CN103740250A - Preparation method of matting leather water-based polyurethane coating agent - Google Patents
Preparation method of matting leather water-based polyurethane coating agent Download PDFInfo
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- CN103740250A CN103740250A CN201310651725.2A CN201310651725A CN103740250A CN 103740250 A CN103740250 A CN 103740250A CN 201310651725 A CN201310651725 A CN 201310651725A CN 103740250 A CN103740250 A CN 103740250A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 80
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 55
- 239000010985 leather Substances 0.000 title claims abstract description 52
- 239000011527 polyurethane coating Substances 0.000 title claims abstract description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 239000004814 polyurethane Substances 0.000 claims abstract description 62
- 229920002635 polyurethane Polymers 0.000 claims abstract description 62
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 108
- 239000000178 monomer Substances 0.000 claims description 100
- 150000003384 small molecules Chemical class 0.000 claims description 65
- 239000000839 emulsion Substances 0.000 claims description 59
- 230000008033 biological extinction Effects 0.000 claims description 56
- 229920002521 macromolecule Polymers 0.000 claims description 44
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 36
- 239000003054 catalyst Substances 0.000 claims description 34
- 239000012948 isocyanate Substances 0.000 claims description 31
- 150000002513 isocyanates Chemical class 0.000 claims description 28
- 238000005829 trimerization reaction Methods 0.000 claims description 28
- 239000007787 solid Substances 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 24
- -1 Polyoxypropylene Polymers 0.000 claims description 20
- 238000005516 engineering process Methods 0.000 claims description 20
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 19
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical group OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 18
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 15
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 15
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical group O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- 150000001298 alcohols Chemical class 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 150000002148 esters Chemical class 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- 150000002009 diols Chemical class 0.000 claims description 11
- 239000013638 trimer Substances 0.000 claims description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 10
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 10
- 230000008719 thickening Effects 0.000 claims description 10
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 9
- 229920001451 polypropylene glycol Polymers 0.000 claims description 9
- 229920001610 polycaprolactone Polymers 0.000 claims description 7
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 5
- 239000004632 polycaprolactone Substances 0.000 claims description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 4
- 239000002245 particle Substances 0.000 abstract description 19
- 230000000694 effects Effects 0.000 abstract description 11
- 239000000126 substance Substances 0.000 abstract description 4
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 230000005484 gravity Effects 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 14
- 239000006185 dispersion Substances 0.000 description 10
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 9
- 238000009775 high-speed stirring Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000003973 paint Substances 0.000 description 8
- 229920001195 polyisoprene Polymers 0.000 description 8
- 239000006224 matting agent Substances 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 7
- JKTORXLUQLQJCM-UHFFFAOYSA-N 4-phosphonobutylphosphonic acid Chemical compound OP(O)(=O)CCCCP(O)(O)=O JKTORXLUQLQJCM-UHFFFAOYSA-N 0.000 description 6
- 238000009835 boiling Methods 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 6
- 230000000149 penetrating effect Effects 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 5
- 239000002131 composite material Substances 0.000 description 4
- ZWVMLYRJXORSEP-LURJTMIESA-N (2s)-hexane-1,2,6-triol Chemical compound OCCCC[C@H](O)CO ZWVMLYRJXORSEP-LURJTMIESA-N 0.000 description 3
- SSYDTHANSGMJTP-ZXZARUISSA-N (3s,4r)-oxolane-3,4-diol Chemical compound O[C@H]1COC[C@H]1O SSYDTHANSGMJTP-ZXZARUISSA-N 0.000 description 3
- WOGVOIWHWZWYOZ-UHFFFAOYSA-N 1,1-diisocyanatoethane Chemical compound O=C=NC(C)N=C=O WOGVOIWHWZWYOZ-UHFFFAOYSA-N 0.000 description 3
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- 241000237502 Ostreidae Species 0.000 description 3
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 3
- 239000004922 lacquer Substances 0.000 description 3
- 235000020636 oyster Nutrition 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003892 spreading Methods 0.000 description 3
- 230000007480 spreading Effects 0.000 description 3
- VDHWOHDSOHPGPC-UHFFFAOYSA-N 3,3-dihydroxyoxepan-2-one Chemical compound OC1(O)CCCCOC1=O VDHWOHDSOHPGPC-UHFFFAOYSA-N 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- 229960001866 silicon dioxide Drugs 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000004033 diameter control Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000036314 physical performance Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
Abstract
The invention provides a preparation method of a matting leather water-based polyurethane coating agent. According to the preparation method, a polyurethane A component with a cross-linked structure and a large particle size is synthesized, and is mixed with a B component with a small particle size. The A component possesses many molecular branched chains, size of micellar particles is relatively large, and specific gravity of the A component is less than that of the component B; so that the A component will float on film surface, roughness of the film surface is relatively high, delustering effect is achieved, no delustering agent is needed, excellent transparency is obtained after coating, and no influence on leather substances is caused as the delustering effect is achieved.
Description
Technical field
The invention belongs to leather chemical industry field, be specifically related to a kind of preparation method from extinction type leather waterborne polyurethane coating agent.
Background technology
Aqueous polyurethane refers to that urethane is dissolved in water or is scattered in water and a kind of polyaminoester emulsion of forming.Since the 60's of 20th century, solvent borne polyurethane has obtained using widely, yet causes atmospheric pollution when organic solvent is used, and has toxicity more or less, and in recent years, people's environmental consciousness constantly strengthens, and this has promoted the exploitation of water-base polyurethane material.Aqueous polyurethane be take water as basic medium, have free from environmental pollution, energy-conservation, operate the advantages such as easy to process, be subject to people's attention.
