CN104448205B - A kind of aqueous polyurethane, its preparation method and its application for finishing agent - Google Patents
A kind of aqueous polyurethane, its preparation method and its application for finishing agent Download PDFInfo
- Publication number
- CN104448205B CN104448205B CN201410815705.9A CN201410815705A CN104448205B CN 104448205 B CN104448205 B CN 104448205B CN 201410815705 A CN201410815705 A CN 201410815705A CN 104448205 B CN104448205 B CN 104448205B
- Authority
- CN
- China
- Prior art keywords
- aqueous polyurethane
- organosilicon
- dihydroxylic alcohols
- present
- oxirane
- 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
- 239000004814 polyurethane Substances 0.000 title claims abstract description 79
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 79
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims description 17
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims abstract description 56
- 150000001298 alcohols Chemical class 0.000 claims abstract description 52
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 33
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000001294 propane Substances 0.000 claims abstract description 28
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 16
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 14
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 12
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims description 31
- 239000000839 emulsion Substances 0.000 claims description 31
- -1 polysiloxanes Polymers 0.000 claims description 31
- 238000006386 neutralization reaction Methods 0.000 claims description 25
- 229920000570 polyether Polymers 0.000 claims description 21
- 229920000642 polymer Polymers 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims description 18
- 239000001257 hydrogen Substances 0.000 claims description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 17
- 239000000178 monomer Substances 0.000 claims description 15
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 14
- 229920001296 polysiloxane Polymers 0.000 claims description 14
- JECYNCQXXKQDJN-UHFFFAOYSA-N 2-(2-methylhexan-2-yloxymethyl)oxirane Chemical compound CCCCC(C)(C)OCC1CO1 JECYNCQXXKQDJN-UHFFFAOYSA-N 0.000 claims description 12
- 239000004970 Chain extender Substances 0.000 claims description 12
- 239000012948 isocyanate Substances 0.000 claims description 12
- 230000009467 reduction Effects 0.000 claims description 12
- 239000007795 chemical reaction product Substances 0.000 claims description 11
- 239000003153 chemical reaction reagent Substances 0.000 claims description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 11
- 239000000376 reactant Substances 0.000 claims description 9
- 150000005846 sugar alcohols Polymers 0.000 claims description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 10
- 239000000203 mixture Substances 0.000 abstract description 9
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 47
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- 239000010985 leather Substances 0.000 description 12
- 238000003860 storage Methods 0.000 description 11
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 10
- 229920006264 polyurethane film Polymers 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical class OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 235000019260 propionic acid Nutrition 0.000 description 6
- 125000000129 anionic group Chemical group 0.000 description 5
- 238000013329 compounding Methods 0.000 description 5
- 150000002009 diols Chemical class 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000003973 paint Substances 0.000 description 5
- 229920000909 polytetrahydrofuran Polymers 0.000 description 5
- 238000005292 vacuum distillation Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 description 4
- 150000001412 amines Chemical group 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229920001610 polycaprolactone Polymers 0.000 description 4
- 239000004632 polycaprolactone Substances 0.000 description 4
- 150000004672 propanoic acids Chemical class 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 125000005442 diisocyanate group Chemical group 0.000 description 3
- 150000002171 ethylene diamines Chemical class 0.000 description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 238000009738 saturating Methods 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- AVUYXHYHTTVPRX-UHFFFAOYSA-N Tris(2-methyl-1-aziridinyl)phosphine oxide Chemical compound CC1CN1P(=O)(N1C(C1)C)N1C(C)C1 AVUYXHYHTTVPRX-UHFFFAOYSA-N 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000004922 lacquer Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 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 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000012974 tin catalyst Substances 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- WOGVOIWHWZWYOZ-UHFFFAOYSA-N 1,1-diisocyanatoethane Chemical compound O=C=NC(C)N=C=O WOGVOIWHWZWYOZ-UHFFFAOYSA-N 0.000 description 1
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- RZYKUPXRYIOEME-UHFFFAOYSA-N CCCCCCCCCCCC[S] Chemical compound CCCCCCCCCCCC[S] RZYKUPXRYIOEME-UHFFFAOYSA-N 0.000 description 1
- USEBIPUIVPERGC-UHFFFAOYSA-N Dibutylone Chemical compound CCC(N(C)C)C(=O)C1=CC=C2OCOC2=C1 USEBIPUIVPERGC-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 239000004425 Makrolon Substances 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- UVNYQSUCIGWUHW-UHFFFAOYSA-N N=C=O.CCCC Chemical compound N=C=O.CCCC UVNYQSUCIGWUHW-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical class CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- QVYARBLCAHCSFJ-UHFFFAOYSA-N butane-1,1-diamine Chemical compound CCCC(N)N QVYARBLCAHCSFJ-UHFFFAOYSA-N 0.000 description 1
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical group CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000027555 hydrotropism Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical class CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000011895 specific detection Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- 229960001124 trientine Drugs 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3225—Polyamines
- C08G18/3228—Polyamines acyclic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4081—Mixtures of compounds of group C08G18/64 with other macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/06—Polyurethanes from polyesters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/08—Polyurethanes from polyethers
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
It is the glycol modified aqueous polyurethane of organosilicon the invention provides a kind of aqueous polyurethane, the organosilicon dihydroxylic alcohols has structure shown in Formulas I, in Formulas I, R1And R2Independently selected from the alkyl that H or carbon number are 1~5；R3And R4Independently selected from H or methyl；N, p and q are the degree of polymerization, independently are 10~100；The organosilicon dihydroxylic alcohols structure includes that mol ratio is (2~4):1 expoxy propane and oxirane.In the present invention, structure is included that mol ratio is (2~4):1 expoxy propane and the organosilicon dihydroxylic alcohols of oxirane are modified to polyurethane, so that organosilicon composition has certain incompatibility with other polyurethane components, organosilicon composition is enriched in film formation surface in film forming procedure, form homogeneous opaque film, so that still covering performance with preferable without the outer doping of addition when the aqueous polyurethane that the present invention is provided is used as finishing agent.
