CN103740250B - From the preparation method of extinction type leather waterborne polyurethane coating agent - Google Patents
From the preparation method of extinction type leather waterborne polyurethane coating agent Download PDFInfo
- Publication number
- CN103740250B CN103740250B CN201310651725.2A CN201310651725A CN103740250B CN 103740250 B CN103740250 B CN 103740250B CN 201310651725 A CN201310651725 A CN 201310651725A CN 103740250 B CN103740250 B CN 103740250B
- Authority
- CN
- China
- Prior art keywords
- preparation
- monomer
- little molecule
- coating agent
- hydrophilic monomer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 73
- 230000008033 biological extinction Effects 0.000 title claims abstract description 55
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 55
- 239000010985 leather Substances 0.000 title claims abstract description 47
- 239000011527 polyurethane coating Substances 0.000 title claims abstract description 42
- 239000004814 polyurethane Substances 0.000 claims abstract description 69
- 229920002635 polyurethane Polymers 0.000 claims abstract description 69
- 239000002245 particle Substances 0.000 claims abstract description 20
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 105
- 239000000178 monomer Substances 0.000 claims description 103
- 239000000839 emulsion Substances 0.000 claims description 56
- 239000012948 isocyanate Substances 0.000 claims description 42
- 229920002521 macromolecule Polymers 0.000 claims description 40
- 150000002513 isocyanates Chemical class 0.000 claims description 39
- 239000003054 catalyst Substances 0.000 claims description 37
- 238000005829 trimerization reaction Methods 0.000 claims description 28
- 239000007787 solid Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 238000005516 engineering process Methods 0.000 claims description 21
- 150000001298 alcohols Chemical class 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 19
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 15
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 13
- 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 13
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 239000000376 reactant Substances 0.000 claims description 12
- -1 Polyoxypropylene Polymers 0.000 claims description 11
- 239000013638 trimer Substances 0.000 claims description 11
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 10
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 9
- 150000002009 diols Chemical class 0.000 claims description 9
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 8
- 235000019260 propionic acid Nutrition 0.000 claims description 8
- 229920001451 polypropylene glycol Polymers 0.000 claims description 6
- 229920001610 polycaprolactone Polymers 0.000 claims description 5
- 239000004632 polycaprolactone Substances 0.000 claims description 5
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims 2
- 230000000694 effects Effects 0.000 abstract description 11
- 238000000034 method Methods 0.000 abstract description 10
- 239000003973 paint Substances 0.000 abstract description 8
- 230000000149 penetrating effect Effects 0.000 abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 27
- 239000006185 dispersion Substances 0.000 description 10
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 229920001195 polyisoprene Polymers 0.000 description 8
- 238000009835 boiling Methods 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- 239000002562 thickening agent Substances 0.000 description 5
- SSYDTHANSGMJTP-ZXZARUISSA-N (3s,4r)-oxolane-3,4-diol Chemical compound O[C@H]1COC[C@H]1O SSYDTHANSGMJTP-ZXZARUISSA-N 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 238000003475 lamination Methods 0.000 description 4
- 229920005749 polyurethane resin Polymers 0.000 description 4
- 239000000377 silicon dioxide 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
- 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
- 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
- UMRZSTCPUPJPOJ-KNVOCYPGSA-N norbornane Chemical compound C1C[C@H]2CC[C@@H]1C2 UMRZSTCPUPJPOJ-KNVOCYPGSA-N 0.000 description 3
- 229920000909 polytetrahydrofuran Polymers 0.000 description 3
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical class CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 3
- 150000004672 propanoic acids Chemical class 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
- 239000000126 substance Substances 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
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000005034 decoration 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
- 150000002148 esters Chemical class 0.000 description 1
- 150000003948 formamides Chemical class 0.000 description 1
- 239000007788 liquid Substances 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
- 238000010422 painting Methods 0.000 description 1
- 230000036314 physical performance Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Landscapes
- Treatment And Processing Of Natural Fur Or Leather (AREA)
- Paints Or Removers (AREA)
Abstract
The invention provides a kind of preparation method from extinction type leather waterborne polyurethane coating agent. The method has been synthesized a kind of polyurethane A component with cross-linked 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 larger volume, and its proportion is less than B component, floats over film surface in film forming procedure, makes film surface have higher roughness, thereby reaches extinction effect, without additional delustering agent; And after covering with paint, there is good penetrating degree, in reaching extinction effect, can not impact scytoblastema color.
Description
Technical field
The invention belongs to leather chemical industry field, be specifically related to a kind of preparation from extinction type leather waterborne polyurethane coating agentMethod.
Background technology
Aqueous polyurethane refers to that polyurethane is dissolved in water or is scattered in water and a kind of polyaminoester emulsion of forming. 20Since the sixties in century, solvent borne polyurethane has obtained widely using, but organic solvent causes air pollution while using,Have toxicity more or less, in recent years, people's environmental consciousness constantly strengthens, and this has promoted the exploitation of water-base polyurethane material.Aqueous polyurethane is taking water as basic medium, have free from environmental pollution, energy-conservation, operate the advantages such as easy to process, be subject to people'sPay attention to.
Delustring waterborne polyurethane coating agent is a kind of staple product in leather finishing agent, and it is mainly used in top finishing,Its performance characteristics is good physical performance, comfortable feel, have water-fast, solvent resistance, light fastness stability energy, wear-resisting resistance to preferablyDry wet rubbing performance. Must have in addition good eliminate optical property and storage stability, after covering with paint, require graining, the pore of leatherClear, 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, thus by light to each Tongfang notTo carrying out scattering, reach extinction effect. At present domestic leather finishing agent manufacturer is producing the painting of extinction type aqueous polyurethaneWhen decorations agent, for reaching good eliminate optical property, generally all need additional delustering agent to realize, as add silica-based delustringPowder, delustring wax etc.