Delustring waterborne polyurethane coating agent is a kind of staple product in hide finishes, it is mainly used in top finishing, and its performance characteristics is good physical performance, hand feel and drape, have water-fast, solvent resistance, light fastness stability energy, wear-resisting Bearable dry and wet wipe performance preferably.Must have good eliminate optical property and stability in storage in addition, after covering with paint, require the graining of leather, pore clear, there is lower glossiness, film forming has good penetrating outward appearance, can not occur the phenomenon of " burnt hair, turn white " after covering with paint.
The delustring mechanism of material film forming is mainly that its film surface has higher roughness, thereby light is carried out to scattering to each different directions, reaches extinction effect.At present domestic hide finishes manufacturer, when producing extinction type waterborne polyurethane coating agent, for reaching good eliminate optical property, generally all needs additional matting agent to realize, as adds silica-based flatting silica, delustring wax etc.
As 201110166205.3, name is called the application for a patent for invention of " goth black delustring treatment agent of special mist and preparation method thereof for leather ", disclose goth black delustring treatment agent of special mist and preparation method thereof for a kind of leather, its formula consists of: urethane resin 30 ~ 60%, auxiliary agent 0 ~ 2%, flatting silica 4% ~ 10%, solvent 30% ~ 60%.
Because the structure of matter and the polyurethane molecular of these matting agents has larger difference, its consistency is poor, easily occurs demixing phenomenon in storage process.In addition, because the refraction coefficient of matting agent and urethane resin has bigger difference, it easily occurs that the penetrating degree of film forming is poor after covering with paint, lacquer, colour wash, etc., and after covering with paint, lacquer, colour wash, etc., colour vividness is inadequate, occurs the phenomenon of " burnt hair, turn white ".
Summary of the invention
In order to solve the problems of the technologies described above, the invention provides a kind of preparation method from extinction type leather waterborne polyurethane coating agent.The method has been synthesized a kind of urethane A component with crosslinking structure greater particle size, and its B component less with particle diameter is mixed.Wherein A component molecular structure side chain is more, and micella particle has comparatively large vol, and its proportion is less than B component, floats over film surface in film process, makes film surface have higher roughness, thereby reaches extinction effect.Simultaneously, because A component and B component are all urethane resin, there is similar physico-chemical property and structure of functional groups, therefore, their consistency is better, and after film forming, refractive index is also comparatively approaching, efficiently solves problems of stability in storage, and after covering with paint, there is good penetrating degree, when reaching extinction effect, can not impact scytoblastema color.
For achieving the above object, the present invention adopts following technical scheme:
A preparation method from extinction type leather waterborne polyurethane coating agent, is characterized in that: preparation method is as follows:
The preparation of A polyurethane component A
A), by isocyanate trimerization body, vulcabond, small molecules hydrophilic monomer, macromolecule dihydric alcohol class monomer, catalyst mix, at 60 ~ 90 ℃, react 2 ~ 8 hours;
B) reaction solution is cooled to 30 ~ 50 ℃, adds triethylamine, reacts 10 ~ 30 minutes;
C) add deionized water, stir, disperse to obtain for 0.5 ~ 2 hour aqueous polyurethane component A emulsion;
The preparation of B polyurethane component B
A), by aliphatic diisocyanate, small molecules hydrophilic monomer, macromolecule dihydric alcohol class monomer, catalyst mix, at 60 ~ 90 ℃, react 2 ~ 8 hours;
B) reaction solution is cooled to 30 ~ 50 ℃, adds triethylamine, reacts 10 ~ 30 minutes;
C) add deionized water, stir, disperse to obtain for 0.5 ~ 2 hour polyurethane component B emulsion;
C blend
Polyurethane component A emulsion and polyurethane component B emulsion, in the ratio blend of 0.8 ~ 1.2:2, are added to thickening material under whipped state, make from extinction type leather waterborne polyurethane coating agent.
It is raw material that preparation method of the present invention adopts aliphatic isocyanates, compares with aromatic isocyanates such as MDI, TDI, and aliphatic isocyanates goods in use can not produce aromatic amine carcinogenic substance, and have good light fastness stability energy.
Component A emulsion described in preparation method of the present invention has extinction effect, compare with general outer silicon-dioxide flatting silica, the delustring wax powder adding, there is similar molecular structure and functional group to urethane resin, therefore, composite rear emulsion consistency is better, refractive index is also comparatively approaching, efficiently solve problems of stability in storage, after covering with paint, film forming has good penetrating degree, when reaching extinction effect, can not impact to scytoblastema color " turn white, burnt hair " phenomenon of having avoided that additional matting agent easily occurs.
The preparation of polyurethane component A of the present invention, the mol ratio of isocyanate trimerization body and vulcabond is 0.2 ~ 0.8:1, and the total amount of two kinds of isocyanic ester and the mol ratio of macromolecule dihydric alcohol are 3 ~ 7:1, small molecules hydrophilic monomer consumption is 1.5 ~ 8% of monomer total mass, the mole number of triethylamine is 80 ~ 120% of small molecules hydrophilic monomer mole number, catalyst levels is 5 ~ 20mg/L, and the solid content of polyaminoester emulsion is 20%.
Preferably, described isocyanate trimerization body and vulcabond mol ratio are 0.3 ~ 0.6:1, and the total amount of two kinds of isocyanic ester and macromolecule dihydric alcohol mol ratio are 3 ~ 5:1, described small molecules hydrophilic monomer consumption is 2 ~ 5% of monomer total mass, the mole number of triethylamine is 100% of small molecules hydrophilic monomer mole number, and described catalyst levels is 10mg/L.
