nature etc. is a kind of come gradually replacement petroleum chemicals
Good solution.
Vegetable oil have recyclability, resource distribution scope it is wide, cheap, from structure analysis with abundant application
Possibility, but because the double bond density and activity that can directly be polymerize in vegetable oil are relatively low, its homopolymer can only obtain molecule
The relatively low polymer of amount, durability is poor, so pure plant oil-based polymers resin is less, typically joins as comonomer
With polymerisation, the renewable carbon restricted levels of the polymeric material obtained by preparation, nonetheless, vegetable oil participate in the anti-of polymerization
Answer system mostly dicyandiamide solution, preparing for the aqueous plant oil-based resin of high content of vegetable oil less sees report.Based on environmental protection
With the consideration of the direct utilization ratio of renewable resource, study significant with plant oil modified waterborne polyurethane resin.
The content of the invention
In order to solve the above problems, the invention provides a kind of leather Aqueous Adhesives and preparation method thereof.
In a first aspect, the invention provides a kind of preparation method of leather Aqueous Adhesives, comprising the following steps：
(1) by epoxidized soybean oil, the first polyalcohol and zeolite molecular sieve catalyst under the conditions of 50~60 DEG C stirring reaction
0.1~1 hour, filter out zeolite molecular sieve catalyst, obtain epoxy soybean oil base polyol, wherein, first polyalcohol with
Quaity of Epoxidized Soybean Oil ratio is 1~5:1；
(2) by the epoxy soybean oil base polyol obtained by the first isocyanates and step (1) in the presence of catalyst in
80~85 DEG C of reactions, 2~4 hours generation polyurethane prepolymers, wherein, first isocyanates and the epoxy obtained by step (1)
The mass ratio of soybean oil base polyol is 1~3:1；
(3) by the polyurethane prepolymer obtained by the first chain extender, the second chain extender, step (2) under the conditions of 80~85 DEG C
3~4h of chain extending reaction, adds neutralization reagent, after being reacted 0.1~2 hour under conditions of 50~60 DEG C, adds hyperbranched poly
Leather Aqueous Adhesives are made in urethane, silane coupler, emulsion dispersion；Wherein, first chain extender and step (2) gained
Polyurethane prepolymer mass ratio be 0.2~1:1；Second chain extender and the polyurethane prepolymer obtained by step (2)
Mass ratio is 0.1~0.5:1；The mass ratio of the neutralization reagent and the polyurethane prepolymer obtained by the step (2) is 0.05
~0.2:1；The mass ratio of polyurethane prepolymer obtained by the super branched polyurethane, silane coupler and step (2) is 0.005
~0.2:0.005~0.1:1.
Preferably, in the step (1), first polyalcohol is 2~3 with Quaity of Epoxidized Soybean Oil ratio:1.
Preferably, in the step (1), first polyalcohol includes but is not limited to polytetramethylene ether diol, gathers oneself
Lactone polyols, polycarbonate polyol, PolyTHF ethoxylated polyhydric alcohol, polyethylene oxide polyol, PPOX are polynary
One or more in alcohol and end hydroxy butadiene.
It is further preferred that in the step (1), first polyalcohol is polytetramethylene ether diol.
Preferably, in the step (1), the zeolite molecular sieve catalyst and Quaity of Epoxidized Soybean Oil ratio be 0.005~
0.02:1。
Preferably, in the step (1), the zeolite molecular sieve catalyst is KY molecular sieve catalysts.
Preferably, in the step (2), first isocyanates include but is not limited to higher alcohols sulfosuccinate,
Toluene di-isocyanate(TDI), IPDI, methyl diphenylene diisocyanate, hexamethylene diisocyanate, benzene two
Methylene diisocyanate, naphthalene -1,5- diisocyanate, polymethylene multi-phenenyl isocyanate, tetramethylxylene two
One or more in isocyanates, Methylcyclohexyl diisocyanate and dicyclohexyl methyl hydride diisocyanate.
Preferably, in the step (2), the matter of the catalyst and the epoxy soybean oil base polyol obtained by step (1)
Amount is than being 0.001~0.05:1.
Preferably, in the step (2), the catalyst is included in organotin catalysts, organic bismuth catalyst at least
It is a kind of.
It is further preferred that in the step (2), the organotin catalysts include but is not limited to di lauric dibutyl
One or more in tin, stannous octoate, two mercaptan tin alkyls, dioctyl tin.
It is further preferred that in the step (2), the organic bismuth catalyst includes but is not limited to Coscat83, organic
One or more in bismuth 1610, organo-bismuth 2010, organo-bismuth 2810, organo-bismuth 2808.