Description
Technical field
The present invention relates to technical field of coatings, more particularly to a kind of aqueous polyurethane, its preparation method and its for covering with paint, lacquer, colour wash, etc.
The application of agent.
Background technology
The effect covered with paint, lacquer, colour wash, etc. in tanning production is very big, can significantly improve the quality and class of leather, increases leather
Kind and commercial value, are last one " lifelines " in tanning production.Finishing agent is used for leather surface beautification, improves durable
Property, corrected grain defect, improve commercial value, while the assorted slurries increased varieties and designs.In leather finish production process,
The covering with paint of second layer leather is essential important procedure.For first layer leather, the production cost of second layer leather is relatively low, warp
Ji benefit is preferable.But second layer leather does not have grain tissue, its mechanical property is poor, and the disability on scytoblastema surface is more, and this is required
In the covering with paint of second layer leather, finishing agent used must have preferable disability to cover performance.
Aqueous emulsion of polyurethane is used as leather finishing agent, and its filming performance is good, is firmly bonded, and coating has high glaze, height resistance to
Mill property, high resiliency, water-fast, weather-proof, cold-resistant, heat-resisting, chemical-resistant resistance.It is the resultant Leather good hand feeling of covering with paint, comfortable, can carry significantly
The class of resultant Leather high.It is nontoxic when using, pollution-free, do not burn simultaneously as with water as medium, therefore, it is a kind of environment friend
Good product, develops very rapid this year.
In the prior art, general aqueous polyurethane film forming is transparent, therefore to the covering poor-performing of scytoblastema disability.For
Solve the outer filled covering to improve to scytoblastema disability of addition in this problem prior art general hydrotropism's polyurethane
Property, but these outer addition filler generally existing compounding stability and problems of stability in storage.
The content of the invention
It is an object of the invention to provide a kind of aqueous polyurethane, its preparation method and its application for finishing agent, this
When the aqueous polyurethane for inventing offer is used as finishing agent, without adding outer doping, still with preferably covering performance,
Also would not there is a problem of due to the compounding stability and storage stability that outer doping brings.
It is the glycol modified aqueous polyurethane of organosilicon, the organosilicon the invention provides a kind of aqueous polyurethane
Dihydroxylic alcohols has structure shown in Formulas I：
In Formulas I, R1And R2Independently selected from the alkyl that H or carbon number are 1~5；
R3And R4Independently selected from H or methyl；
N, p and q are the degree of polymerization, independently are 10~100；
The organosilicon dihydroxylic alcohols structure includes expoxy propane and oxirane, the expoxy propane and oxirane
Mol ratio is (2~4):1.
Preferably, R1And R2Independently selected from the alkyl that H or carbon number are 1~3.
Preferably, described n, p and q independently are 20~80.
Preferably, the preparation method of the organosilicon dihydroxylic alcohols is comprised the following steps：
The polyethers that the polysiloxanes that double hydrogen are blocked is blocked with monoene alkyl is reacted in the presence of catalyst, is obtained
Organosilicon dihydroxylic alcohols；
The mono-vinyl end capped polyether monomer includes expoxy propane and oxirane, the expoxy propane and epoxy second
The mol ratio of alkane is (2~4):1.
Preferably, the temperature of the polysiloxanes of described pair of hydrogen end-blocking and the polyether reactant of monoene alkyl end-blocking for 90 DEG C~
100℃；
The described pair of polysiloxanes of hydrogen end-blocking and the time of the polyether reactant of monoene alkyl end-blocking are 4h~6h.
Preferably, the catalyst is platinum metal catalyst；
The consumption of the catalyst is 1ppm~10ppm.
The invention provides a kind of preparation method of aqueous polyurethane, comprise the following steps：
A) in the presence of catalyst, by organosilicon dihydroxylic alcohols, aliphatic isocyanates, polyalcohol with Formulas I structure
Prepolymerization reaction is carried out with anionic hydrophilic monomer chain extender, performed polymer is obtained, the aliphatic isocyanates at least include one kind
Diisocyanate；
B) neutralization reaction will be carried out with neutralization reagent after the performed polymer viscosity reduction, obtains neutralization reaction product；
C) after the neutralization reaction product is mixed with water, emulsion chain extension is carried out, obtains aqueous polyurethane；
In Formulas I, R1And R2Independently selected from the alkyl that H or carbon number are 1~5；
R3And R4Independently selected from H or methyl；
N, p and q are the degree of polymerization, independently are 10~100；
The organosilicon dihydroxylic alcohols structure includes expoxy propane and oxirane, the expoxy propane and oxirane
Mol ratio is (2~4):1.
Preferably, the temperature of the prepolymerization reaction is 70 DEG C~100 DEG C
Preferably, the time of the prepolymerization reaction is 2h~5h.
The invention provides the application that aqueous polyurethane is used for finishing agent, the aqueous polyurethane is above-mentioned technical proposal institute
The aqueous polyurethane that preparation method described in stating aqueous polyurethane or above-mentioned technical proposal is obtained.
It is the glycol modified aqueous polyurethane of organosilicon, the organosilicon the invention provides a kind of aqueous polyurethane
Dihydroxylic alcohols has structure shown in Formulas I, in Formulas I, R1And R2Independently selected from the alkyl that H or carbon number are 1~5；R3And R4It is independent
Ground is selected from H or methyl；N, p and q are the degree of polymerization, independently are 10~100；The organosilicon dihydroxylic alcohols structure includes epoxy third
Alkane and oxirane, the expoxy propane are (2~4) with the mol ratio of oxirane:1.In the present invention, by organosilicon binary
Alcohol is modified to polyurethane, and the structure of the organosilicon dihydroxylic alcohols includes that mol ratio is (2~4):1 expoxy propane and ring
Oxidative ethane so that the polarity of organosilicon dihydroxylic alcohols there occurs change, so as in making the glycol modified polyurethane of organosilicon for obtaining
There is certain molecular-chain polarr difference in organosilicon composition, have certain incompatibility, in film forming mistake with other polyurethane components
Produced in journey and be slightly separated, organosilicon composition is enriched in film formation surface, so as to form homogeneous opaque film so that the present invention
Outer doping need not be added when the aqueous polyurethane of offer is used as finishing agent, still with preferably covering performance and comfortably
Feel, so as to would not also there is the poor storage stability feel and compounding stability that outer doping brings.