As 201110166205.3, it is special that name is called the invention of " goth black delustring inorganic agent of the special mist of leather and preparation method thereof "Profit application, discloses goth black delustring inorganic agent of the special mist of a kind of leather and preparation method thereof, and its formula consists of: polyurethane treeFat 30 ~ 60%, auxiliary agent 0 ~ 2%, flatting silica 4% ~ 10%, solvent 30% ~ 60%.
Because the structure of matter and the polyurethane molecular of these delustering agents have larger difference, its compatibility is poor, is storingIn process, easily there is lamination. In addition, because the refraction coefficient of delustering agent and polyurethane resin has bigger difference, its covering with paintEasily occur that afterwards the penetrating degree of film forming is poor, 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 system from extinction type leather waterborne polyurethane coating agentPreparation Method. The method has been synthesized a kind of polyurethane A component with cross-linked structure greater particle size, makes the B group that itself and particle diameter are lessDivide and mix. Wherein A component molecular structure side chain is more, and micella particle has larger volume, and its proportion is less than B component,On in film forming procedure, float over film surface, make film surface there is higher roughness, thereby reach extinction effect. Meanwhile, due to A groupDividing with B component is all polyurethane resin, has similar physico-chemical property and structure of functional groups, and therefore, their compatibility is better,After film forming, index of refraction is also comparatively approaching, efficiently solves problems of stability in storage, and after covering with paint, has good penetrating degree,When reaching extinction effect, can not impact scytoblastema color.
For achieving the above object, the present invention adopts following technical scheme:
From a preparation method for 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, little molecule hydrophilic monomer, macromolecule dihydric alcohol class monomer, catalysisAgent mixes, and reacts 2 ~ 8 hours at 60 ~ 90 DEG C;
B) reactant liquor is cooled to 30 ~ 50 DEG C, 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, little molecule hydrophilic monomer, macromolecule dihydric alcohol class monomer, catalyst mix,At 60 ~ 90 DEG C, react 2 ~ 8 hours;
B) reactant liquor is cooled to 30 ~ 50 DEG C, 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 under stirringEnter thickener, make from extinction type leather waterborne polyurethane coating agent.
It is raw material that preparation method of the present invention adopts aliphatic isocyanates, with the aromatic isocyanate such as MDI, TDI phaseRatio, aliphatic isocyanates goods in use can not produce aromatic amine carcinogen, and have fast light preferablyStability.
Component A emulsion described in preparation method of the present invention has extinction effect, disappears with the general outer silica addingLight powder, delustring wax powder are compared, and have similar molecular structure and functional group to polyurethane resin, and therefore, composite rear emulsion is compatibleProperty is better, and index of refraction is also comparatively approaching, efficiently solves problems of stability in storage, and after covering with paint, film forming has penetrating preferablyDegree can not impact scytoblastema color in reaching extinction effect, has avoided easily " sending out of appearance of additional delustering agentBurnt hair in vain, " phenomenon.
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 isocyanates and the mol ratio of macromolecule dihydric alcohol be 3 ~ 7:1, little molecule hydrophilic monomer consumption is1.5 ~ 8% of monomer gross mass, the molal quantity of triethylamine is 80 ~ 120% of little molecule hydrophilic monomer molal quantity, catalyst amount is5 ~ 20mg/L, the solid content of polyaminoester emulsion is 20%.
Preferably, described isocyanate trimerization body and vulcabond mol ratio are 0.3 ~ 0.6:1, and two kinds of isocyanic acidsThe total amount of ester and macromolecule dihydric alcohol mol ratio are 3 ~ 5:1, described little molecule hydrophilic monomer consumption be 2 of monomer gross mass ~5%, the molal quantity of triethylamine is 100% of little molecule hydrophilic monomer molal quantity, and described catalyst amount 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, little molecule hydrophilic monomer consumption is 2.5 ~ 7% of monomer gross mass, the molal quantity of triethylamine is little molecule hydrophilic monomer mole80 ~ 120% of number, catalyst amount is 5 ~ 20mg/L, 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 little molecule parentAqueous monomer consumption is 3 ~ 6% of monomer gross mass, and the molal quantity of triethylamine is 100% of little molecule hydrophilic monomer molal quantity, described inCatalyst amount be 10mg/L.
Preparation technology of the present invention make from extinction type leather waterborne polyurethane coating agent viscosity be 500 ~5000pa.s。
Isocyanate trimerization body of the present invention is hexamethylene diisocyanate (HDI) tripolymer or isophoroneVulcabond (IPDI) tripolymer.
Little molecule hydrophilic monomer of the present invention is dihydromethyl propionic acid or dimethylolpropionic acid.
Catalyst of the present invention is dibutyl tin laurate.
Macromolecule dihydric alcohol of the present invention is Polyoxypropylene diol, the molecular weight of molecular weight 1000 ~ 40001000 ~ 3000 polycaprolactone dihydroxylic alcohols, the PCDL of molecular weight 1000 ~ 2000, molecular weight 500 ~ 2000 poly-Any one in erythritan, molecular weight 500 ~ 2000 polyethylene 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 titanium dioxideSilicon flatting silica or delustring wax, poor with polyurethane compatibility, thus cause 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, it has beneficial effectFruit is:
1, technique of the present invention, by Molecular Design, synthesizes the large particle diameter polyurethane component A with extinction effect, poly-The molecular structure side chain of ammonia ester component A is more, and micella particle has larger volume, and its proportion is less, in film forming procedure, floatsOn film surface, make film surface there is higher roughness, thereby reach extinction effect, without additional delustering agent.