It is further preferred that in the step (2), the organic bismuth catalyst is organo-bismuth 1610.
Preferably, in the step (2), the super branched polyurethane is to be made using following methods：
After second isocyanates is mixed with the dihydric alcohol containing hydrophilic radical, under inert gas conditions, in 60~90 DEG C
0.5~4h of lower reaction, is cooled to not higher than 0 DEG C, adds secondary amine, adds the second polyalcohol, be warming up to 80~100 DEG C of reactions
Super branched polyurethane is made in 0.5~2h；Wherein, the mass ratio of the dihydric alcohol containing hydrophilic radical and second isocyanates
For 0.05~0.2:1；The mass ratio of the secondary amine and second isocyanates is 0.2~0.5:1；Second polyalcohol with
The mass ratio of the isocyanates is 1~2:1.
It is understood that in step (2) of the present invention, to by the second isocyanates and the dihydric alcohol containing hydrophilic radical
The method of mixing is not particularly limited, using conventional method well-known to those skilled in the art.
It is further preferred that in the step (2), it is described to mix the second isocyanates with the dihydric alcohol containing hydrophilic radical
The step of, specifically include：Second isocyanates and the dihydric alcohol containing hydrophilic radical are dissolved in organic solvent, stirring mixing；Its
In, organic solvent is DMF.
It is further preferred that in the step (2), second isocyanates includes but is not limited to higher alcohols sulfosuccinic
Acid esters, toluene di-isocyanate(TDI), IPDI, methyl diphenylene diisocyanate, hexamethylene diisocyanate,
XDI, naphthalene -1,5- diisocyanate, polymethylene multi-phenenyl isocyanate, the methylene of durol two
One or more in group diisocyanate, Methylcyclohexyl diisocyanate and dicyclohexyl methyl hydride diisocyanate.
It is further preferred that in the step (1) and (2), second isocyanates is with first isocyanates
Identical or different compound.
It is further preferred that in the step (2), second polyalcohol includes but is not limited to polytetramethylene ether two
Alcohol, polycaprolactone polyol, polycarbonate polyol, PolyTHF ethoxylated polyhydric alcohol, polyethylene oxide polyol, polycyclic oxygen third
The one or more in epoxy soybean oil base polyol obtained by alkane polyalcohol and end hydroxy butadiene, step (1).
It is further preferred that in the step (2), the dihydric alcohol containing hydrophilic radical includes but is not limited to dihydroxy first
One or more in base propionic acid, dihydroxy half ester, 1,4- butanediol -2- sodium sulfonates.
It is further preferred that in the step (2), the secondary amine includes but is not limited in diethanol amine, diisopropanolamine (DIPA)
One or more.
Preferably, in the step (3), first chain extender includes but is not limited to dihydromethyl propionic acid, dihydroxymethyl
One or more in butyric acid, dihydroxymethyl valeric acid and dihydroxymethyl octanoic acid.
It is further preferred that in the step (3), first chain extender is dihydromethyl propionic acid.
Preferably, in the step (3), second chain extender includes but is not limited to ethylene glycol, diglycol, 1,
4- butanediols, 2,3- butanediols, 1,6-HD, neopentyl glycol, diethylene glycol (DEG), glycerine, sorbierite, trimethylolpropane and dihydroxy
One or more in hexahydrotoluene.
It is further preferred that in the step (3), second chain extender is BDO.
Preferably, in the step (3), the neutralization reagent includes but is not limited to triethylamine, sodium hydroxide, potassium hydroxide
With the one or more in ammoniacal liquor.
It is further preferred that in the step (3), the neutralization reagent is triethylamine.
Preferably, in the step (3), the silane coupler include 3- NCOs propyl-triethoxysilicane,
N- β-(aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane, aminopropyl triethoxysilane, glycidol fan's epoxide propyl group
One or more in trimethoxy silane, VTES.Silane in leather Aqueous Adhesives of the present invention
Coupling agent composition is conducive to increasing wellability and adhesion strength of adhesive etc..
Second aspect, present invention also offers a kind of leather Aqueous Adhesives, the leather Aqueous Adhesives are to adopt
It is made with the preparation method of the leather Aqueous Adhesives described in first aspect.