And the aqueous polyurethane film caudacoria that the present invention is provided has preferable mechanical property.The embodiment of the present invention 4
The tensile strength of the aqueous polyurethane for arriving point reagent film forming caudacoria is 17Mpa, and elongation at break is 560%.
Specific embodiment
It is the glycol modified aqueous polyurethane of organosilicon, the organosilicon the invention provides a kind of aqueous polyurethane
Dihydroxylic alcohols has structure shown in Formulas I：
In Formulas I, R1And R2Independently selected from the alkyl that H or carbon number are 1~5；
R3And R4Independently selected from H or methyl；
N, p and q are the degree of polymerization, independently are 10~100；
The organosilicon dihydroxylic alcohols structure includes expoxy propane and oxirane, the expoxy propane and oxirane
Mol ratio is (2~4):1.
In the present invention, organosilicon dihydroxylic alcohols is modified to polyurethane, is wrapped in the structure of the organosilicon dihydroxylic alcohols
Mol ratio is included for (2~4):1 expoxy propane and oxirane so that the polarity of organosilicon dihydroxylic alcohols there occurs change, so that
In making the glycol modified polyurethane of the organosilicon for obtaining there is certain strand pole in organosilicon composition with other polyurethane components
Sex differernce, there is certain incompatibility, is produced in film forming procedure and is slightly separated, and organosilicon composition is enriched in film formation surface, from
And forming homogeneous opaque film so that the aqueous polyurethane that the present invention is provided need not add additional when being used as finishing agent
Additive, still with performance and comfortable feel is preferably covered, so as to would not also there is the storage that outer doping brings
The problem of stability difference feel and compounding stability.And the aqueous polyurethane film caudacoria that the present invention is provided has preferable power
Learn performance.
The aqueous polyurethane that the present invention is provided is the glycol modified aqueous polyurethane of organosilicon, the organosilicon dihydroxylic alcohols
With structure shown in Formulas I, in Formulas I, R1And R2Independently selected from the alkyl that H or carbon number are 1~5, preferably independently it is selected from
H, methyl, ethyl, n-propyl or isopropyl；
In Formulas I of the present invention, R3And R4Independently selected from H or methyl.In the present invention, it is described with Formulas I structure
Organosilicon dihydroxylic alcohols includes expoxy propane and oxirane, and the expoxy propane is preferably with the mol ratio of the oxirane
(2~4):1, more preferably (2.5~3.5):1.
In the present invention, n, p and q are the degree of polymerization, 10~100 independently are, preferably independently for 20~80 is more preferably only
It is on the spot 30~60.
In the present invention, the preparation method of the organosilicon dihydroxylic alcohols preferably includes following steps：
The polyethers that the polysiloxanes that double hydrogen are blocked is blocked with monoene alkyl is reacted in the presence of catalyst, is obtained
Organosilicon dihydroxylic alcohols；
The mono-vinyl end capped polyether monomer includes expoxy propane and oxirane, the expoxy propane and epoxy second
The mol ratio of alkane is (2~4):1.
In the present invention, the polysiloxanes of described pair of hydrogen end-blocking has structure shown in Formula II：
In Formula II, R1And R2It is preferably independently former selected from H or carbon independently selected from the alkyl that H or carbon number are 1~20
Subnumber is 1~20 alkyl, more preferably independently selected from the alkyl that H or carbon number are 1~10, most preferably independently selected from H,
Methyl, ethyl, n-propyl or isopropyl.
In the present invention, n is the degree of polymerization, is 10~100, preferably 20~80, more preferably 30~60.Of the invention
In embodiment, the number-average molecular weight that the siloxanes that double hydrogen are blocked can be specially Best Co., Ltd's sale is 1000 double hydrogen end-blocking
Siloxanes (HPDMS).
In the present invention, the polyethers of the monoene alkyl end-blocking has structure shown in formula III：
In formula III, R5Selected from H or or methyl.In the present invention, it is described with formula III structure but the dilute end-blocking of second poly-
Ether includes expoxy propane and oxirane, and the expoxy propane is preferably (2~4) with the mol ratio of the oxirane:1,
More preferably (2.5~3.5):1.
In the present invention, p and q is the degree of polymerization, 10~100 independently is, preferably independently for 20~80 is more preferably independent
Ground is 30~60.In an embodiment of the present invention, the polyethers of monoene alkyl end-blocking can be specially monoallyl end-blocking polyoxyethylene
Dilute-propylene ether, number-average molecular weight is 600, EO and the ratio of PO is 1:2.5.Polyethers of the present invention to monoene alkyl end-blocking
Source without special limitation, using the commercial goods of the polyethers of above-mentioned monoene alkyl end-blocking.
In the present invention, the polysiloxanes of double hydrogen end-blocking and the mol ratio of the polyethers of monoene alkyl end-blocking be preferably (1~
5):(1~5), more preferably (1~4):(1~4).
In the present invention, the polysiloxanes of double hydrogen end-blockings is preferred with the catalyst that the polyether reactant that monoene alkyl is blocked is used
Be platinum metal catalyst, in the present invention, the platinum metal catalyst can be specially simple platinum metal catalyst, or
The composite catalyst that the load of platinum activated feedstock is obtained on a catalyst support.In an embodiment of the present invention, the platinum
Catalyst can be specially chloroplatinic acid catalyst, and the content of platinum is preferably 1000ppm~10000ppm in the chloroplatinic acid catalyst,
More preferably 1050ppm~9000ppm, most preferably 3000ppm~8000ppm.In the present invention, the consumption of the catalyst
Preferably 1ppm~10ppm, more preferably 3ppm~8ppm.