2, synthetic polyurethane component A and the matrix resin B component of the present invention is composite, final formation from the poly-ammonia of extinction type water-basedEster finishing agent. Because two kinds of components are all polyurethane resin, there is approximate physico-chemical property and structure of functional groups, it is at composite rear toolThere is close refraction coefficient after good compatibility and film forming, efficiently solve the problem that outer interpolation delustering agent brings. Covering with paint, lacquer, colour wash, etc.The penetrating degree of rear film forming well, can not impact scytoblastema color in reaching extinction effect, has avoided additional delustering agent" turn white, the burnt hair " phenomenon easily occurring.
3, preparation method of the present invention adopts particle diameter control technology, by the ratio of strict control raw material, particularly tripolymerThe consumption of isocyanates and hydrophilic monomer, thus polyurethane component A particle diameter is controlled to 500 ~ 3000nm, polyurethane component B'sParticle diameter is controlled at 20 ~ 200nm, makes polyurethane component A float over film surface on well in film forming procedure, thereby has ensured covering with paintAgent from extinction effect.
Detailed description of the invention
Below in conjunction with detailed description of the invention, 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, little molecule hydrophilic monomer, macromolecule dihydric alcohol class monomer, catalysisAgent mixes, and reacts 8 hours at 60 DEG C;
B) reactant liquor is cooled to 30 DEG C, 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, little molecule hydrophilic monomer, macromolecule dihydric alcohol class monomer, catalyst mix,At 60 DEG C, react 8 hours;
B) reactant liquor is cooled to 30 DEG C, 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 increasing under stirringThick dose, 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, little molecule hydrophilic monomer, macromolecule dihydric alcohol class monomer, catalysisAgent mixes, and reacts 2 hours at 90 DEG C;
B) reactant liquor is cooled to 50 DEG C, 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, little molecule hydrophilic monomer, macromolecule dihydric alcohol class monomer, catalyst mix,At 90 DEG C, react 2 hours;
B) reactant liquor is cooled to 50 DEG C, 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 increasing under stirringThick dose, make from extinction type leather waterborne polyurethane coating agent.
Vulcabond of the present invention comprises at least one vulcabond, and it is selected from IPDIAnd derivative, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI) and derivative thereof, trans-hexamethylene (IPDI)Alkane-Isosorbide-5-Nitrae-vulcabond (TMI), phosphorous vulcabond, tetramethoxy butane-Isosorbide-5-Nitrae-vulcabond, butane-Isosorbide-5-Nitrae-Vulcabond, hexane-1,6-vulcabond, dicyclohexyl methyl hydride diisocyanate, cyclohexane-Isosorbide-5-Nitrae-vulcabond,Cyclohexane-1,2-vulcabond, cyclohexane-1,3-vulcabond, ethylidene diisocyanate, norbornane two isocyanic acidsEster.
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, little molecule hydrophilic monomer, macromolecule dihydric alcohol class monomer, catalysisAgent mixes, and reacts 3 hours at 70 DEG C;
B) reactant liquor is cooled to 40 DEG C, 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, little molecule hydrophilic monomer, macromolecule dihydric alcohol class monomer, catalyst mix,At 75 DEG C, react 4 hours;
B) reactant liquor is cooled to 45 DEG C, 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 under stirringAgent, makes from extinction type leather waterborne polyurethane coating agent.
Vulcabond of the present invention comprises at least one vulcabond, and it is selected from IPDIAnd derivative, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI) and derivative thereof, trans-hexamethylene (IPDI)Alkane-Isosorbide-5-Nitrae-vulcabond (TMI), phosphorous vulcabond, tetramethoxy butane-Isosorbide-5-Nitrae-vulcabond, butane-Isosorbide-5-Nitrae-Vulcabond, hexane-1,6-vulcabond, dicyclohexyl methyl hydride diisocyanate, cyclohexane-Isosorbide-5-Nitrae-vulcabond,Cyclohexane-1,2-vulcabond, cyclohexane-1,3-vulcabond, ethylidene diisocyanate, norbornane two isocyanic acidsEster.
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, little molecule hydrophilic monomer, macromolecule dihydric alcohol class monomer, catalysisAgent mixes, and reacts 5 hours at 80 DEG C;
B) reactant liquor is cooled to 35 DEG C, 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, little molecule hydrophilic monomer, macromolecule dihydric alcohol class monomer, catalyst mix,At 85 DEG C, react 6 hours;
B) reactant liquor is cooled to 36 DEG C, 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 increasing under stirringThick dose, make from extinction type leather waterborne polyurethane coating agent.
Vulcabond of the present invention comprises at least one vulcabond, and it is selected from IPDIAnd derivative, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI) and derivative thereof, trans-hexamethylene (IPDI)Alkane-Isosorbide-5-Nitrae-vulcabond (TMI), phosphorous vulcabond, tetramethoxy butane-Isosorbide-5-Nitrae-vulcabond, butane-Isosorbide-5-Nitrae-Vulcabond, hexane-1,6-vulcabond, dicyclohexyl methyl hydride diisocyanate, cyclohexane-Isosorbide-5-Nitrae-vulcabond,Cyclohexane-1,2-vulcabond, cyclohexane-1,3-vulcabond, ethylidene diisocyanate, norbornane two isocyanic acidsEster.
