CN116041713A - Triblock fluorine-silicon synergistic modified waterborne polyurethane-acrylate emulsion and preparation method thereof - Google Patents
Triblock fluorine-silicon synergistic modified waterborne polyurethane-acrylate emulsion and preparation method thereof Download PDFInfo
- Publication number
- CN116041713A CN116041713A CN202211649424.1A CN202211649424A CN116041713A CN 116041713 A CN116041713 A CN 116041713A CN 202211649424 A CN202211649424 A CN 202211649424A CN 116041713 A CN116041713 A CN 116041713A
- Authority
- CN
- China
- Prior art keywords
- parts
- polyurethane
- triblock
- acrylate
- acrylic ester
- 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.)
- Pending
Links
- 239000000839 emulsion Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000004945 emulsification Methods 0.000 title claims description 10
- ZHPNWZCWUUJAJC-UHFFFAOYSA-N fluorosilicon Chemical compound [Si]F ZHPNWZCWUUJAJC-UHFFFAOYSA-N 0.000 title claims description 8
- 230000002195 synergetic effect Effects 0.000 title description 8
- 229920002635 polyurethane Polymers 0.000 claims abstract description 42
- 239000004814 polyurethane Substances 0.000 claims abstract description 42
- -1 acrylic ester Chemical class 0.000 claims abstract description 37
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002904 solvent Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 10
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 8
- 239000011737 fluorine Substances 0.000 claims abstract description 8
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000004812 organic fluorine compounds Chemical class 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 29
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 20
- 239000000178 monomer Substances 0.000 claims description 16
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- 239000003999 initiator Substances 0.000 claims description 14
- 238000004321 preservation Methods 0.000 claims description 13
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 11
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 8
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 7
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 6
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 6
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 6
- 230000001105 regulatory effect Effects 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 238000006386 neutralization reaction Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 229920005862 polyol Polymers 0.000 claims description 5
- 150000003077 polyols Chemical class 0.000 claims description 5
- 238000010008 shearing Methods 0.000 claims description 5
- DEQJNIVTRAWAMD-UHFFFAOYSA-N 1,1,2,4,4,4-hexafluorobutyl prop-2-enoate Chemical compound FC(F)(F)CC(F)C(F)(F)OC(=O)C=C DEQJNIVTRAWAMD-UHFFFAOYSA-N 0.000 claims description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 4
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 claims description 4
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 claims description 4
- 150000005215 alkyl ethers Chemical class 0.000 claims description 4
- 239000003431 cross linking reagent Substances 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 4
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 4
- 239000003995 emulsifying agent Substances 0.000 claims description 4
- BITPLIXHRASDQB-UHFFFAOYSA-N ethenyl-[ethenyl(dimethyl)silyl]oxy-dimethylsilane Chemical compound C=C[Si](C)(C)O[Si](C)(C)C=C BITPLIXHRASDQB-UHFFFAOYSA-N 0.000 claims description 4
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 4
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 4
- 239000004970 Chain extender Substances 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- 239000005056 polyisocyanate Substances 0.000 claims description 3
- 229920001228 polyisocyanate Polymers 0.000 claims description 3
- HEBRGEBJCIKEKX-UHFFFAOYSA-M sodium;2-hexadecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HEBRGEBJCIKEKX-UHFFFAOYSA-M 0.000 claims description 3
- SKCLLGJQGVZWHD-UHFFFAOYSA-L zinc;2-methoxybenzoate Chemical compound [Zn+2].COC1=CC=CC=C1C([O-])=O.COC1=CC=CC=C1C([O-])=O SKCLLGJQGVZWHD-UHFFFAOYSA-L 0.000 claims description 3
- LCPUCXXYIYXLJY-UHFFFAOYSA-N 1,1,2,4,4,4-hexafluorobutyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(F)(F)C(F)CC(F)(F)F LCPUCXXYIYXLJY-UHFFFAOYSA-N 0.000 claims description 2
- YJKHMSPWWGBKTN-UHFFFAOYSA-N 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)F YJKHMSPWWGBKTN-UHFFFAOYSA-N 0.000 claims description 2
- BVTLTBONLZSBJC-UHFFFAOYSA-N 2,4,6-tris(ethenyl)-2,4,6-trimethyl-1,3,5,2,4,6-trioxatrisilinane Chemical compound C=C[Si]1(C)O[Si](C)(C=C)O[Si](C)(C=C)O1 BVTLTBONLZSBJC-UHFFFAOYSA-N 0.000 claims description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 2