The preparation of polyurethane component B of the present invention, the mol ratio of vulcabond and macromolecule dihydric alcohol is 2.5 ~ 5:1, small molecules hydrophilic monomer consumption is 2.5 ~ 7% of monomer total mass, the mole number of triethylamine is 80 ~ 120% of small molecules hydrophilic monomer mole number, catalyst levels is 5 ~ 20mg/L, and the solid content of polyaminoester emulsion is 20%.
Preferably, described vulcabond and the mol ratio of macromolecule dihydric alcohol are 2.8 ~ 4:1, described small molecules hydrophilic monomer consumption is 3 ~ 6% of monomer total mass, and the mole number of triethylamine is 100% of small molecules hydrophilic monomer mole number, and described catalyst levels is 10mg/L.
What preparation technology of the present invention made is 500 ~ 5000pa.s from extinction type leather waterborne polyurethane coating agent viscosity.
Isocyanate trimerization body of the present invention is hexamethylene diisocyanate (HDI) tripolymer or isophorone diisocyanate (IPDI) tripolymer.
Small molecules hydrophilic monomer of the present invention is dimethylol propionic acid or dimethylolpropionic acid.
Catalyzer of the present invention is dibutyl tin laurate.
Macromolecule dihydric alcohol of the present invention be the Polyoxypropylene diol of molecular weight 1000 ~ 4000, the PCDL of the polycaprolactone dibasic alcohol of molecular weight 1000 ~ 3000, molecular weight 1000 ~ 2000, any one in the polytetrahydrofuran diol of molecular weight 500 ~ 2000, molecular weight 500 ~ 2000 polyoxyethylene glycol or two or more combinations.
The production technology of existing water-based delustring polyurethane finishing agent, for making eliminate optical property reach requirement, need to be added silicon-dioxide flatting silica or delustring wax, poor with urethane consistency, thereby causes composite stability and cover with paint, lacquer, colour wash, etc. the rear penetrating degree of film forming poor.The present invention is directed to the problems referred to above, a kind of preparation method from extinction type Aqueous Polyurethane Leather Finishing Agent is provided, its beneficial effect is:
1, technique of the present invention is passed through Molecular Structure Design, synthesize the large particle diameter polyurethane component A with extinction effect, the molecular structure side chain of polyurethane component A is more, micella particle has comparatively large vol, its proportion is less, floats over film surface in film process, makes film surface have higher roughness, thereby reach extinction effect, without additional matting agent.
2, synthetic polyurethane component A and the matrix resin B component of the present invention is composite, finally forms from extinction type waterborne polyurethane coating agent.Be all urethane resin because of two kinds of components, have approximate physico-chemical property and structure of functional groups, close refraction coefficient after it has good consistency and film forming after composite, efficiently solves the problem that outer interpolation matting agent brings.After covering with paint, the penetrating degree of film forming well, can not impact scytoblastema color when reaching extinction effect, " turn white, burnt hair " phenomenon of having avoided that additional matting agent easily occurs.
3, preparation method of the present invention adopts particle diameter control techniques, by the ratio of strict control raw material, the consumption of tripolymer isocyanic ester and hydrophilic monomer particularly, thereby polyurethane component A particle diameter is controlled to 500 ~ 3000nm, the particle diameter of polyurethane component B is controlled at 20 ~ 200nm, make polyurethane component A float over film surface on well in film process, thus guaranteed finishing agent from extinction effect.
Embodiment
Below in conjunction with embodiment, essentiality content of the present invention is described in further detail.
Embodiment 1
From the preparation method of extinction type leather waterborne polyurethane coating agent, preparation method is as follows:
The preparation of A polyurethane component A
A), by isocyanate trimerization body, vulcabond, small molecules hydrophilic monomer, macromolecule dihydric alcohol class monomer, catalyst mix, at 60 ℃, react 8 hours;
B) reaction solution is cooled to 30 ℃, adds triethylamine, reacts 30 minutes;
C) add deionized water, stir, disperse to obtain for 2 hours aqueous polyurethane component A emulsion;
The preparation of B polyurethane component B
A), by aliphatic diisocyanate, small molecules hydrophilic monomer, macromolecule dihydric alcohol class monomer, catalyst mix, at 60 ℃, react 8 hours;
B) reaction solution is cooled to 30 ℃, adds triethylamine, reacts 30 minutes;
C) add deionized water, stir, disperse to obtain for 2 hours polyurethane component B emulsion;
C blend
Polyurethane component A emulsion and polyurethane component B emulsion, in the ratio blend of 0.8:2, are added to thickening material under whipped state, make from extinction type leather waterborne polyurethane coating agent.
Embodiment 2
From the preparation method of extinction type leather waterborne polyurethane coating agent, preparation method is as follows:
The preparation of A polyurethane component A
A), by isocyanate trimerization body, vulcabond, small molecules hydrophilic monomer, macromolecule dihydric alcohol class monomer, catalyst mix, at 90 ℃, react 2 hours;
B) reaction solution is cooled to 50 ℃, adds triethylamine, reacts 10 minutes;
C) add deionized water, stir, disperse to obtain for 0.5 hour aqueous polyurethane component A emulsion;
The molecule segment structure of component A is as follows:
Wherein, R is straight chained alkyl.
The preparation of B polyurethane component B
A), by aliphatic diisocyanate, small molecules hydrophilic monomer, macromolecule dihydric alcohol class monomer, catalyst mix, at 90 ℃, react 2 hours;
B) reaction solution is cooled to 50 ℃, adds triethylamine, reacts 10 minutes;
C) add deionized water, stir, disperse to obtain for 0.5 hour polyurethane component B emulsion;
C blend
Polyurethane component A emulsion and polyurethane component B emulsion, in the ratio blend of 1.2:2, are added to thickening material under whipped state, make from extinction type leather waterborne polyurethane coating agent.