Beneficial effect of the present invention relative to prior art：
Leather Aqueous Adhesives provided by the present invention and preparation method thereof, using epoxidized soybean oil as synthesis material, system
Epoxy soybean oil base polyol is obtained, is conducive to environmental protection and economic sustainable development；Obtained adhesive has very high
Bio-based content, with good viscoplasticity；And synthetic adhesive is used for using super branched polyurethane, it can both promote poly- ammonia
The chain extending reaction of ester prepolymer and chain extender, and super branched polyurethane enhances chemical crosslinking and the thing of leather Aqueous Adhesives
Crosslinking degree is managed, cementability of the leather Aqueous Adhesives to leather is improved；The aqueous gluing of leather of the present invention
Surface drying time is moderate, gluing superior performance, with very high practicality；On the other hand, raw material sources are simple, cheap, institute
Obtained leather is with aqueous gluing high financial profit.
Embodiment
The technical scheme in the embodiment of the present invention will be clearly and completely described below.Obviously, described implementation
Example only a part of embodiment of the invention, rather than whole embodiments.Based on the embodiment in the present invention, this area is common
The every other embodiment that technical staff is obtained under the premise of creative work is not made, belongs to the model that the present invention is protected
Enclose.
Influence of the consumption of the different epoxidized soybean oils of embodiment 1 to leather Aqueous Adhesives
The embodiments of the invention provide a kind of preparation method of leather Aqueous Adhesives, comprise the following steps：
(1) preparation of epoxy soybean oil base polyol：
Take 50 parts of epoxidized soybean oils, 125 parts of polytetramethylene ether diols and 0.5 part of KY molecular sieve catalyst；By what is taken
Epoxidized soybean oil, polytetramethylene ether diol and KY molecular sieve catalysts are added in autoclave, the stirring reaction under the conditions of 50 DEG C
0.5 hour, catalyst is filtered out after the completion of reaction, epoxy soybean oil base polyol is obtained, after tested the ring of the epoxidized soybean oil
Oxygen value is 0.38；
(2) preparation of polyurethane prepolymer：
Take the raw material of following portions by weight：160 parts of higher alcohols sulfosuccinates, 2 parts of organo-bismuths 1610,100 parts of steps
(1) epoxy soybean oil base polyol obtained by, by the epoxy obtained by higher alcohols sulfosuccinate, organo-bismuth 1610, step (1)
Soybean oil base polyol is added in reaction bulb, in 85 DEG C of reactions, 3 hours generation polyurethane prepolymers in the presence of organo-bismuth 1610
Thing；
(3) preparation of super branched polyurethane：
Take the raw material of following portions by weight：1 part of bishydroxymethyl propionic acid, 10 parts of Toluene-2,4-diisocyanates, 4- diisocyanate, 10 parts of N,
Dinethylformamide, 3 parts of diethanol amine, the epoxy soybean oil base polyol obtained by 15 parts of steps (1), by the second isocyanates
It is dissolved in the dihydric alcohol containing hydrophilic radical in DMF, after stirring, under nitrogen protective condition, in 60~
2h is reacted at 90 DEG C, under the conditions of ice-water bath (- 5~0 DEG C), is slowly dropped into the DMF solution being dissolved with,
Then the epoxy soybean oil base polyol obtained by step (1) is added, 90 DEG C is warming up to and reacts 1h, it is obtained hyperbranched through isolating and purifying
Polyurethane；
(4) preparation of leather Aqueous Adhesives：
Take the raw material of following portions by weight：20 parts of dihydromethyl propionic acids, 40 parts of diglycols, 100 parts of step (2) institutes
Polyurethane prepolymer, 5 parts of triethylamines, the super branched polyurethane obtained by 1 part of step (3), 1 part of 3- NCOs propyl group three
Ethoxysilane；Polyurethane prepolymer obtained by dihydromethyl propionic acid, diglycol, step (2) is added in reaction bulb,
Chain extending reaction 3.5h, adds triethylamine under the conditions of 80 DEG C, after being reacted 0.5 hour under conditions of 55 DEG C, adds step
(3) super branched polyurethane, 3- NCO propyl-triethoxysilicanes obtained by, emulsification point is carried out using high speed dispersor
Dissipate, obtained leather Aqueous Adhesives.
In order to further illustrate beneficial effects of the present invention, repeat the above steps (1), big using epoxy as shown in table 1
Soya-bean oil and polytetramethylene ether diol mass ratio, are made epoxy soybean oil base polyol；The step of repeating the embodiment of the present invention 1
(2)~(4), obtained leather Aqueous Adhesives.The epoxide number of the epoxy soybean oil base polyol is as shown in table 1 after tested.