In the present invention, the polysiloxanes of double hydrogen end-blockings is preferably 90 DEG C with the temperature of the polyether reactant of monoene alkyl end-blocking
~100 DEG C, more preferably 93 DEG C~98 DEG C；In an embodiment of the present invention, the polysiloxanes of double hydrogen end-blockings is sealed with monoene alkyl
The temperature of the polyether reactant at end can be specially 90 DEG C, 93 DEG C, 95 DEG C, 98 DEG C or 100 DEG C.In the present invention, described pair of hydrogen end-blocking
Time of polyether reactant of polysiloxanes and monoene alkyl end-blocking be preferably 4h~6h, more preferably 4.5h~5.5h；At this
In inventive embodiment, polysiloxanes and the time of the polyether reactant of monoene alkyl end-blocking of double hydrogen end-blocking can be specially 4h,
4.25h, 4.5h, 4.75h, 5h, 5.25h, 5.5h, 5.75h or 6h.
After completing the reaction, the product that will preferably obtain of the present invention is washed, remove catalyst therein and
Residual monomer.The present invention does not have special limitation to the method for the washing, using washing well known to those skilled in the art
Technical scheme, in an embodiment of the present invention, the washing can be specially deionized water washing.
Present invention also offers a kind of preparation method of aqueous polyurethane, comprise the following steps：
A) in the presence of catalyst, by organosilicon dihydroxylic alcohols, aliphatic isocyanates, polyalcohol with Formulas I structure
Prepolymerization reaction is carried out with anionic hydrophilic monomer chain extender, performed polymer is obtained, the aliphatic isocyanates at least include one kind
Diisocyanate；
B) neutralization reaction will be carried out with neutralization reagent after the performed polymer viscosity reduction, obtains neutralization reaction product；
C) after the neutralization reaction product is mixed with water, emulsion chain extension is carried out, obtains aqueous polyurethane；
In Formulas I, R1And R2Independently selected from the alkyl that H or carbon number are 1~5；
R3And R4Independently selected from H or methyl；
N, p and q are the degree of polymerization, independently are 10~100；
The organosilicon dihydroxylic alcohols structure includes expoxy propane and oxirane, the expoxy propane and oxirane
Mol ratio is (2~4):1.
The present invention in the presence of catalyst, by the organosilicon dihydroxylic alcohols with Formulas I structure, aliphatic diisocyanate,
Polyalcohol and anionic hydrophilic monomer chain extender carry out prepolymerization reaction, obtain performed polymer.In the present invention, the organosilicon binary
Alcohol is have the organosilicon dihydroxylic alcohols shown in Formulas I described in above-mentioned technical proposal, be will not be repeated here.
In the present invention, the aliphatic isocyanates at least include a kind of diisocyanate, are preferably selected from from different Fo Er
Ketone diisocyanate (IPDI) and its derivative, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI) and its spread out
Biological, trans- hexamethylene-Isosorbide-5-Nitrae-diisocyanate (TMI), phosphorous diisocyanate, the tetramethoxy butane-isocyanic acid of Isosorbide-5-Nitrae-two
Ester, butane-Isosorbide-5-Nitrae-diisocyanate, hexane -1,6- diisocyanate, dicyclohexyl methyl hydride diisocyanate, hexamethylene-Isosorbide-5-Nitrae -
Diisocyanate, hexamethylene -1,2- diisocyanate, hexamethylene -1,3- diisocyanate, ethylidene diisocyanate and drop ice
One or more in piece alkane diisocyanate.
In the present invention, the polyalcohol is preferably one or more in dihydroxylic alcohols and trihydroxylic alcohol, more preferably polyoxy
Change propylene dihydroxylic alcohols, polycaprolactone diols, PCDL, polytetrahydrofuran diol, the equal molecule of polyethylene glycol sum
Amount less than 400 dihydroxylic alcohols in one or more.In the present invention, the number-average molecular weight of the Polyoxypropylene diol is excellent
Elect 1000~4000, more preferably 1500~3500, most preferably 2000~3000 as；The number of the polycaprolactone diols is equal
Molecular weight is preferably 1000~3000, more preferably 1300~2800, most preferably 1600~2000；The makrolon binary
The number-average molecular weight of alcohol is preferably 1000~2000, more preferably 1200~1800, most preferably 1400~1600；Described poly- four
The number-average molecular weight of hydrogen furans glycol is preferably 500~2000, more preferably 1000~1800, most preferably 1200~1500；
The number-average molecular weight of the polyethylene glycol is preferably 500~2000, more preferably 1000~1800, most preferably 1200~
1500；Dihydroxylic alcohols of the molecular weight less than 400 is preferably ethylene glycol, propane diols, 1,4- butanediols, 1,6-HD, 1,5-
One or more in pentanediol, hexylene glycol, diglycol and neopentyl glycol.
In the present invention, the anionic hydrophilic monomer chain extender is preferably dihydroxy methylpropane and/or dihydroxymethyl fourth
Alkane.
In the present invention, the organosilicon dihydroxylic alcohols with Formulas I structure, aliphatic isocyanates, polyalcohol and the moon from
The catalyst that sub- hydrophilic monomer chain extender is reacted preferably organic tin catalyst, more preferably di lauric dibutyl
One or more in tin, stannous octoate, two (dodecyl sulphur) dibutyl tins and dibutyltin diacetate.In the present invention,
The consumption of the organic tin catalyst is preferably 10ppm~30ppm, more preferably 15ppm~25ppm.
In the present invention, the mol ratio of the aliphatic isocyanates, organosilicon dihydroxylic alcohols and polyalcohol be preferably (3~
7):(0.05~0.5):1, more preferably (4~6):(0.1~0.3):1.The polyalcohol and hydrophilic monomer chain extender mole
Than being preferably (0.5~3):1, more preferably (1~2):1.The consumption of the hydrophilic monomer chain extender is preferably reaction system and consolidates
2.5wt%~the 8wt%, more preferably 4wt%~6wt% of body part gross mass.
The present invention is preferably by the organosilicon dihydroxylic alcohols, aliphatic isocyanates, polyalcohol, anionic hydrophilic monomer and expansion
After chain agent mixing, catalyst is added, the mixed material that will be obtained carries out prepolymerization reaction, obtains performed polymer.In the present invention, institute
The temperature for stating prepolymerization reaction is preferably 70 DEG C~100 DEG C, more preferably 75 DEG C~95 DEG C, most preferably 80 DEG C~90 DEG C；It is described
The time of prepolymerization reaction is preferably 2h~5h, most preferably more preferably 2.5h~4.5h, 3h~4h.