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, andThe total amount of two kinds of isocyanates and the mol ratio of macromolecule dihydric alcohol are 4:1, and little molecule hydrophilic monomer consumption is monomer gross mass5%, the molal quantity of triethylamine is 90% of little molecule hydrophilic monomer molal quantity, catalyst amount is 10mg/L, polyaminoester emulsionSolid content be 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, little moleculeHydrophilic monomer consumption is 5% of monomer gross mass, and the molal quantity of triethylamine is 85% of little molecule hydrophilic monomer molal quantity, catalystConsumption 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, andThe total amount of two kinds of isocyanates and the mol ratio of macromolecule dihydric alcohol are 3:1, and little molecule hydrophilic monomer consumption is monomer gross mass1.5%, the molal quantity of triethylamine is 80% of little molecule hydrophilic monomer molal quantity, catalyst amount is 5mg/L, polyaminoester emulsionSolid content be 20%.
The preparation of described polyurethane component B, the mol ratio of vulcabond and macromolecule dihydric alcohol is 2.5:1, little pointSub-hydrophilic monomer consumption is 2.5% of monomer gross mass, and the molal quantity of triethylamine is 80% of little molecule hydrophilic monomer molal quantity, urgesAgent consumption 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, andThe total amount of two kinds of isocyanates and the mol ratio of macromolecule dihydric alcohol are 7:1, and little molecule hydrophilic monomer consumption is monomer gross mass8%, the molal quantity of triethylamine is 120% of little molecule hydrophilic monomer molal quantity, catalyst amount is 20mg/L, polyaminoester emulsionSolid content be 20%.
The preparation of described polyurethane component B, the mol ratio of vulcabond and macromolecule dihydric alcohol is 5:1, little moleculeHydrophilic monomer consumption is 7% of monomer gross mass, and the molal quantity of triethylamine is 120% of little molecule hydrophilic monomer molal quantity, catalysisAgent consumption 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, andThe total amount of two kinds of isocyanates and the mol ratio of macromolecule dihydric alcohol are 6:1, and little molecule hydrophilic monomer consumption is monomer gross mass3.5%, the molal quantity of triethylamine is 95% of little molecule hydrophilic monomer molal quantity, catalyst amount is 12mg/L, polyurethane breastThe solid content of liquid is 20%.
The preparation of described polyurethane component B, the mol ratio of vulcabond and macromolecule dihydric alcohol is 4:1, little moleculeHydrophilic monomer consumption is 3% of monomer gross mass, and the molal quantity of triethylamine is 95% of little molecule hydrophilic monomer molal quantity, catalystConsumption 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 isocyanates withMacromolecule dihydric alcohol mol ratio is 3:1, and described little molecule hydrophilic monomer consumption is 2% of monomer gross mass, triethylamine moleNumber is 100% of little molecule hydrophilic monomer molal quantity, and described catalyst amount is 10mg/L, and the solid content of polyaminoester emulsion is20%。
Described vulcabond and the mol ratio of macromolecule dihydric alcohol are 2.8:1, and described little molecule hydrophilic monomer is usedAmount is 3% of monomer gross mass, and the molal quantity of triethylamine is 100% of little molecule hydrophilic monomer molal quantity, and described catalyst is usedAmount 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 isocyanates withMacromolecule dihydric alcohol mol ratio is 5:1, and described little molecule hydrophilic monomer consumption is 5% of monomer gross mass, triethylamine moleNumber is 100% of little molecule hydrophilic monomer molal quantity, and described catalyst amount is 10mg/L, and the solid content of polyaminoester emulsion is20%。
Described vulcabond and the mol ratio of macromolecule dihydric alcohol are 4:1, described little molecule hydrophilic monomer consumptionFor 6% of monomer gross mass, the molal quantity of triethylamine is 100% of little molecule hydrophilic monomer molal quantity, described catalyst amountFor 10mg/L, 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 isocyanates withMacromolecule dihydric alcohol mol ratio is 4:1, and described little molecule hydrophilic monomer consumption is 3% of monomer gross mass, triethylamine moleNumber is 100% of little molecule hydrophilic monomer molal quantity, and described catalyst amount is 10mg/L, and the solid content of polyaminoester emulsion is20%。
Described vulcabond and the mol ratio of macromolecule dihydric alcohol are 3:1, described little molecule hydrophilic monomer consumptionFor 5% of monomer gross mass, the molal quantity of triethylamine is 100% of little molecule hydrophilic monomer molal quantity, described catalyst amountFor 10mg/L, 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 little molecule hydrophilic monomer is dihydromethyl propionic acid.
Described macromolecule dihydric alcohol is the polycaprolactone dihydroxylic alcohols 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 little molecule hydrophilic monomer is dimethylolpropionic acid.
Described catalyst 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 little molecule hydrophilic monomer is dimethylolpropionic acid.
Described catalyst 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 little molecule hydrophilic monomer is dimethylolpropionic acid.
Described catalyst is dibutyl tin laurate.
Described macromolecule dihydric alcohol is molecular weight 500 ~ 2000 polyethylene 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 little molecule hydrophilic monomer is dimethylolpropionic acid.
Described catalyst is dibutyl tin laurate.
Described macromolecule dihydric alcohol be the Polyoxypropylene diol of molecular weight 1000 ~ 4000 and molecular weight 1000 ~3000 polycaprolactone dihydroxylic alcohols.
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 little molecule hydrophilic monomer is dimethylolpropionic acid.
Described catalyst is dibutyl tin laurate.