Viscosity is evaluated with reference to part B/T2790-1995 adhesive 180 degree peeling strength test method, the thick adhesives of 0.1mm are applied to
On smooth flat board, record film surface has sticking time (min), and its result is as shown in table 1.
As shown in Table 1, it is raw material that the leather that the embodiment of the present invention is provided, which employs epoxidized soybean oil with Aqueous Adhesives,
Synthesis, obtained adhesive has very high Bio-based content, with good viscoplasticity.Specifically, polytetramethylene ether
The mass ratio of glycol and epoxidized soybean oil is 2.5:When 1, obtained leather shows high peel strength with Aqueous Adhesives,
Illustrate that the leather Aqueous Adhesives have more polar ester groups, cohesive energy is larger, can form stronger intramolecular hydrogen bond, because
And peel strength and surface drying time are significantly better than leather made from the polytetramethylene ether diol and epoxidized soybean oil of other ratios
Aqueous Adhesives, and appropriate extension surface drying time is conducive to bonding object positioning, coheres.
Embodiment 2
The embodiments of the invention provide a kind of preparation method of leather Aqueous Adhesives, comprise the following steps：
(1) preparation of epoxy soybean oil base polyol：
Epoxy soybean oil base polyol is made in the step of repeating the embodiment of the present invention 1 (1)；
(2) preparation of polyurethane prepolymer：
Take the raw material of following portions by weight：200 parts of higher alcohols sulfosuccinates, 2 parts of organo-bismuths 1610,100 parts of steps
(1) epoxy soybean oil base polyol obtained by, by the epoxy obtained by higher alcohols sulfosuccinate, organo-bismuth 1610, step (1)
Soybean oil base polyol is added in reaction bulb, in 80 DEG C of reactions, 4 hours generation polyurethane prepolymers in the presence of organo-bismuth 1610
Thing；
(3) preparation of super branched polyurethane：
Take the raw material of following portions by weight：2 parts of bishydroxymethyl propionic acid, 10 parts of higher alcohols sulfosuccinates, 15 parts of N,
Dinethylformamide, 2 parts of diethanol amine, the epoxy soybean oil base polyol obtained by 10 parts of steps (1), by the second isocyanates
It is dissolved in the dihydric alcohol containing hydrophilic radical in DMF, after stirring, under nitrogen protective condition, in 90 DEG C
Lower reaction 2h, under the conditions of ice-water bath (- 5~0 DEG C), is slowly dropped into the DMF solution being dissolved with, then
The epoxy soybean oil base polyol obtained by step (1) is added, 90 DEG C of reaction 1h are warming up to, through isolating and purifying obtained hyperbranched poly ammonia
Ester；
(4) preparation of leather Aqueous Adhesives：
Take the raw material of following portions by weight：10 parts of dihydromethyl propionic acids, 30 parts of diglycols, 100 parts of step (2) institutes
Polyurethane prepolymer, 10 parts of triethylamines, the super branched polyurethane obtained by 2 parts of steps (3), 1 part of 3- NCO propyl group
Triethoxysilane；Polyurethane prepolymer obtained by dihydromethyl propionic acid, diglycol, step (2) is added into reaction bulb
In, chain extending reaction 3.5h, adds triethylamine under the conditions of 80 DEG C, after being reacted 1.5 hours under conditions of 60 DEG C, adds step
Suddenly super branched polyurethane, 3- NCO propyl-triethoxysilicanes obtained by (3), emulsification point is carried out using high speed dispersor
Dissipate, obtained leather Aqueous Adhesives.