Vulcabond of the present invention comprises at least one vulcabond, it is selected from isophorone diisocyanate (IPDI) and derivative thereof, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI) and derivative thereof, trans-hexanaphthene-1, 4-vulcabond (TMI), phosphorous vulcabond, tetramethoxy butane-1, 4-vulcabond, butane-1, 4-vulcabond, hexane-1, 6-vulcabond, dicyclohexyl methane diisocyanate, hexanaphthene-1, 4-vulcabond, hexanaphthene-1, 2-vulcabond, hexanaphthene-1, 3-vulcabond, ethylidene diisocyanate, norbornene alkyl diisocyanate.
Embodiment 3
From the preparation method of extinction type leather waterborne polyurethane coating agent, preparation method is as follows:
The preparation of A polyurethane component A
A), by isocyanate trimerization body, vulcabond, small molecules hydrophilic monomer, macromolecule dihydric alcohol class monomer, catalyst mix, at 70 ℃, react 3 hours;
B) reaction solution is cooled to 40 ℃, adds triethylamine, reacts 20 minutes;
C) add deionized water, stir, disperse to obtain for 1 hour aqueous polyurethane component A emulsion;
The preparation of B polyurethane component B
A), by aliphatic diisocyanate, small molecules hydrophilic monomer, macromolecule dihydric alcohol class monomer, catalyst mix, at 75 ℃, react 4 hours;
B) reaction solution is cooled to 45 ℃, adds triethylamine, reacts 20 minutes;
C) add deionized water, stir, disperse to obtain for 1.2 hours polyurethane component B emulsion;
C blend
Polyurethane component A emulsion and polyurethane component B emulsion, in the ratio blend of 1:2, are added to thickening material under whipped state, make from extinction type leather waterborne polyurethane coating agent.
Vulcabond of the present invention comprises at least one vulcabond, it is selected from isophorone diisocyanate (IPDI) and derivative thereof, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI) and derivative thereof, trans-hexanaphthene-1, 4-vulcabond (TMI), phosphorous vulcabond, tetramethoxy butane-1, 4-vulcabond, butane-1, 4-vulcabond, hexane-1, 6-vulcabond, dicyclohexyl methane diisocyanate, hexanaphthene-1, 4-vulcabond, hexanaphthene-1, 2-vulcabond, hexanaphthene-1, 3-vulcabond, ethylidene diisocyanate, norbornene alkyl diisocyanate.
Embodiment 4
From the preparation method of extinction type leather waterborne polyurethane coating agent, preparation method is as follows:
The preparation of A polyurethane component A
A), by isocyanate trimerization body, vulcabond, small molecules hydrophilic monomer, macromolecule dihydric alcohol class monomer, catalyst mix, at 80 ℃, react 5 hours;
B) reaction solution is cooled to 35 ℃, adds triethylamine, reacts 25 minutes;
C) add deionized water, stir, disperse to obtain for 1.5 hours aqueous polyurethane component A emulsion;
The preparation of B polyurethane component B
A), by aliphatic diisocyanate, small molecules hydrophilic monomer, macromolecule dihydric alcohol class monomer, catalyst mix, at 85 ℃, react 6 hours;
B) reaction solution is cooled to 36 ℃, adds triethylamine, reacts 16 minutes;
C) add deionized water, stir, disperse to obtain for 1.8 hours polyurethane component B emulsion;
C blend
Polyurethane component A emulsion and polyurethane component B emulsion, in the ratio blend of 0.9:2, are added to thickening material under whipped state, make from extinction type leather waterborne polyurethane coating agent.
Vulcabond of the present invention comprises at least one vulcabond, it is selected from isophorone diisocyanate (IPDI) and derivative thereof, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI) and derivative thereof, trans-hexanaphthene-1, 4-vulcabond (TMI), phosphorous vulcabond, tetramethoxy butane-1, 4-vulcabond, butane-1, 4-vulcabond, hexane-1, 6-vulcabond, dicyclohexyl methane diisocyanate, hexanaphthene-1, 4-vulcabond, hexanaphthene-1, 2-vulcabond, hexanaphthene-1, 3-vulcabond, ethylidene diisocyanate, norbornene alkyl diisocyanate.
Embodiment 5
The embodiment of the present embodiment is substantially the same manner as Example 3, on this basis:
The preparation of described polyurethane component A, the mol ratio of isocyanate trimerization body and vulcabond is 0.5:1, and the total amount of two kinds of isocyanic ester and the mol ratio of macromolecule dihydric alcohol are 4:1, small molecules hydrophilic monomer consumption is 5% of monomer total mass, the mole number of triethylamine is 90% of small molecules hydrophilic monomer mole number, catalyst levels is 10mg/L, and the solid content of polyaminoester emulsion is 20%.
Embodiment 6
The embodiment of the present embodiment is substantially the same manner as Example 3, on this basis:
The preparation of described polyurethane component B, the mol ratio of vulcabond and macromolecule dihydric alcohol is 3:1, small molecules hydrophilic monomer consumption is 5% of monomer total mass, the mole number of triethylamine is 85% of small molecules hydrophilic monomer mole number, catalyst levels is 15mg/L, and the solid content of polyaminoester emulsion is 20%.
Embodiment 7
The embodiment of the present embodiment is substantially the same manner as Example 3, on this basis:
The preparation of described polyurethane component A, the mol ratio of isocyanate trimerization body and vulcabond is 0.2:1, and the total amount of two kinds of isocyanic ester and the mol ratio of macromolecule dihydric alcohol are 3:1, small molecules hydrophilic monomer consumption is 1.5% of monomer total mass, the mole number of triethylamine is 80% of small molecules hydrophilic monomer mole number, catalyst levels is 5mg/L, and the solid content of polyaminoester emulsion is 20%.