Described macromolecule dihydric alcohol is the PCDL of molecular weight 1000 ~ 2000 and molecular weight 500 ~ 2000Polytetrahydrofuran diol.
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 little molecule hydrophilic monomer is dimethylolpropionic acid.
Described catalyst is dibutyl tin laurate.
Described macromolecule dihydric alcohol is Polyoxypropylene diol, the molecular weight 500 ~ 2000 of molecular weight 1000 ~ 4000Polytetrahydrofuran diol and molecular weight 500 ~ 2000 polyethylene 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: being equipped with in the 500m1 four-hole boiling flask of agitator, condensing reflux pipe, thermocouple, add IPDI10 grams of 32.6 grams, HDI tripolymer, 2000 PPG100 gram of molecular weight polyisoprene propane diols, 0.01 gram of T12 catalyst, dihydromethyl propionic acid30 grams of 3.5 grams, N-METHYLFORMAMIDE react 4 hours at 80 DEG C, are then cooled to 45 degree and add 2.65 grams of triethylamines, insulation 30After minute, 570 grams of water are added in performed polymer under 1000r/min high-speed stirred with emulsify at a high speed dispersion machine, disperse after 30 minutesObtain milky polyaminoester emulsion stand-by. Recording emulsion solid content is 20%, particle diameter 900-1100nm.
B component is synthetic: being equipped with in the 500m1 four-hole boiling flask of agitator, condensing reflux pipe, thermocouple, add IPDI32Gram, 2000 PCL40 gram of molecular weight polyisoprene caprolactone diol, PCL20 gram of 1000 molecular weight polyisoprene caprolactone diol, T12 catalyst20 grams of 0.01 grams, 6 grams of dihydromethyl propionic acids, N-METHYLFORMAMIDE react 4 hours at 80 DEG C, are then cooled to 45 degree and add4.5 grams of triethylamines, are incubated after 30 minutes and 350 grams of water are added in advance under 1000r/min high-speed stirred with emulsify at a high speed dispersion machineIn aggressiveness, disperse to obtain spreading unchecked optical transparency polyaminoester emulsion after 30 minutes stand-by. Recording emulsion solid content is 20%, particle diameter 40-60nm。
Under 800r/min high-speed stirred, 100 grams of A components and 200 grams of B components are uniformly mixed with emulsify at a high speed dispersion machine15 minutes, reduce rotating speed and add 6 grams of TT935 thickeners to 300r/min, stirs standing froth breaking after 30 minutes and obtain final products.Recording viscosity is 3100pa.s, gloss unit 2.4 after scytoblastema top finishing, obviously lamination 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: being equipped with in the 500m1 four-hole boiling flask of agitator, condensing reflux pipe, thermocouple, add IPDI8 grams of 20.5 grams, HDI tripolymer, 1000 PPG50 gram of molecular weight polyisoprene propane diols, 0.01 gram of T12 catalyst, dihydromethyl propionic acid20 grams of 2.2 grams, N-METHYLFORMAMIDE react 4 hours at 80 DEG C, are then cooled to 45 degree and add 1.65 grams of triethylamines, insulation 30After minute, 320 grams of water are added in performed polymer under 1000r/min high-speed stirred with emulsify at a high speed dispersion machine, disperse after 30 minutesObtain milky polyaminoester emulsion stand-by. Recording emulsion solid content is 20%, particle diameter 800-1000nm.
B component is synthetic: being equipped with in the 500m1 four-hole boiling flask of agitator, condensing reflux pipe, thermocouple, add IPDI34Gram, 2000 PTMEG30 gram of molecular weight polyisoprene erythritan, PTMEG30 gram of 1000 molecular weight polyisoprene erythritan, T1220 grams of 0.01 gram of catalyst, 6 grams of dihydromethyl propionic acids, N-METHYLFORMAMIDE react 4 hours at 80 DEG C, are then cooled to 45 degreeAdd 4.5 grams of triethylamines, be incubated after 30 minutes and 360 grams of water added under 1000r/min high-speed stirred with emulsify at a high speed dispersion machineEnter in performed polymer, disperse to obtain spreading unchecked optical transparency polyaminoester emulsion after 30 minutes stand-by. Recording emulsion solid content is 20%, particle diameter40-50nm。
Under 800r/min high-speed stirred, 100 grams of A components and 200 grams of B components are uniformly mixed with emulsify at a high speed dispersion machine15 minutes, reduce rotating speed and add 5.6 grams of TT935 thickeners to 300r/min, stirs and after 30 minutes, leave standstill froth breaking and obtain finally productProduct. Recording viscosity is 2500pa.s, gloss unit 2.8 after scytoblastema top finishing, obviously lamination 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: being equipped with in the 500m1 four-hole boiling flask of agitator, condensing reflux pipe, thermocouple, add IPDI22Gram, 10 grams of IPDI tripolymers, 1000 PPG60 gram of molecular weight polyisoprene propane diols, 0.01 gram of T12 catalyst, dihydromethyl propionic acid 2.2Gram, 20 grams of N-METHYLFORMAMIDEs react 4 hours at 80 DEG C, are then cooled to 45 degree and add 1.65 grams of triethylamines, are incubated 30 pointsZhong Houyong emulsify at a high speed dispersion machine adds 370 grams of water in performed polymer under 1000r/min high-speed stirred, disperses to obtain after 30 minutesStand-by to milky polyaminoester emulsion. Recording emulsion solid content is 20%, particle diameter 1000-1200nm.