Embodiment 3
The embodiments of the invention provide a kind of preparation method of leather Aqueous Adhesives, comprise the following steps：
(1) preparation of epoxy soybean oil base polyol：
Epoxy soybean oil base polyol is made in the step of repeating the embodiment of the present invention 1 (1)；
(2) preparation of polyurethane prepolymer：
Take the raw material of following portions by weight：125 parts of Toluene-2,4-diisocyanates, 4- diisocyanate, 1 part of organo-bismuth 1610,100 parts of steps
(1) epoxy soybean oil base polyol obtained by, by Toluene-2,4-diisocyanate, 4- diisocyanate, organo-bismuth 1610, the ring obtained by step (1)
Oxygen soybean oil base polyol is added in reaction bulb, pre- in 80 DEG C of reactions, 3 hours generation polyurethane in the presence of organo-bismuth 1610
Polymers；
(3) preparation of super branched polyurethane：
Take the raw material of following portions by weight：2 parts of bishydroxymethyl propionic acid, 10 parts of Toluene-2,4-diisocyanates, 4- diisocyanate, 15 parts of N,
Dinethylformamide, 4 parts of diethanol amine, the epoxy soybean oil base polyol obtained by 12.5 parts of steps (1), by Toluene-2,4-diisocyanate, 4-
Diisocyanate, bishydroxymethyl propionic acid are dissolved in DMF, after stirring, under nitrogen protective condition,
In reacting 2h at 90 DEG C, under the conditions of ice-water bath (- 5~0 DEG C), the DMF solution being dissolved with is slowly dropped into
In, the epoxy soybean oil base polyol obtained by step (1) is then added, 85 DEG C of reaction 1h is warming up to, is made super through isolating and purifying
Branched polyurethanes；
(4) preparation of leather Aqueous Adhesives：
Take the raw material of following portions by weight：15 parts of dihydromethyl propionic acids, 30 parts of diglycols, 100 parts of step (2) institutes
Polyurethane prepolymer, 10 parts of triethylamines, the super branched polyurethane obtained by 1.5 parts of steps (3), 1 part of N- β-(aminoethyl)-
γ-aminopropyltriethoxy dimethoxysilane；By the polyurethane prepolymer obtained by dihydromethyl propionic acid, diglycol, step (2)
Thing is added in reaction bulb, and chain extending reaction 4h, adds triethylamine under the conditions of 80 DEG C, after being reacted 2 hours under conditions of 60 DEG C,
Super branched polyurethane, the N- β-(aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane obtained by step (3) are added, height is used
Fast dispersion machine carries out emulsion dispersion, obtained leather Aqueous Adhesives.
Embodiment 4
The embodiments of the invention provide a kind of preparation method of leather Aqueous Adhesives, comprise the following steps：
(1) preparation of epoxy soybean oil base polyol：
Epoxy soybean oil base polyol is made in the step of repeating the embodiment of the present invention 1 (1)；
(2) preparation of polyurethane prepolymer：
Take the raw material of following portions by weight：125 parts of higher alcohols sulfosuccinates, 1 part of organo-bismuth 2808,100 parts of steps
(1) epoxy soybean oil base polyol obtained by, by the epoxy obtained by higher alcohols sulfosuccinate, organo-bismuth 1610, step (1)
Soybean oil base polyol is added in reaction bulb, in 80 DEG C of reactions, 3 hours generation polyurethane prepolymers in the presence of organo-bismuth 2808
Thing；
(3) preparation of super branched polyurethane：
Take the raw material of following portions by weight：2 parts of bishydroxymethyl propionic acid, 10 parts of higher alcohols sulfosuccinates, 15 parts of N,
Dinethylformamide, 4 parts of diethanol amine, the epoxy soybean oil base polyol obtained by 8 parts of steps (1), by higher alcohols sulfo group amber
Amber acid esters, bishydroxymethyl propionic acid are dissolved in DMF, after stirring, under nitrogen protective condition, in 90
2h is reacted at DEG C, under the conditions of ice-water bath (- 5~0 DEG C), is slowly dropped into the DMF solution being dissolved with, so
The epoxy soybean oil base polyol obtained by step (1) is added afterwards, 85 DEG C of reaction 1h is warming up to, through isolating and purifying obtained hyperbranched poly
Urethane；
(4) preparation of leather Aqueous Adhesives：
Take the raw material of following portions by weight：20 parts of dihydromethyl propionic acids, 40 parts of diglycols, 100 parts of step (2) institutes
Polyurethane prepolymer, 10 parts of triethylamines, the super branched polyurethane obtained by 1.5 parts of steps (3), 1 part of N- β-(aminoethyl)-
γ-aminopropyltriethoxy dimethoxysilane；By the polyurethane prepolymer obtained by dihydromethyl propionic acid, diglycol, step (2)
Thing is added in reaction bulb, and chain extending reaction 4h, adds triethylamine under the conditions of 80 DEG C, after being reacted 2 hours under conditions of 60 DEG C,
Super branched polyurethane, the N- β-(aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane obtained by step (3) are added, height is used
Fast dispersion machine carries out emulsion dispersion, obtained leather Aqueous Adhesives.