The preparation of described polyurethane component B, the mol ratio of vulcabond and macromolecule dihydric alcohol is 2.5:1, small molecules hydrophilic monomer consumption is 2.5% of monomer total mass, the mole number of triethylamine is 80% of small molecules hydrophilic monomer mole number, catalyst levels is 5mg/L, and the solid content of polyaminoester emulsion is 20%.
The viscosity from extinction type leather waterborne polyurethane coating agent that described preparation technology makes is 500pa.s.
Embodiment 8
The embodiment of the present embodiment is substantially the same manner as Example 3, on this basis:
The preparation of described polyurethane component A, the mol ratio of isocyanate trimerization body and vulcabond is 0.8:1, and the total amount of two kinds of isocyanic ester and the mol ratio of macromolecule dihydric alcohol are 7:1, small molecules hydrophilic monomer consumption is 8% of monomer total mass, the mole number of triethylamine is 120% of small molecules hydrophilic monomer mole number, catalyst levels is 20mg/L, and the solid content of polyaminoester emulsion is 20%.
The preparation of described polyurethane component B, the mol ratio of vulcabond and macromolecule dihydric alcohol is 5:1, small molecules hydrophilic monomer consumption is 7% of monomer total mass, the mole number of triethylamine is 120% of small molecules hydrophilic monomer mole number, catalyst levels is 20mg/L, and the solid content of polyaminoester emulsion is 20%.
The viscosity from extinction type leather waterborne polyurethane coating agent that described preparation technology makes is 5000pa.s.
Embodiment 9
The embodiment of the present embodiment is substantially the same manner as Example 3, on this basis:
The preparation of described polyurethane component A, the mol ratio of isocyanate trimerization body and vulcabond is 0.6:1, and the total amount of two kinds of isocyanic ester and the mol ratio of macromolecule dihydric alcohol are 6:1, small molecules hydrophilic monomer consumption is 3.5% of monomer total mass, the mole number of triethylamine is 95% of small molecules hydrophilic monomer mole number, catalyst levels is 12mg/L, and the solid content of polyaminoester emulsion is 20%.
The preparation of described polyurethane component B, the mol ratio of vulcabond and macromolecule dihydric alcohol is 4:1, small molecules hydrophilic monomer consumption is 3% of monomer total mass, the mole number of triethylamine is 95% of small molecules hydrophilic monomer mole number, catalyst levels is 12mg/L, and the solid content of polyaminoester emulsion is 20%.
The viscosity from extinction type leather waterborne polyurethane coating agent that described preparation technology makes is 1000pa.s.
Embodiment 10
The embodiment of the present embodiment is substantially the same manner as Example 3, on this basis:
Described isocyanate trimerization body and vulcabond mol ratio are 0.3:1, and the total amount of two kinds of isocyanic ester and macromolecule dihydric alcohol mol ratio are 3:1, described small molecules hydrophilic monomer consumption is 2% of monomer total mass, the mole number of triethylamine is 100% of small molecules hydrophilic monomer mole number, described catalyst levels is 10mg/L, and the solid content of polyaminoester emulsion is 20%.
Described vulcabond and the mol ratio of macromolecule dihydric alcohol are 2.8:1, described small molecules hydrophilic monomer consumption is 3% of monomer total mass, the mole number of triethylamine is 100% of small molecules hydrophilic monomer mole number, described catalyst levels is 10mg/L, and the solid content of polyaminoester emulsion is 20%.
The viscosity from extinction type leather waterborne polyurethane coating agent that described preparation technology makes is 2000pa.s.
Embodiment 11
The embodiment of the present embodiment is substantially the same manner as Example 3, on this basis:
Described isocyanate trimerization body and vulcabond mol ratio are 0.6:1, and the total amount of two kinds of isocyanic ester and macromolecule dihydric alcohol mol ratio are 5:1, described small molecules hydrophilic monomer consumption is 5% of monomer total mass, the mole number of triethylamine is 100% of small molecules hydrophilic monomer mole number, described catalyst levels is 10mg/L, and the solid content of polyaminoester emulsion is 20%.
Described vulcabond and the mol ratio of macromolecule dihydric alcohol are 4:1, described small molecules hydrophilic monomer consumption is 6% of monomer total mass, the mole number of triethylamine is 100% of small molecules hydrophilic monomer mole number, and described catalyst levels is 10mg/L, and the solid content of polyaminoester emulsion is 20%.
The viscosity from extinction type leather waterborne polyurethane coating agent that described preparation technology makes is 1500pa.s.
Embodiment 12
The embodiment of the present embodiment is substantially the same manner as Example 3, on this basis:
Described isocyanate trimerization body and vulcabond mol ratio are 0.4:1, and the total amount of two kinds of isocyanic ester and macromolecule dihydric alcohol mol ratio are 4:1, described small molecules hydrophilic monomer consumption is 3% of monomer total mass, the mole number of triethylamine is 100% of small molecules hydrophilic monomer mole number, described catalyst levels is 10mg/L, and the solid content of polyaminoester emulsion is 20%.
Described vulcabond and the mol ratio of macromolecule dihydric alcohol are 3:1, described small molecules hydrophilic monomer consumption is 5% of monomer total mass, the mole number of triethylamine is 100% of small molecules hydrophilic monomer mole number, and described catalyst levels is 10mg/L, and the solid content of polyaminoester emulsion is 20%.
The viscosity from extinction type leather waterborne polyurethane coating agent that described preparation technology makes is 2500pa.s.
Embodiment 13
The embodiment of the present embodiment is substantially the same manner as Example 3, on this basis:
Described isocyanate trimerization body is hexamethylene diisocyanate trimer.
The viscosity from extinction type leather waterborne polyurethane coating agent that described preparation technology makes is 2500pa.s.