B component is synthetic: being equipped with in the 500m1 four-hole boiling flask of agitator, condensing reflux pipe, thermocouple, add IPDI30Gram, 2000 PTMEG60 gram of molecular weight polyisoprene erythritan, 0.01 gram of T12 catalyst, 5.5 grams of dihydromethyl propionic acids, N-first20 grams of base formamides react 4 hours at 80 DEG C, are then cooled to 45 degree and add 4.1 grams of triethylamines, are incubated after 30 minutes with highSpeed emulsion dispersion machine adds 350 grams of water in performed polymer under 1000r/min high-speed stirred, disperses to obtain spreading unchecked light after 30 minutesTransparent polyurethane emulsion is stand-by. Recording emulsion solid content is 20%, particle diameter 50-70nm.
Under 800r/min high-speed stirred, 100 grams of A components and 200 grams of B components are uniformly mixed with emulsify at a high speed dispersion machine15 minutes, reduce rotating speed and add 6.4 grams of TT935 thickeners to 300r/min, stirs and after 30 minutes, leave standstill froth breaking and obtain finally productProduct. Recording viscosity is 3200pa.s, gloss unit 2 after scytoblastema top finishing, obviously lamination of nothing after centrifugal test.
Primary raw material source related in the embodiment of the present invention is as follows:
HDI tripolymer, BAYERN3300; IPDI tripolymer, VESTANATT1890, 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.
Dihydromethyl propionic acid, GEO S.R.L. of the U.S., industrial goods. .
Thickener: TT935, LANXESS company, industrial goods.
Catalyst: dibutyl tin laurate (T12), U.S.'s gas, technical grade.
SDF400 emulsify at a high speed dispersion machine.
Solid content method of testing: according to GB/T1725-79.
Emulsion particle diameter test: tester is the ZEN1690 of Ma Erwen instrument company particle size analyzer, and probe temperature is 25℃。
Storage stability: get emulsion and be placed in centrifugal separator, centrifugation 15 minutes under 3000rpm/min, if nothingPrecipitation produces and illustrates that storage stability is more than 6 months.
Glossiness test: tester adopts the German BYK AG-4446 of company, enters according to ISO2813, GB9754 standardRow test.
Claims (5)
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) isocyanate trimerization body, vulcabond, little molecule hydrophilic monomer, macromolecule dihydric alcohol class monomer, catalyst are mixedClose, at 60 ~ 90 DEG C, react 2 ~ 8 hours;
B) reactant liquor is cooled to 30 ~ 50 DEG C, 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, little molecule hydrophilic monomer, macromolecule dihydric alcohol class monomer, catalyst mix, 60 ~At 90 DEG C, react 2 ~ 8 hours;
B) reactant liquor is cooled to 30 ~ 50 DEG C, 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 increasing under stirringThick dose, make from extinction type leather waterborne polyurethane coating agent;
The viscosity from extinction type leather waterborne polyurethane coating agent that described preparation technology makes is 500 ~ 5000Pas;
Described little molecule hydrophilic monomer is dihydromethyl propionic acid or dimethylolpropionic acid;
Described macromolecule dihydric alcohol class monomer be molecular weight 1000 ~ 4000 Polyoxypropylene diol, molecular weight 1000 ~The poly-tetrahydrochysene furan of 3000 polycaprolactone dihydroxylic alcohols, the PCDL of molecular weight 1000 ~ 2000, molecular weight 500 ~ 2000Any one or the two or more combinations of muttering in glycol, molecular weight 500 ~ 2000 polyethylene glycol;
Polyurethane component A particle diameter is controlled at 500 ~ 3000nm, and the particle diameter of polyurethane component B is controlled at 20 ~ 200nm;
The preparation of described polyurethane component A, the mol ratio of isocyanate trimerization body and vulcabond is 0.2 ~ 0.8:1, andThe mol ratio of the total amount of two kinds of isocyanates and macromolecule dihydric alcohol class monomer is 3 ~ 7:1, and little molecule hydrophilic monomer consumption is single1.5 ~ 8% of body gross mass, the molal quantity of triethylamine is 80 ~ 120% of little molecule hydrophilic monomer molal quantity, catalyst amount is 5 ~20mg/L, the solid content of polyaminoester emulsion is 20%;
The preparation of described polyurethane component B, the mol ratio of aliphatic diisocyanate and macromolecule dihydric alcohol class monomer is 2.5~ 5:1, little molecule hydrophilic monomer consumption is 2.5 ~ 7% of monomer gross mass, the molal quantity of triethylamine is that little molecule hydrophilic monomer rubs80 ~ 120% of that number, catalyst amount is 5 ~ 20mg/L, the solid content of polyaminoester emulsion is 20%.
2. the preparation method from extinction type leather waterborne polyurethane coating agent according to claim 1, is characterized in that: instituteThe isocyanate trimerization body of stating and vulcabond mol ratio are 0.3 ~ 0.6:1, and the total amount of two kinds of isocyanates and large moleculeDi-alcohols monomer mole ratio is 3 ~ 5:1, and described little molecule hydrophilic monomer consumption is 2 ~ 5% of monomer gross mass, triethylamineMolal quantity is 100% of little molecule hydrophilic monomer molal quantity, and described catalyst amount is 10mg/L.
3. the preparation method from extinction type leather waterborne polyurethane coating agent according to claim 1, is characterized in that: instituteThe mol ratio of the aliphatic diisocyanate of stating and macromolecule dihydric alcohol class monomer is 2.8 ~ 4:1, the described hydrophilic list of little moleculeBody consumption is 3 ~ 6% of monomer gross mass, and the molal quantity of triethylamine is 100% of little molecule hydrophilic monomer molal quantity, and described urgesAgent consumption is 10mg/L.