Comparative example 1
Comparative example of the present invention provides a kind of preparation method of leather Aqueous Adhesives, comprises the following steps：
(1) preparation of polyurethane prepolymer：
Take the raw material of following portions by weight：160 parts of higher alcohols sulfosuccinates, 2 parts of organo-bismuths 1610,100 parts poly- four
Methylene ether glycol, higher alcohols sulfosuccinate, organo-bismuth 1610, polytetramethylene ether diol are added in reaction bulb,
In 85 DEG C of reactions, 3 hours generation polyurethane prepolymers in the presence of organo-bismuth 1610；
(2) preparation of leather Aqueous Adhesives：
Take the raw material of following portions by weight：20 parts of dihydromethyl propionic acids, 40 parts of diglycols, 100 parts of step (2) institutes
Polyurethane prepolymer, the 5 parts of triethylamines obtained；Polyurethane obtained by dihydromethyl propionic acid, diglycol, step (2) is pre-
Polymers is added in reaction bulb, and chain extending reaction 3.5h, adds triethylamine under the conditions of 80 DEG C, and 0.5 is reacted under conditions of 55 DEG C
After hour, emulsion dispersion, obtained leather Aqueous Adhesives are carried out using high speed dispersor.
Comparative example 2
Comparative example of the present invention provides a kind of preparation method of leather Aqueous Adhesives, comprises the following steps：
(1) preparation of epoxy soybean oil base polyol：
Epoxy soybean oil base polyol is made in the step of repeating the embodiment of the present invention 1 (1)；
(2) preparation of polyurethane prepolymer：
Polyurethane prepolymer is made in the step of repeating the embodiment of the present invention 1 (2)；
(3) preparation of leather Aqueous Adhesives：
Take the raw material of following portions by weight：20 parts of dihydromethyl propionic acids, 40 parts of diglycols, 100 parts of step (2) institutes
Polyurethane prepolymer, the 5 parts of triethylamines obtained；Polyurethane obtained by dihydromethyl propionic acid, diglycol, step (2) is pre-
Polymers is added in reaction bulb, and chain extending reaction 3.5h, adds triethylamine under the conditions of 80 DEG C, and 0.5 is reacted under conditions of 55 DEG C
After hour, emulsion dispersion, obtained leather Aqueous Adhesives are carried out using high speed dispersor.
Viscosity is evaluated with reference to part B/T2790-1995 adhesive 180 degree peeling strength test method, by the thick glue of 0.1mm
Glutinous agent is applied on smooth flat board, and record film surface has sticking time (min), and its result is as shown in table 2.
As shown in Table 2, the leather that the embodiment of the present invention 2~4 is provided employs epoxidized soybean oil with Aqueous Adhesives and is
Material synthesis, obtained adhesive has very high Bio-based content, and with good viscoplasticity, the stripping obtained by test is strong
Degree and surface drying time are significantly better than the leather Aqueous Adhesives that comparative example 1,2 of the present invention is provided；This explanation is big with epoxy
Soya-bean oil is synthesis material, and epoxy soybean oil base polyol is made, and obtained adhesive has very high Bio-based content, had
Good viscoplasticity；And synthetic adhesive is used for using super branched polyurethane, it can both promote polyurethane prepolymer and chain extender
Chain extending reaction, and super branched polyurethane enhances chemical crosslinking and the physical crosslinking degree of leather Aqueous Adhesives, improves
Cementabilities of the leather Aqueous Adhesives to leather, suitably extend the surface drying time of adhesive.
The test result of leather Aqueous Adhesives obtained by each embodiment of table 2
| Sequence number | Leather Aqueous Adhesives | Peel strength/N/cm | Surface drying time/min |
| 1 | Leather Aqueous Adhesives obtained by embodiment 2 | 41.65 | 15 |
| 2 | Leather Aqueous Adhesives obtained by embodiment 3 | 44.91 | 12 |
| 3 | Leather Aqueous Adhesives obtained by embodiment 4 | 37.32 | 13 |
| 4 | Leather Aqueous Adhesives obtained by comparative example 1 | 23.89 | 8 |
| 5 | Leather Aqueous Adhesives obtained by comparative example 2 | 26.25 | 7 |
Above content is to combine specific preferred embodiment further description made for the present invention, it is impossible to assert
The specific implementation of the present invention is confined to these explanations.For general technical staff of the technical field of the invention,
On the premise of not departing from present inventive concept, some simple deduction or replace can also be made, should all be considered as belonging to the present invention's
Protection domain.