Embodiment 14
The embodiment of the present embodiment is substantially the same manner as Example 12, on this basis:
Described isocyanate trimerization body is isophorone diisocyanate trimer.
Described macromolecule dihydric alcohol is the Polyoxypropylene diol of molecular weight 1000 ~ 4000.
The viscosity from extinction type leather waterborne polyurethane coating agent that described preparation technology makes is 2500pa.s.
Embodiment 15
The embodiment of the present embodiment is substantially the same manner as Example 12, on this basis:
Described isocyanate trimerization body is hexamethylene diisocyanate trimer.
Described small molecules hydrophilic monomer is dimethylol propionic acid.
Described macromolecule dihydric alcohol is the polycaprolactone dibasic alcohol of molecular weight 1000 ~ 3000.
The viscosity from extinction type leather waterborne polyurethane coating agent that described preparation technology makes is 800pa.s.
Embodiment 16
The embodiment of the present embodiment is substantially the same manner as Example 12, on this basis:
Described isocyanate trimerization body is hexamethylene diisocyanate trimer.
Described small molecules hydrophilic monomer is dimethylolpropionic acid.
Described catalyzer is dibutyl tin laurate.
Described macromolecule dihydric alcohol is the PCDL of molecular weight 1000 ~ 2000.
The viscosity from extinction type leather waterborne polyurethane coating agent that described preparation technology makes is 4000pa.s.
Embodiment 17
The embodiment of the present embodiment is substantially the same manner as Example 12, on this basis:
Described isocyanate trimerization body is isophorone diisocyanate trimer.
Described small molecules hydrophilic monomer is dimethylolpropionic acid.
Described catalyzer is dibutyl tin laurate.
Described macromolecule dihydric alcohol is the polytetrahydrofuran diol of molecular weight 500 ~ 2000.
The viscosity from extinction type leather waterborne polyurethane coating agent that described preparation technology makes is 2500pa.s.
Embodiment 18
The embodiment of the present embodiment is substantially the same manner as Example 12, on this basis:
Described isocyanate trimerization body is isophorone diisocyanate trimer.
Described small molecules hydrophilic monomer is dimethylolpropionic acid.
Described catalyzer is dibutyl tin laurate.
Described macromolecule dihydric alcohol is molecular weight 500 ~ 2000 polyoxyethylene glycol.
The viscosity from extinction type leather waterborne polyurethane coating agent that described preparation technology makes is 3500pa.s.
Embodiment 19
The embodiment of the present embodiment is substantially the same manner as Example 12, on this basis:
Described isocyanate trimerization body is isophorone diisocyanate trimer.
Described small molecules hydrophilic monomer is dimethylolpropionic acid.
Described catalyzer is dibutyl tin laurate.
Described macromolecule dihydric alcohol is the Polyoxypropylene diol of molecular weight 1000 ~ 4000 and the polycaprolactone dibasic alcohol of molecular weight 1000 ~ 3000.
The viscosity from extinction type leather waterborne polyurethane coating agent that described preparation technology makes is 3500pa.s.
Embodiment 20
The embodiment of the present embodiment is substantially the same manner as Example 12, on this basis:
Described isocyanate trimerization body is isophorone diisocyanate trimer.
Described small molecules hydrophilic monomer is dimethylolpropionic acid.
Described catalyzer is dibutyl tin laurate.
Described macromolecule dihydric alcohol is the PCDL of molecular weight 1000 ~ 2000 and the polytetrahydrofuran diol of molecular weight 500 ~ 2000.
The viscosity from extinction type leather waterborne polyurethane coating agent that described preparation technology makes is 2500pa.s.
Embodiment 21
The embodiment of the present embodiment is substantially the same manner as Example 12, on this basis:
Described isocyanate trimerization body is isophorone diisocyanate trimer.
Described small molecules hydrophilic monomer is dimethylolpropionic acid.
Described catalyzer is dibutyl tin laurate.
Described macromolecule dihydric alcohol is that the Polyoxypropylene diol of molecular weight 1000 ~ 4000 is, the polytetrahydrofuran diol of molecular weight 500 ~ 2000 and molecular weight 500 ~ 2000 polyoxyethylene glycol.
The viscosity from extinction type leather waterborne polyurethane coating agent that described preparation technology makes is 2500pa.s.
Embodiment 22
From the preparation method of extinction type leather waterborne polyurethane coating agent, preparation method is as follows:
A component is synthetic: in the 500m1 four-hole boiling flask of agitator, condensing reflux pipe, thermopair is housed, add 32.6 grams of IPDI, 10 grams of HDI tripolymers, 30 grams of 2000 100 grams of molecular weight polyisoprene propylene glycol PPG, 0.01 gram of T12 catalyzer, 3.5 grams of dimethylol propionic acids, N-METHYLFORMAMIDE react 4 hours at 80 ℃, then be cooled to 45 degree and add 2.65 grams of triethylamines, be incubated and with emulsify at a high speed dispersion machine, under 1000r/min high-speed stirring, 570 grams of water added in performed polymer after 30 minutes, disperse to obtain oyster white polyaminoester emulsion after 30 minutes stand-by.Recording emulsion solid content is 20%, particle diameter 900-1100nm.
B component is synthetic: agitator is being housed, condensing reflux pipe, in the 500m1 four-hole boiling flask of thermopair, add 32 grams of IPDI, 2000 40 grams of molecular weight polyisoprene caprolactone diol PCL, 1000 20 grams of molecular weight polyisoprene caprolactone diol PCL, 0.01 gram of T12 catalyzer, 6 grams of dimethylol propionic acids, 20 grams of N-METHYLFORMAMIDEs react 4 hours at 80 ℃, then be cooled to 45 degree and add 4.5 grams of triethylamines, be incubated and with emulsify at a high speed dispersion machine, under 1000r/min high-speed stirring, 350 grams of water added in performed polymer after 30 minutes, disperse to obtain spreading unchecked optical transparency polyaminoester emulsion after 30 minutes stand-by.Recording emulsion solid content is 20%, particle diameter 40-60nm.