4. the preparation method from extinction type leather waterborne polyurethane coating agent according to claim 1, is characterized in that: instituteThe isocyanate trimerization body of stating is hexamethylene diisocyanate trimer or isophorone diisocyanate trimer.
5. the preparation method from extinction type leather waterborne polyurethane coating agent according to claim 1, is characterized in that: instituteThe catalyst of stating is dibutyl tin laurate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310651725.2A CN103740250B (en) | 2013-12-06 | 2013-12-06 | From the preparation method of extinction type leather waterborne polyurethane coating agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310651725.2A CN103740250B (en) | 2013-12-06 | 2013-12-06 | From the preparation method of extinction type leather waterborne polyurethane coating agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103740250A CN103740250A (en) | 2014-04-23 |
| CN103740250B true CN103740250B (en) | 2016-05-18 |
Family
ID=50497321
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310651725.2A Active CN103740250B (en) | 2013-12-06 | 2013-12-06 | From the preparation method of extinction type leather waterborne polyurethane coating agent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103740250B (en) |
Families Citing this family (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104018359B (en) * | 2014-05-30 | 2015-04-29 | 昆山阿基里斯人造皮有限公司 | Surface self-extinction artificial leather material |
| CN104974324A (en) * | 2015-06-30 | 2015-10-14 | 中科院广州化学有限公司南雄材料生产基地 | Reactive self-delustering waterborne polyurethane resin, and preparation method and application thereof |
| CN105330812B (en) * | 2015-12-03 | 2017-12-01 | 上海蓝欧化工科技有限公司 | A kind of low gloss aqueous polyurethane with skin sense effect and preparation method thereof |
| CN105694699B (en) * | 2016-01-27 | 2018-11-27 | 优美特（北京）环境材料科技股份公司 | A kind of extinction type aqueous polyurethane emulsion and preparation method thereof |
| CN105601881A (en) * | 2016-03-28 | 2016-05-25 | 福建东泰高分子材料有限公司 | Preparation method of water-based polyurethane, emulsion and product |
| EP3235844A1 (en) * | 2016-04-20 | 2017-10-25 | ALLNEX AUSTRIA GmbH | Aqueous polyurethane dispersion |
| CN105949426A (en) * | 2016-06-26 | 2016-09-21 | 江阴市诺科科技有限公司 | Matte resin for artificial leather surface coatings |
| CN106432667B (en) * | 2016-10-03 | 2019-03-05 | 辽宁恒星精细化工有限公司 | From delustring soft feeling Aqueous Polyurethane Leather Finishing Agent and preparation method |
| CN106750080A (en) * | 2017-01-19 | 2017-05-31 | 佛山市功能高分子材料与精细化学品专业中心 | It is a kind of from extinction type modified aqueous polyurethane coating and preparation method and application |
| CN108300058B (en) * | 2017-09-07 | 2020-10-09 | 惠州长联新材料科技有限公司 | Inorganic matting powder-free water-based matting finishing agent for artificial leather surface treatment and preparation method thereof |
| PT3680299T (en) * | 2017-10-27 | 2022-03-07 | Dainichiseika Color Chem | Lusterless paint and skin material |
| CN107987699B (en) * | 2017-12-01 | 2020-07-10 | 上海三恩化工有限公司 | Water-based surface coating agent suitable for polyvinyl chloride artificial leather of automobile seat and preparation method thereof |
| CN108546323B (en) * | 2018-04-18 | 2020-08-28 | 万华化学集团股份有限公司 | Cation self-extinction resin and preparation method and application thereof |
| CN109054618A (en) * | 2018-07-19 | 2018-12-21 | 张家港市东方高新聚氨酯有限公司 | A kind of aqueous matt surface inorganic agent of skin sense no-solvent polyurethane from delustring |
| CN109180901A (en) * | 2018-08-23 | 2019-01-11 | 洛阳盛嘉新材料有限公司 | From delustring aqueous polyurethane and preparation method thereof |
| CN109553747B (en) * | 2018-12-05 | 2021-06-08 | 长春工业大学 | Preparation method of high-solid content biodegradable waterborne polyurethane |
| CN110240688A (en) * | 2019-05-24 | 2019-09-17 | 合肥科天水性科技有限责任公司 | Agent waterborne polyurethane resin and preparation method thereof at a kind of table |
| CN110627986A (en) * | 2019-09-18 | 2019-12-31 | 合肥科天水性科技有限责任公司 | Cationic self-extinction waterborne polyurethane resin and preparation method thereof |
| CN110863359B (en) * | 2019-11-29 | 2022-05-31 | 江苏宝泽高分子材料股份有限公司 | Water-based transparent polishing treatment agent for clothing leather and preparation method thereof |
| CN111138963B (en) * | 2019-12-04 | 2021-10-26 | 安徽圣达生物药业有限公司 | Synthesis process of high-performance self-crosslinking waterborne polyurethane self-extinction resin |
| CN111072996A (en) * | 2019-12-09 | 2020-04-28 | 兴业皮革科技股份有限公司 | Polyurethane micro-powder emulsification method, polyurethane micro-powder emulsion, leather mending agent and application thereof |
| CN111718646A (en) * | 2020-07-07 | 2020-09-29 | 上海金狮化工有限公司 | Waterborne polyurethane leather brightener and preparation method thereof |
| CN115820097B (en) * | 2021-09-16 | 2024-01-19 | 海洋化工研究院有限公司 | Self-extinction elastic weather-proof polyurethane coating and preparation method thereof |
| CN114276519B (en) * | 2021-12-27 | 2023-09-22 | 安徽匠星联创新材料科技有限公司 | Self-extinction waterborne polyurethane and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1735642A (en) * | 2003-01-04 | 2006-02-15 | 帝斯曼知识产权资产管理有限公司 | The aqueous polyurethane composition that is used for coatings with low gloss finish |