After obtaining performed polymer, the present invention will carry out neutralization reaction after the performed polymer viscosity reduction with neutralization reagent.In the present invention
In, the viscosity reduction is preferably specially：
The performed polymer is mixed with thinner, is carried out with regard to viscosity reduction.
In the present invention, the thinner is preferably acetone, DMF, butanone and 1-METHYLPYRROLIDONE
In one or more.In the present invention, the quality of the thinner and all participation reaction monomers gross masses than water
10%~20%, more preferably 12%~18%, most preferably 14%~16%.The temperature of the viscosity reduction is preferably 30 DEG C~55
DEG C, more preferably 35 DEG C~50 DEG C, most preferably 40 DEG C~45 DEG C.
After viscosity reduction, viscosity reduction product and neutralization reagent are carried out neutralization reaction by the present invention, obtain neutralization reaction product.In this hair
In bright, the neutralization reagent is preferably aminated compounds, more preferably triethylamine.In the present invention, the neutralization reagent rubs
The ratio between molal quantity of that number and dihydromethyl propionic acid is preferably (80~120):100, more preferably (90~115):100, it is optimal
Elect as (95~100):100.The temperature of the neutralization reaction is preferably 30 DEG C~50 DEG C, more preferably 35 DEG C~45 DEG C；It is described
The time of neutralization reaction is preferably 0.5h~1h, and in an embodiment of the present invention, the time of the neutralization reaction can be specially
0.5h, 0.75h or 1h.
After obtaining neutralization reaction product, after the present invention mixes the neutralization reaction product with water, emulsion chain extension is carried out, obtained
To aqueous polyurethane.The present invention does not have special limitation to the species of the water, is using water well known to those skilled in the art
Can, such as can be deionized water.Those skilled in the art can be as needed aqueous polyurethane solid content, it is determined that adding water
Quality；In an embodiment of the present invention, the water addition preferably so that the aqueous polyurethane for arriving solid content for 20%~
35%, most preferably 25%~30%.The present invention mixes the neutralization reaction product with water preferably under conditions of stirring；
It is preferred that carrying out emulsion chain extension after scattering.In the present invention, the speed of the stirring is preferably 800r/min~1500r/
Min, more preferably 900r/min~1300r/min, most preferably 1000r/min~1200r/min.
In the present invention, the emulsion chain extension is preferably specially：
The neutralized reaction product is mixed with the mixture of water with amine chain extender, emulsion chain extension is carried out.
In the present invention, the amine chain extender is preferably polyamine, most preferably ethylenediamine, Putriscine, 1,6-
One or more in hexamethylene diamine, diethylenetriamine, triethylene tetramine and TEPA.In the present invention, the amine expands
Depending on the consumption of chain agent is according to the mole of remaining isocyanate in the performed polymer, in the present invention, the amine chain extender
Middle amino is preferably (0.6~0.9) with the mol ratio of remaining isocyanate in performed polymer:1, more preferably (0.7~0.8):1.
In the present invention, the emulsion chain extension is carried out under conditions of stirring, and in the present invention, the speed of the stirring is preferably
800r/min~1500r/min, more preferably 900r/min~1300r/min, most preferably 1000r/min~1200r/min.
In the present invention, the time of the emulsion chain extension be preferably 0.5h~2h, more preferably 1h~1.5h；In embodiments of the invention
In, the time of the emulsion chain extension can be specially 0.5h, 0.75h, 1h, 1.25h, 1.5h, 1.75h or 2h.
After completing the emulsion chain extension, the chain extension product that the present invention will preferably be obtained carries out vacuum distillation and removes drop therein
Stick, obtains aqueous polyurethane.The present invention does not have special limitation to the method for the vacuum distillation, can remove the chain extension
Thinner in product.In an embodiment of the present invention, when the thinner is acetone, the temperature of vacuum distillation is preferred
It is 40 DEG C~50 DEG C；The vacuum of the vacuum distillation is preferably 10kpa~30kpa, more preferably 15kpa~25kpa；It is described
The time of vacuum distillation is preferably 1h~3h, more preferably 1.5h~2.5h.
In the present invention, the aqueous polyurethane is Blue-Color Semitransparent aqueous polyurethane emulsion.
After obtaining aqueous polyurethane, the present invention detects that specific detection method is to aqueous polyurethane：
Solid content test is carried out according to the method in standard GB/T/T 1725-79；
The tensile property of aqueous polyurethane film is tested according to ASTM D882 standards, tester uses GOTECH
GT-7010-AEP；
The light transmittance of aqueous polyurethane film is tested according to ASTM D1003-61 standards, tester uses GZTEK
GZ502A；
Storage stability test is carried out by the following method：Aqueous polyurethane emulsion is placed in centrifugal separator,
Centrifugation 15min under 3000rpm/min, illustrates storage stability more than 6 months if being produced without precipitation.
It is the glycol modified aqueous polyurethane of organosilicon, the organosilicon the invention provides a kind of aqueous polyurethane
Dihydroxylic alcohols has structure shown in Formulas I, in Formulas I, R1And R2Independently selected from the alkyl that H or carbon number are 1~20；R3And R4Solely
On the spot selected from H or alkyl that carbon number is 1~10；N, p and q are the degree of polymerization, independently are 10~100.In the present invention, will
Organosilicon dihydroxylic alcohols is modified to polyurethane, due to the effect of organosilicon dihydroxylic alcohols, so as to get aqueous polyurethane occur without
Lamination, the component containing organosilicon can be slightly separated with other aqueous polyurethane components during film forming, make
Organosilicon is enriched in film surface, so as to form homogeneous opaque film so that the present invention provide aqueous polyurethane have compared with
Good covering performance and comfortable feel.
And the aqueous polyurethane film caudacoria that the present invention is provided has preferable mechanical property and preferable stable storing
Property.The tensile strength of the aqueous polyurethane that the embodiment of the present invention 4 is obtained point reagent film forming caudacoria is 17Mpa, and elongation at break is
560%.