With emulsify at a high speed dispersion machine, under 800r/min high-speed stirring, 100 grams of A components and 200 grams of B components are uniformly mixed to 15 minutes, reduce rotating speed and add 6 grams of TT935 thickening materials to 300r/min, stir standing froth breaking after 30 minutes and obtain the finished product.Recording viscosity is 3100pa.s, and after scytoblastema surface daub on a wall, gloss unit 2.4, the obvious demixing phenomenon of nothing after centrifugal test.
Embodiment 23
From the preparation method of extinction type leather waterborne polyurethane coating agent, preparation method is as follows:
A component is synthetic: in the 500m1 four-hole boiling flask of agitator, condensing reflux pipe, thermopair is housed, add 20.5 grams of IPDI, 8 grams of HDI tripolymers, 20 grams of 1000 50 grams of molecular weight polyisoprene propylene glycol PPG, 0.01 gram of T12 catalyzer, 2.2 grams of dimethylol propionic acids, N-METHYLFORMAMIDE react 4 hours at 80 ℃, then be cooled to 45 degree and add 1.65 grams of triethylamines, be incubated and with emulsify at a high speed dispersion machine, under 1000r/min high-speed stirring, 320 grams of water added in performed polymer after 30 minutes, disperse to obtain oyster white polyaminoester emulsion after 30 minutes stand-by.Recording emulsion solid content is 20%, particle diameter 800-1000nm.
B component is synthetic: agitator is being housed, condensing reflux pipe, in the 500m1 four-hole boiling flask of thermopair, add 34 grams of IPDI, 2000 30 grams of molecular weight polyisoprene erythritan PTMEG, 1000 30 grams of molecular weight polyisoprene erythritan PTMEG, 0.01 gram of T12 catalyzer, 6 grams of dimethylol propionic acids, 20 grams of N-METHYLFORMAMIDEs react 4 hours at 80 ℃, then be cooled to 45 degree and add 4.5 grams of triethylamines, be incubated and with emulsify at a high speed dispersion machine, under 1000r/min high-speed stirring, 360 grams of water added in performed polymer after 30 minutes, disperse to obtain spreading unchecked optical transparency polyaminoester emulsion after 30 minutes stand-by.Recording emulsion solid content is 20%, particle diameter 40-50nm.
With emulsify at a high speed dispersion machine, under 800r/min high-speed stirring, 100 grams of A components and 200 grams of B components are uniformly mixed to 15 minutes, reduce rotating speed and add 5.6 grams of TT935 thickening materials to 300r/min, stir standing froth breaking after 30 minutes and obtain the finished product.Recording viscosity is 2500pa.s, and after scytoblastema surface daub on a wall, gloss unit 2.8, the obvious demixing phenomenon of nothing after centrifugal test.
Embodiment 24
From the preparation method of extinction type leather waterborne polyurethane coating agent, preparation method is as follows:
A component is synthetic: in the 500m1 four-hole boiling flask of agitator, condensing reflux pipe, thermopair is housed, add 22 grams of IPDI, 10 grams of IPDI tripolymers, 20 grams of 1000 60 grams of molecular weight polyisoprene propylene glycol PPG, 0.01 gram of T12 catalyzer, 2.2 grams of dimethylol propionic acids, N-METHYLFORMAMIDE react 4 hours at 80 ℃, then be cooled to 45 degree and add 1.65 grams of triethylamines, be incubated and with emulsify at a high speed dispersion machine, under 1000r/min high-speed stirring, 370 grams of water added in performed polymer after 30 minutes, disperse to obtain oyster white polyaminoester emulsion after 30 minutes stand-by.Recording emulsion solid content is 20%, particle diameter 1000-1200nm.
B component is synthetic: in the 500m1 four-hole boiling flask of agitator, condensing reflux pipe, thermopair is housed, add 30 grams of IPDI, 20 grams of 2000 60 grams of molecular weight polyisoprene erythritan PTMEG, 0.01 gram of T12 catalyzer, 5.5 grams of dimethylol propionic acids, N-METHYLFORMAMIDE react 4 hours at 80 ℃, then be cooled to 45 degree and add 4.1 grams of triethylamines, be incubated and with emulsify at a high speed dispersion machine, under 1000r/min high-speed stirring, 350 grams of water added in performed polymer after 30 minutes, disperse to obtain spreading unchecked optical transparency polyaminoester emulsion after 30 minutes stand-by.Recording emulsion solid content is 20%, particle diameter 50-70nm.
With emulsify at a high speed dispersion machine, under 800r/min high-speed stirring, 100 grams of A components and 200 grams of B components are uniformly mixed to 15 minutes, reduce rotating speed and add 6.4 grams of TT935 thickening materials to 300r/min, stir standing froth breaking after 30 minutes and obtain the finished product.Recording viscosity is 3200pa.s, and after scytoblastema surface daub on a wall, gloss unit 2, the obvious demixing phenomenon of nothing after centrifugal test.
Main raw material source related in the embodiment of the present invention is as follows:
HDI tripolymer, BAYER N3300; IPDI tripolymer, VESTANAT T1890, industrial goods
Polytetrahydrofuran diol (PTMEG, molecular weight 1000,2000) Korea S PTG produces, industrial goods;
Polypropylene glycol (molecular weight 1000,2000), Historic Area of Zhongshan in Nanjing City petrochemical iy produced, industrial goods.