| CN102108246A (en) * | 2010-12-26 | 2011-06-29 | 华南理工大学 | Double-component polyurethane water-based paint |
| CN102924683A (en) * | 2012-11-22 | 2013-02-13 | 山西省应用化学研究所 | Aqueous polyurethane dispersoid for coating yellowing-resistant leather and preparation method thereof |
| CN103319682A (en) * | 2013-07-11 | 2013-09-25 | 清远市美乐仕油墨有限公司 | Low-luster aqueous polyurethane dispersion for leather, and preparation method and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012165569A1 (en) * | 2011-05-31 | 2012-12-06 | 宇部興産株式会社 | Aqueous polyurethane resin dispersion and coating composition comprising same |
-
2013
- 2013-12-06 CN CN201310651725.2A patent/CN103740250B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1735642A (en) * | 2003-01-04 | 2006-02-15 | 帝斯曼知识产权资产管理有限公司 | The aqueous polyurethane composition that is used for coatings with low gloss finish |
| CN102108246A (en) * | 2010-12-26 | 2011-06-29 | 华南理工大学 | Double-component polyurethane water-based paint |
| CN102924683A (en) * | 2012-11-22 | 2013-02-13 | 山西省应用化学研究所 | Aqueous polyurethane dispersoid for coating yellowing-resistant leather and preparation method thereof |
| CN103319682A (en) * | 2013-07-11 | 2013-09-25 | 清远市美乐仕油墨有限公司 | Low-luster aqueous polyurethane dispersion for leather, and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103740250A (en) | 2014-04-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103740250B (en) | From the preparation method of extinction type leather waterborne polyurethane coating agent | |
| CN103232584B (en) | High-performance environment-friendly type water-borne polyurethane and preparation method thereof | |
| CN101381581B (en) | Polyurethane transparent matt topcoat, preparation method and use method thereof | |
| CN102898613B (en) | Method for preparing water-soluble organosilicone modified polyurethane resin | |
| CN103724583B (en) | Synthetic leather is high temperature resistant super black and misty treatment agent aliphatic polyurethane resin and preparation method thereof | |
| CN105968306A (en) | Preparation method of nano-silicon-dioxide-modified water-based polyurethane | |
| CN106366291B (en) | A kind of self-emulsifying type anion aqueous polyurethane curing agent and preparation method thereof | |
| CN103726330B (en) | Use for synthetic leather is high temperature resistant super black and misty finishing agent | |
| CN102746780B (en) | Aqueous comprehensive resin and preparation method of aqueous comprehensive resin | |
| CN103589319B (en) | A kind of locomotive interior trim urethane soft-feel coating and preparation method | |
| CN102898937A (en) | High-hardness scratch-resistant double-component waterborne polyurethane woodwork varnish and preparation method thereof | |
| CN103965715A (en) | Water-based glass coating | |
| CN108864400A (en) | A kind of high-performance cationic water polyurethane resin and preparation method thereof | |
| CN102675979A (en) | Water-based ink for water transfer printing and preparation method for water-based ink | |
| CN105440779A (en) | Friction-resistant matt varnish and preparation method thereof | |
| WO2017088085A1 (en) | Aqueous ultra-misty ultra-black treatment agent for synthetic leather and preparation method for same | |
| CN103590248A (en) | Waterborne skin-touch and scratch-resistant synthetic leather surface treating agent free of hand marks | |
| CN102409553B (en) | Method for preparing solvent-free vehicle interior leather based on in-situ polymerization | |
| CN102383309A (en) | Water-based surface treatment agent for calendered PVC (polyvinyl chloride) leather | |
| CN102796447B (en) | Aqueous Polyurethane Leather Finishing Agent and preparation method thereof | |
| CN109207047A (en) | Dedicated super sub- skin sense abrasion-resistance water coating of a kind of PVC surface decoration and preparation method thereof | |
| CN109401559A (en) | A kind of stainless steel vacuum cup aqueous amino-stoving varnish and preparation method thereof | |
| CN102363705B (en) | Water-based single-component full-gloss clear finishing paint and preparation method thereof | |
| CN102363684B (en) | Aqueous two-component white priming paint and preparation method thereof | |
| CN104725592B (en) | A kind of preparation method of maleopimaric acid dual-component aqueous polyurethane |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Preparation method of self extinction leather waterborne polyurethane finishing agent Effective date of registration: 20220225 Granted publication date: 20160518 Pledgee: Industrial Bank Limited by Share Ltd. Chengdu branch Pledgor: DOWELL TECHNOLOGY Co.,Ltd. Registration number: Y2022510000047 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20231007 Granted publication date: 20160518 Pledgee: Industrial Bank Limited by Share Ltd. Chengdu branch Pledgor: DOWELL TECHNOLOGY Co.,Ltd. Registration number: Y2022510000047 |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Preparation method of self extinction water-based polyurethane finishing agent for leather Effective date of registration: 20231009 Granted publication date: 20160518 Pledgee: Industrial Bank Limited by Share Ltd. Chengdu branch Pledgor: DOWELL TECHNOLOGY Co.,Ltd. Registration number: Y2023980060498 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right |