In order to further illustrate the present invention, the aqueous polyurethane to present invention offer and its preparation side with reference to embodiment
Method is described in detail, but they can not be interpreted as into limiting the scope of the present invention.
In the embodiment of the present invention, IPDI is purchased from Ying Chuan companies；Polytetrahydrofuran diol (PTMEG),
Number-average molecular weight is 600,1000 and 2000, is industrial goods purchased from South Korea PTG；Polypropylene glycol, number-average molecular weight be 1000,
2000th, 3000 and 4000, it is industrial goods purchased from Historic Area of Zhongshan in Nanjing City petrochemical industry；Dihydromethyl propionic acid is industrial goods, public purchased from PERSTORP
Department；Triethylamine is industrial goods, purchased from western Gansu Province chemical industry；Polycaprolactone glycol is industrial goods, and number-average molecular weight is 1000 and 2000, purchase
From PERSTORP companies；Double hydrogen endcapped siloxanes (HPDMS) are experiment reagent, and number-average molecular weight is 1000, are tried purchased from bass is special
Agent；Monoallyl end-blocking polyethylene glycol oxide-propylene ether (MAPO) is industrial goods, and number-average molecular weight is that 600, EO/PO ratios are about
1:2.5, created purchased from winning；Chain extender is BDO (BDO), hexamethylene diamine and ethylenediamine, experiment reagent is, purchased from Tianjin section
Mi Ou chemical reagent Co., Ltd；Catalyst is dibutyl tin laurate (T12), technical grade, purchased from U.S.'s gas.In this reality
In applying example, using the high speed emulsion dispersion machine of model SDF400.
Embodiment 1
By in 100g HPDMS and 120g MAPO addition there-necked flasks, stirring is added thereto to chloroplatinic acid when being warming up to 85 DEG C
Catalyst 0.2ml, is continuously heating to 95 DEG C and insulation reaction 5h, the product that will be obtained through deionized water elute catalyst and
Residual monomer, obtains polyether block modified organic silicon dihydroxylic alcohols.
Embodiment 2
In the 250m1 four-hole boiling flasks equipped with agitator, condensing reflux pipe and thermocouple, add 25gIPDI, 50g number equal
Molecular weight is 2000 PTMEG, 0.01g T12 catalyst, 4g dihydromethyl propionic acids, 0.5g BDO and 10g embodiment 1 be prepared into
The organosilicon dihydroxylic alcohols for arriving, the mixed material that will be obtained reacts 4h at 80 DEG C, is cooled to 55 DEG C and is added thereto to 20g acetone again
Viscosity reduction, continues to be cooled to 45 DEG C, is added thereto to 3g triethylamines, and performed polymer is obtained after 0.5h；
During 330g water is added into the performed polymer for obtaining under the high-speed stirred of 1000r/min with high speed emulsion dispersion machine, point
1.4g ethylenediamines are added dropwise after scattering thereto, the painting of Blue-Color Semitransparent aqueous polyurethane emulsion is obtained after continuing dispersed with stirring 30min
Decorations agent.
The present invention detects that as a result show, emulsion solid content is 20% to the aqueous polyurethane emulsion finishing agent for obtaining,
Film forming light transmittance is 38%, and film stretching is by force 14Mpa, and elongation at break is 670%, and storage stability is more than 6 months.
Embodiment 3
The preparation of organosilicon dihydroxylic alcohols is carried out using the technical scheme of embodiment 1, unlike, in the present embodiment, reaction
Temperature is 90 DEG C, and the reaction time is 4h.
Embodiment 4
In the 250m1 four-hole boiling flasks equipped with agitator, condensing reflux pipe and thermocouple, add 27gIPDI, 45g number equal
Molecular weight is 2000 PTMEG, 0.01g T12 catalyst, 4g dihydromethyl propionic acids, 0.5g BDO and 15g embodiment 2 be prepared into
The organosilicon dihydroxylic alcohols for arriving, the mixed material that will be obtained reacts 4h at 80 DEG C, is cooled to 55 DEG C and is added thereto to 20g acetone drop
It is viscous, continue to be cooled to 45 DEG C, then 3g triethylamines are added thereto to, performed polymer is obtained after 0.5h；
During 340g water is added into performed polymer under the high-speed stirred of 1000r/min with high speed emulsion dispersion machine, after scattering
1.6g ethylenediamines are added dropwise thereto, Blue-Color Semitransparent aqueous polyurethane emulsion finishing agent is obtained after continuing dispersed with stirring 30min.
The aqueous polyurethane emulsion finishing agent that present invention detection is obtained, as a result shows, emulsion solid content is 20%, and film forming is saturating
Light rate is 32%, and film stretching intensity is 17Mpa, and elongation at break is 560%, and storage stability is more than 6 months.
Embodiment 5
The preparation of organosilicon dihydroxylic alcohols is carried out using the technical scheme of embodiment 1, unlike, in the present embodiment, reaction
Temperature is 100 DEG C, and the reaction time is 6h.
Embodiment 6
In the 250m1 four-hole boiling flasks equipped with agitator, condensing reflux pipe and thermocouple, add 23gIPDI, 55g number equal
Molecular weight is 1000 polycaprolactone glycol, 0.01g T12 catalyst, 4g dihydromethyl propionic acids, 0.5g BDO and 5g embodiment 1
The organosilicon dihydroxylic alcohols for preparing, the mixed material that will be obtained reacts 4h at 80 DEG C, is cooled to 55 DEG C and is added thereto to 20g
Acetone viscosity reduction, continues to be cooled to 45 DEG C, then is added thereto to 3g triethylamines, and performed polymer is obtained after reaction 0.5h；
During 320g water is added into performed polymer under the high-speed stirred of 1000r/min with high speed emulsion dispersion machine, after scattering
1g ethylenediamines are added dropwise thereto again, continue to obtain Blue-Color Semitransparent aqueous polyurethane emulsion finishing agent after disperseing 30min.