Polycaprolactone glycol (molecular weight 1000,2000): PERSTORP company, industrial goods.
Dimethylol propionic acid, U.S. GEO S.R.L., industrial goods.。
Thickening material: TT935, LANXESS company, industrial goods.
Catalyzer: dibutyl tin laurate (T12), U.S.'s gas, technical grade.
SDF400 emulsify at a high speed dispersion machine.
Solid content testing method: according to GB/T 1725-79.
Emulsion particle diameter test: testing tool is the ZEN of Ma Erwen instrument company 1690 particle size analyzers, and probe temperature is 25 ℃.
Stability in storage: get emulsion and be placed in separating centrifuge, centrifugation is 15 minutes under 3000rpm/min, if produce and illustrate that stability in storage is more than 6 months without precipitation.
Glossiness test: testing tool adopts the German BYK AG-4446 of company, tests according to ISO 2813, GB 9754 standards.
Claims (10)
1. from the preparation method of extinction type leather waterborne polyurethane coating agent, it is characterized in that: preparation method is as follows:
The preparation of A polyurethane component A
A), by isocyanate trimerization body, vulcabond, small molecules hydrophilic monomer, macromolecule dihydric alcohol class monomer, catalyst mix, at 60 ~ 90 ℃, react 2 ~ 8 hours;
B) reaction solution is cooled to 30 ~ 50 ℃, adds triethylamine, reacts 10 ~ 30 minutes;
C) add deionized water, stir, disperse to obtain for 0.5 ~ 2 hour aqueous polyurethane component A emulsion;
The preparation of B polyurethane component B
A), by aliphatic diisocyanate, small molecules hydrophilic monomer, macromolecule dihydric alcohol class monomer, catalyst mix, at 60 ~ 90 ℃, react 2 ~ 8 hours;
B) reaction solution is cooled to 30 ~ 50 ℃, adds triethylamine, reacts 10 ~ 30 minutes;
C) add deionized water, stir, disperse to obtain for 0.5 ~ 2 hour polyurethane component B emulsion;
C blend
Polyurethane component A emulsion and polyurethane component B emulsion, in the ratio blend of 0.8 ~ 1.2:2, are added to thickening material under whipped state, make from extinction type leather waterborne polyurethane coating agent.
2. the preparation method from extinction type leather waterborne polyurethane coating agent according to claim 1, it is characterized in that: the preparation of described polyurethane component A, the mol ratio of isocyanate trimerization body and vulcabond is 0.2 ~ 0.8:1, and the total amount of two kinds of isocyanic ester and the mol ratio of macromolecule dihydric alcohol are 3 ~ 7:1, small molecules hydrophilic monomer consumption is 1.5 ~ 8% of monomer total mass, the mole number of triethylamine is 80 ~ 120% of small molecules hydrophilic monomer mole number, catalyst levels is 5 ~ 20mg/L, and the solid content of polyaminoester emulsion is 20%.
3. the preparation method from extinction type leather waterborne polyurethane coating agent according to claim 1, it is characterized in that: the preparation of described polyurethane component B, the mol ratio of vulcabond and macromolecule dihydric alcohol is 2.5 ~ 5:1, small molecules hydrophilic monomer consumption is 2.5 ~ 7% of monomer total mass, the mole number of triethylamine is 80 ~ 120% of small molecules hydrophilic monomer mole number, catalyst levels is 5 ~ 20mg/L, and the solid content of polyaminoester emulsion is 20%.
4. the preparation method from extinction type leather waterborne polyurethane coating agent according to claim 2, it is characterized in that: described isocyanate trimerization body and vulcabond mol ratio are 0.3 ~ 0.6:1, and the total amount of two kinds of isocyanic ester and macromolecule dihydric alcohol mol ratio are 3 ~ 5:1, described small molecules hydrophilic monomer consumption is 2 ~ 5% of monomer total mass, the mole number of triethylamine is 100% of small molecules hydrophilic monomer mole number, and described catalyst levels is 10mg/L.
5. the preparation method from extinction type leather waterborne polyurethane coating agent according to claim 3, it is characterized in that: described vulcabond and the mol ratio of macromolecule dihydric alcohol are 2.8 ~ 4:1, described small molecules hydrophilic monomer consumption is 3 ~ 6% of monomer total mass, the mole number of triethylamine is 100% of small molecules hydrophilic monomer mole number, and described catalyst levels is 10mg/L.
6. the preparation method from extinction type leather waterborne polyurethane coating agent according to claim 1, is characterized in that: the viscosity from extinction type leather waterborne polyurethane coating agent that described preparation technology makes is 500 ~ 5000pa.s.
7. the preparation method from extinction type leather waterborne polyurethane coating agent according to claim 1, is characterized in that: described isocyanate trimerization body is hexamethylene diisocyanate trimer or isophorone diisocyanate trimer.
8. the preparation method from extinction type leather waterborne polyurethane coating agent according to claim 1, is characterized in that: described small molecules hydrophilic monomer is dimethylol propionic acid or dimethylolpropionic acid.
9. the preparation method from extinction type leather waterborne polyurethane coating agent according to claim 1, is characterized in that: described catalyzer is dibutyl tin laurate.
10. the preparation method from extinction type leather waterborne polyurethane coating agent according to claim 1, is characterized in that: described macromolecule dihydric alcohol be the Polyoxypropylene diol of molecular weight 1000 ~ 4000, the PCDL of the polycaprolactone dibasic alcohol of molecular weight 1000 ~ 3000, molecular weight 1000 ~ 2000, any one in the polytetrahydrofuran diol of molecular weight 500 ~ 2000, molecular weight 500 ~ 2000 polyoxyethylene glycol or two or more combinations.
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