Claims (10)
1. a kind of preparation method of leather Aqueous Adhesives, it is characterised in that comprise the following steps：
(1) by epoxidized soybean oil, the first polyalcohol and zeolite molecular sieve catalyst under the conditions of 50~60 DEG C stirring reaction 0.1~
1 hour, zeolite molecular sieve catalyst is filtered out after the completion of reaction, epoxy soybean oil base polyol is obtained, wherein, described more than first yuan
Alcohol is 1~5 with Quaity of Epoxidized Soybean Oil ratio:1；
(2) it is 1~3 according to the mass ratio of the epoxy soybean oil base polyol obtained by the first isocyanates and step (1):1 ratio
Example, by the epoxy soybean oil base polyol obtained by the first isocyanates, step (1) in the presence of catalyst it is anti-in 80~85 DEG C
Answer 2~4 hours generation polyurethane prepolymers；
(3) by the polyurethane prepolymer obtained by the first chain extender, the second chain extender, step (2) under the conditions of 80~85 DEG C chain extension
React 3~4h after, add neutralization reagent, under conditions of 50~60 DEG C react 0.1~2 hour, add super branched polyurethane,
Leather Aqueous Adhesives are made in silane coupler, emulsion dispersion；Wherein, first chain extender and gathering obtained by step (2)
The mass ratio of urethane prepolymer is 0.2~1:1；The quality of second chain extender and the polyurethane prepolymer obtained by step (2)
Than for 0.1~0.5:1；The mass ratio of polyurethane prepolymer obtained by the neutralization reagent and the step (2) for 0.05~
0.2:1；The mass ratio of polyurethane prepolymer obtained by the super branched polyurethane, silane coupler and step (2) be 0.005~
0.2:0.005~0.1:1.
2. the preparation method of leather Aqueous Adhesives as claimed in claim 1, it is characterised in that in the step (1), institute
State the first polyalcohol many including polytetramethylene ether diol, polycaprolactone polyol, polycarbonate polyol, PTMG
One or more in first alcohol, polyethylene oxide polyol, polyoxypropylene polyol and end hydroxy butadiene.
3. the preparation method of leather Aqueous Adhesives as claimed in claim 1, it is characterised in that in the step (2), institute
Stating the first isocyanates includes higher alcohols sulfosuccinate, toluene di-isocyanate(TDI), IPDI, diphenyl
Methane diisocyanate, hexamethylene diisocyanate, XDI, naphthalene -1,5- diisocyanate, many methylenes
Quito phenyl isocyanate, tetramethylxylylene diisocyanate, Methylcyclohexyl diisocyanate and dicyclohexyl first
One or more in alkane diisocyanate.
4. the preparation method of leather Aqueous Adhesives as claimed in claim 1, it is characterised in that in the step (2), institute
Stating catalyst includes at least one of organotin catalysts, organic bismuth catalyst.
5. the preparation method of leather Aqueous Adhesives as claimed in claim 1, it is characterised in that in the step (2), institute
It is to be made using following methods to state super branched polyurethane：
After second isocyanates is mixed with the dihydric alcohol containing hydrophilic radical, under inert gas conditions, in anti-at 60~90 DEG C
Answer 0.5~4h, be cooled to not higher than 0 DEG C, add secondary amine, add the second polyalcohol, be warming up to 80~100 DEG C of reactions 0.5~
Super branched polyurethane is made in 2h；Wherein, the mass ratio of the dihydric alcohol containing hydrophilic radical and second isocyanates is
0.05~0.2:1；The mass ratio of the secondary amine and second isocyanates is 0.2~0.5:1；Second polyalcohol and institute
The mass ratio for stating the second isocyanates is 0.75~1.2:1.
6. the preparation method of leather Aqueous Adhesives as claimed in claim 1, it is characterised in that in the step (2), institute
Stating the second isocyanates includes higher alcohols sulfosuccinate, toluene di-isocyanate(TDI), IPDI, diphenyl
Methane diisocyanate, hexamethylene diisocyanate, XDI, naphthalene -1,5- diisocyanate, many methylenes
Quito phenyl isocyanate, tetramethylxylylene diisocyanate, Methylcyclohexyl diisocyanate and dicyclohexyl first
One or more in alkane diisocyanate.
7. the preparation method of leather Aqueous Adhesives as claimed in claim 1, it is characterised in that in the step (3), institute
Stating the first chain extender includes one kind in dihydromethyl propionic acid, dimethylolpropionic acid, dihydroxymethyl valeric acid and dihydroxymethyl octanoic acid
Or it is several.
8. the preparation method of leather Aqueous Adhesives as claimed in claim 1, it is characterised in that in the step (3), institute
Stating the second chain extender includes ethylene glycol, diglycol, 1,4- butanediols, 2,3- butanediols, 1,6-HD, new penta 2
One or more in alcohol, diethylene glycol (DEG), glycerine, sorbierite, trimethylolpropane and hydroxymethyl-cyclohexane；The neutralization reagent
Including the one or more in triethylamine, sodium hydroxide, potassium hydroxide and ammoniacal liquor.