The aqueous polyurethane emulsion finishing agent that present invention detection is obtained, as a result shows, emulsion solid content is 20%, and film forming is saturating
Light rate is 43%, and film stretching intensity is 12Mpa, and elongation at break is 750%, and storage stability is more than 6 months.
Embodiment 7
In the 250m1 four-hole boiling flasks equipped with agitator, condensing reflux pipe and thermocouple, add 26gIPDI, 40g number equal
Molecular weight be 600 PCDL, 0.01g T12 catalyst, 4g dihydromethyl propionic acids, 0.5g trimethylolpropanes and
The organosilicon dihydroxylic alcohols that 20g embodiments 1 are prepared, the mixed material that will be obtained reacts 4h at 80 DEG C, be cooled to 55 DEG C to
20g acetone viscosity reductions are wherein added, continues to be cooled to 45 DEG C, then be added thereto to 3g triethylamines, performed polymer is obtained after 0.5h；
During 330g water is added into performed polymer under the high-speed stirred of 1000r/min with high speed emulsion dispersion machine, after scattering
1.8g butanediamine is added dropwise thereto again, continues to obtain Blue-Color Semitransparent aqueous polyurethane emulsion finishing agent after disperseing 30min.
The aqueous polyurethane emulsion finishing agent that present invention detection is obtained, as a result shows, emulsion solid content is 20%, and film forming is saturating
Light rate be 28%, film stretching intensity be 22Mpa, elongation at break 430%, storage stability is more than 6 months.
As seen from the above embodiment,
In the present invention, organosilicon dihydroxylic alcohols is modified to polyurethane, is wrapped in the structure of the organosilicon dihydroxylic alcohols
Mol ratio is included for (2~4):1 expoxy propane and oxirane so that the polarity of organosilicon dihydroxylic alcohols there occurs change, so that
In making the glycol modified polyurethane of the organosilicon for obtaining there is certain strand pole in organosilicon composition with other polyurethane components
Sex differernce, there is certain incompatibility, is produced in film forming procedure and is slightly separated, and organosilicon composition is enriched in film formation surface, from
And forming homogeneous opaque film so that the aqueous polyurethane that the present invention is provided need not add additional when being used as finishing agent
Additive, still with performance and comfortable feel is preferably covered, so as to would not also there is the storage that outer doping brings
The problem of stability difference feel and compounding stability.And the aqueous polyurethane film caudacoria that the present invention is provided has preferable power
Learn performance.
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of aqueous polyurethane, is the glycol modified aqueous polyurethane of organosilicon, and the organosilicon dihydroxylic alcohols has Formulas I institute
Show structure：
In Formulas I, R1And R2Independently selected from the alkyl that H or carbon number are 1~5；
R3And R4Independently selected from H or methyl；
N, p and q are the degree of polymerization, independently are 10~100；
The organosilicon dihydroxylic alcohols structure includes expoxy propane and oxirane, the expoxy propane and oxirane mole
Than being (2~4):1.
2. aqueous polyurethane according to claim 1, it is characterised in that R1And R2It is 1 independently selected from H or carbon number
~3 alkyl.
3. aqueous polyurethane according to claim 1, it is characterised in that described n, p and q independently are 20~80.
4. aqueous polyurethane according to claim 1, it is characterised in that the preparation method of the organosilicon dihydroxylic alcohols includes
Following steps：
The polyethers that the polysiloxanes that double hydrogen are blocked is blocked with monoene alkyl is reacted in the presence of catalyst, is obtained organic
Silicon dihydroxylic alcohols；
The monoene alkyl end capped polyether monomer includes expoxy propane and oxirane, the expoxy propane and oxirane
Mol ratio is (2~4):1.
5. aqueous polyurethane according to claim 4, it is characterised in that described pair of polysiloxanes and monoolefine of hydrogen end-blocking
The temperature of the polyether reactant of base end-blocking is 90 DEG C~100 DEG C；
The described pair of polysiloxanes of hydrogen end-blocking and the time of the polyether reactant of monoene alkyl end-blocking are 4h~6h.
6. aqueous polyurethane according to claim 4, it is characterised in that the catalyst is platinum metal catalyst；
The consumption of the catalyst is 1ppm~10ppm.
7. a kind of preparation method of aqueous polyurethane, comprises the following steps：
A) in the presence of catalyst, by the organosilicon dihydroxylic alcohols with Formulas I structure, aliphatic isocyanates, polyalcohol and the moon
Ionic hydrophilic monomer chain extender carries out prepolymerization reaction, obtains performed polymer, and the aliphatic isocyanates at least include that a kind of two is different
Cyanate；
B) neutralization reaction will be carried out with neutralization reagent after the performed polymer viscosity reduction, obtains neutralization reaction product；
C) after the neutralization reaction product is mixed with water, emulsion chain extension is carried out, obtains aqueous polyurethane；
In Formulas I, R1And R2Independently selected from the alkyl that H or carbon number are 1~5；
R3And R4Independently selected from H or methyl；
N, p and q are the degree of polymerization, independently are 10~100；
The organosilicon dihydroxylic alcohols structure includes expoxy propane and oxirane, the expoxy propane and oxirane mole
Than being (2~4):1.
8. preparation method according to claim 7, it is characterised in that the temperature of the prepolymerization reaction is 70 DEG C~100 DEG C.
9. preparation method according to claim 7, it is characterised in that the time of the prepolymerization reaction is 2h~5h.
10. aqueous polyurethane is used for the application of finishing agent, and the aqueous polyurethane is water described in claim 1~6 any one
The aqueous polyurethane that property polyurethane or preparation method described in any one of claim 7~9 are obtained.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410815705.9A CN104448205B (en) | 2014-12-24 | 2014-12-24 | A kind of aqueous polyurethane, its preparation method and its application for finishing agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410815705.9A CN104448205B (en) | 2014-12-24 | 2014-12-24 | A kind of aqueous polyurethane, its preparation method and its application for finishing agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104448205A CN104448205A (en) | 2015-03-25 |
| CN104448205B true CN104448205B (en) | 2017-06-16 |
Family
ID=52895004
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410815705.9A Active CN104448205B (en) | 2014-12-24 | 2014-12-24 | A kind of aqueous polyurethane, its preparation method and its application for finishing agent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104448205B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105237725B (en) * | 2015-09-14 | 2018-08-28 | 合肥安利聚氨酯新材料有限公司 | A kind of middle hard height resists cold heat resistanceheat resistant adhesion agreeable type minute surface face layer polyurethane resin and preparation method thereof |
| CN106519169B (en) * | 2016-11-17 | 2019-03-26 | 上海佰奥聚新材料科技有限公司 | Waterborne organic silicon dispersions of polyurethanes and its preparation and application |
| CN107383375B (en) * | 2017-08-11 | 2021-03-30 | 烟台德邦科技股份有限公司 | Preparation method of organic silicon modified polyester for modifying TPU (thermoplastic polyurethane) |
| CN107307487B (en) * | 2017-09-02 | 2018-12-14 | 泉州万商服饰有限公司 | A kind of corrosion-resistant gloves |
| CN109666127B (en) * | 2018-12-05 | 2021-09-10 | 上海华峰新材料研发科技有限公司 | Self-leveling light-cured polyurethane resin for synthetic leather and preparation method thereof |
| CN110467842A (en) * | 2019-07-30 | 2019-11-19 | 清远市美佳乐环保新材股份有限公司 | There is one kind wetting to thicken multifunctional aqueous auxiliary agent and preparation method thereof |
| CN112030567A (en) * | 2020-09-07 | 2020-12-04 | 清远市美佳乐环保新材股份有限公司 | Surface coating agent for multi-velvet-feeling Yangbuck and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1772785A (en) * | 2005-11-11 | 2006-05-17 | 华中师范大学 | Prepn of dihydroxy dialkyl siloxane polymer modified water-base polyurethane |
| CN101225150A (en) * | 2008-01-28 | 2008-07-23 | 浙江大学 | Method for synthesizing water-dispersion organosilicon-polyurethane block copolymer |
| CN101381462A (en) * | 2008-09-10 | 2009-03-11 | 中国科学技术大学 | Polysiloxane binary alcohol with polyether block and preparation method thereof |
-
2014
- 2014-12-24 CN CN201410815705.9A patent/CN104448205B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1772785A (en) * | 2005-11-11 | 2006-05-17 | 华中师范大学 | Prepn of dihydroxy dialkyl siloxane polymer modified water-base polyurethane |
| CN101225150A (en) * | 2008-01-28 | 2008-07-23 | 浙江大学 | Method for synthesizing water-dispersion organosilicon-polyurethane block copolymer |
| CN101381462A (en) * | 2008-09-10 | 2009-03-11 | 中国科学技术大学 | Polysiloxane binary alcohol with polyether block and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 基于EPDMS的水性聚氨酯合成与表面性能研究;李维虎等;《中国涂料》;20101231;第25卷(第6期);40-44 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104448205A (en) | 2015-03-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104448205B (en) | A kind of aqueous polyurethane, its preparation method and its application for finishing agent | |
| CN104356342B (en) | Organic silicon modified aqueous polyurethane leather finishing agent and preparation method | |
| CN108676144B (en) | Water-proof moisture-permeable aqueous polyurethane dispersoid and preparation method and application thereof | |
| CN102417595B (en) | Preparation method of novel polyurethane-modified organic silica gel | |
| Zhu et al. | Preparation and properties of a novel low crystallinity cross-linked network waterborne polyurethane for water-based ink | |
| CN106146785B (en) | Leather finishing agent organic-silicon-modified carboxylic acid/sulfonic acid type water-based polyurethane and its method | |
| CN106397780B (en) | Preparation method of functional epoxy resin curing agent | |
| CN106432665A (en) | High-performance waterborne polyurethane resin and preparation method thereof | |
| CN107057032A (en) | A kind of high-performance water-based polyurethane resin and preparation method for spinning coating | |
| CN107141434A (en) | It is a kind of for waterborne polyurethane resin of synthetic leather fabric and preparation method thereof | |
| CN103436168A (en) | Polysiloxane and glycidol-containing strong-hydrophobicity gelatin leather finishing agent and preparation method | |
| CN106279620A (en) | A kind of modified aqueous polyurethane resin for woodcare paint and preparation method thereof | |
| CN107022297A (en) | A kind of water-fast aqueous polyurethane coating with bi component and preparation method thereof | |
| CN105218774B (en) | Polysiloxane-modified terpenyl epoxy resin polyalcohol water dispersoid of anionic and preparation method thereof | |
| CN110982414B (en) | Food contact water-based wood coating and preparation method thereof | |
| CN107141442A (en) | A kind of method of terminal hydroxy liquid modified rubber aqueous polyurethane matting resin | |
| CN109898343A (en) | Super soft use for synthetic leather no-solvent polyurethane intermediate layer resin of one kind and preparation method thereof | |
| CN106432667A (en) | Self-delustering soft waterborne polyurethane leather finishing agent and preparation method thereof | |
| CN112770720B (en) | Gelled aerosol articles and gel forming kits | |
| CN107880242A (en) | Solvent-free Modification waterborne polyurethane resin for leather finish and preparation method thereof | |
| US20180271191A1 (en) | High-elasticity polyurethane material | |
| CN106674468A (en) | A HEUR thickener | |
| CN107602814A (en) | A kind of cationic water polyurethane resin for spinning coating and preparation method thereof | |
| CN114716910B (en) | Organic silicon scratch-resistant antifouling coating for synthetic leather and preparation method thereof | |
| CN110467842A (en) | There is one kind wetting to thicken multifunctional aqueous auxiliary agent and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| PE01 | Entry into force 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: The invention relates to an aqueous polyurethane, a preparation method thereof and its application in a finishing agent Effective date of registration: 20220225 Granted publication date: 20170616 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 | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20231007 Granted publication date: 20170616 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 | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: A water-based polyurethane, its preparation method, and its application as a finishing agent Effective date of registration: 20231009 Granted publication date: 20170616 Pledgee: Industrial Bank Limited by Share Ltd. Chengdu branch Pledgor: DOWELL TECHNOLOGY Co.,Ltd. Registration number: Y2023980060498 |