9. the preparation method of leather Aqueous Adhesives as claimed in claim 1, it is characterised in that in the step (3), institute
Stating silane coupler includes 3- NCOs propyl-triethoxysilicane, N- β-(aminoethyl)-γ-aminopropyltriethoxy dimethoxy
In base silane, aminopropyl triethoxysilane, glycidyl ester oxy propyl trimethoxysilane, VTES
One or more.
10. a kind of leather Aqueous Adhesives, it is characterised in that the leather is using such as claim 1 with Aqueous Adhesives
The preparation method of~9 any described leather Aqueous Adhesives is made.
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Cited By (6)
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|---|---|---|---|---|
| CN108913082A (en) * | 2018-08-09 | 2018-11-30 | 郭婷婷 | Aqueous, environmental protective adhesive for polyurethane, preparation method and application |
| CN110105519A (en) * | 2019-04-26 | 2019-08-09 | 浙江华峰热塑性聚氨酯有限公司 | A kind of hot melt adhesive film particle and preparation method thereof |
| CN110154458A (en) * | 2019-04-24 | 2019-08-23 | 溧阳市山湖实业有限公司 | A kind of automobile-used bamboo fiber reinforcement bio-based polyurethane composite panel of low VOC and preparation method |
| CN110627995A (en) * | 2019-10-10 | 2019-12-31 | 临沂大学 | Organosilane coupling agent modified ultraviolet curing material |
| CN112175564A (en) * | 2020-10-29 | 2021-01-05 | 江苏东邦科技有限公司 | High-wear-resistance environment-friendly adhesive for bonding seat leather |
| CN112335998A (en) * | 2020-10-22 | 2021-02-09 | 广州晨骐鞋业有限公司 | Method for preparing women's shoes capable of maintaining three-dimensional state for a long time by using natural leather |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108913082A (en) * | 2018-08-09 | 2018-11-30 | 郭婷婷 | Aqueous, environmental protective adhesive for polyurethane, preparation method and application |
| CN110154458A (en) * | 2019-04-24 | 2019-08-23 | 溧阳市山湖实业有限公司 | A kind of automobile-used bamboo fiber reinforcement bio-based polyurethane composite panel of low VOC and preparation method |
| CN110105519A (en) * | 2019-04-26 | 2019-08-09 | 浙江华峰热塑性聚氨酯有限公司 | A kind of hot melt adhesive film particle and preparation method thereof |
| CN110627995A (en) * | 2019-10-10 | 2019-12-31 | 临沂大学 | Organosilane coupling agent modified ultraviolet curing material |
| CN110627995B (en) * | 2019-10-10 | 2021-06-25 | 临沂大学 | Organosilane coupling agent modified ultraviolet curing material |
| CN112335998A (en) * | 2020-10-22 | 2021-02-09 | 广州晨骐鞋业有限公司 | Method for preparing women's shoes capable of maintaining three-dimensional state for a long time by using natural leather |
| CN112335998B (en) * | 2020-10-22 | 2022-02-18 | 广州晨骐鞋业有限公司 | Method for preparing women's shoes capable of maintaining three-dimensional state for a long time by using natural leather |
| CN112175564A (en) * | 2020-10-29 | 2021-01-05 | 江苏东邦科技有限公司 | High-wear-resistance environment-friendly adhesive for bonding seat leather |
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| CB03 | Change of inventor or designer information | ||
| CB03 | Change of inventor or designer information |
Inventor after: Xiong Shaowen Inventor after: He Ruifang Inventor after: Chen Shiheng Inventor after: Deng Xiaolu Inventor after: Zheng Jianming Inventor after: Liu Hongan Inventor before: Liu Hongan Inventor before: He Ruifang Inventor before: Chen Shiheng Inventor before: Deng Xiaolu Inventor before: Zheng Jianming |
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| CB02 | Change of applicant information | ||
| CB02 | Change of applicant information |
Address after: 510000 Building A, No. 19 Guannan Yong Industrial Road, Shiji Town, Panyu District, Guangzhou City, Guangdong Province Applicant after: Guangdong Meiji Fashion Leather Co., Ltd. Address before: 510000 Building A, No. 19 Guannan Yong Industrial Road, Shiji Town, Panyu District, Guangzhou City, Guangdong Province Applicant before: GUANGZHOU MINGZHI LEATHER PRODUCTS CO., LTD. |
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| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20171003 |