- BTBJBAZGXNKLQC-UHFFFAOYSA-N ammonium lauryl sulfate Chemical compound [NH4+].CCCCCCCCCCCCOS([O-])(=O)=O BTBJBAZGXNKLQC-UHFFFAOYSA-N 0.000 claims description 2
- JJRDHFIVAPVZJN-UHFFFAOYSA-N cyclotrisiloxane Chemical compound O1[SiH2]O[SiH2]O[SiH2]1 JJRDHFIVAPVZJN-UHFFFAOYSA-N 0.000 claims description 2
- 230000001804 emulsifying effect Effects 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- DUIOKRXOKLLURE-UHFFFAOYSA-N 2-octylphenol Chemical compound CCCCCCCCC1=CC=CC=C1O DUIOKRXOKLLURE-UHFFFAOYSA-N 0.000 claims 1
- STSCVKRWJPWALQ-UHFFFAOYSA-N TRIFLUOROACETIC ACID ETHYL ESTER Chemical compound CCOC(=O)C(F)(F)F STSCVKRWJPWALQ-UHFFFAOYSA-N 0.000 claims 1
- WFGNYCOGRUOTEB-UHFFFAOYSA-N ethyl 2-(trifluoromethyl)prop-2-enoate Chemical compound CCOC(=O)C(=C)C(F)(F)F WFGNYCOGRUOTEB-UHFFFAOYSA-N 0.000 claims 1
- 150000005846 sugar alcohols Polymers 0.000 claims 1
- 229920002554 vinyl polymer Polymers 0.000 abstract description 4
- 238000005260 corrosion Methods 0.000 abstract description 3
- 230000007797 corrosion Effects 0.000 abstract description 3
- 238000006116 polymerization reaction Methods 0.000 abstract description 3
- 238000004383 yellowing Methods 0.000 abstract description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 150000002009 diols Chemical class 0.000 description 4
- 125000001153 fluoro group Chemical group F* 0.000 description 4
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 description 3
- VDRSDNINOSAWIV-UHFFFAOYSA-N [F].[Si] Chemical group [F].[Si] VDRSDNINOSAWIV-UHFFFAOYSA-N 0.000 description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 description 3
- 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 3
- 239000003973 paint Substances 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
- 229920000515 polycarbonate Polymers 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- 229920000909 polytetrahydrofuran Polymers 0.000 description 3
- KKTUQAYCCLMNOA-UHFFFAOYSA-N 2,3-diaminobenzoic acid Chemical compound NC1=CC=CC(C(O)=O)=C1N KKTUQAYCCLMNOA-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000011527 polyurethane coating Substances 0.000 description 2
- 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 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 229920006222 acrylic ester polymer Polymers 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- FMFMWMOBOFPQMW-UHFFFAOYSA-N ethyl 2,3,3-trifluoroprop-2-enoate Chemical compound CCOC(=O)C(F)=C(F)F FMFMWMOBOFPQMW-UHFFFAOYSA-N 0.000 description 1
- ZYMKZMDQUPCXRP-UHFFFAOYSA-N fluoro prop-2-enoate Chemical compound FOC(=O)C=C ZYMKZMDQUPCXRP-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- SCFQUKBBGYTJNC-UHFFFAOYSA-N heptyl prop-2-enoate Chemical compound CCCCCCCOC(=O)C=C SCFQUKBBGYTJNC-UHFFFAOYSA-N 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010257 thawing Methods 0.000 description 1
- KEROTHRUZYBWCY-UHFFFAOYSA-N tridecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCOC(=O)C(C)=C KEROTHRUZYBWCY-UHFFFAOYSA-N 0.000 description 1
- XOALFFJGWSCQEO-UHFFFAOYSA-N tridecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCOC(=O)C=C XOALFFJGWSCQEO-UHFFFAOYSA-N 0.000 description 1
Images
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
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
Abstract
The invention discloses a triblock fluorosilicone acrylic ester modified polyurethane emulsion and a preparation method thereof, wherein the method utilizes double-end vinyl siloxane modified polyacrylate and fluorine-containing acrylic ester to cooperatively modify polyurethane, and adopts a segmented polymerization method to prepare aqueous polyurethane-acrylic ester emulsion with a triblock structure; the middle of the obtained product is polyurethane, one end of the polyurethane is connected with an organosilicon modified polyacrylate segment, and the other end of the polyurethane is connected with an organofluorine modified polyacrylate segment. According to the invention, the acrylic ester chain segment is introduced, and simultaneously, the organic fluorine and organic silicon groups are introduced, so that the hardness, corrosion resistance, light resistance and yellowing resistance of the aqueous polyurethane emulsion are improved, and the high temperature resistance, stain resistance, solvent resistance and water resistance of the traditional WPUA are greatly improved.
Description
Technical Field
The invention belongs to the field of water-based paint, and particularly relates to a triblock fluorine-silicon synergistic modified water-based polyurethane-acrylate emulsion and a preparation method thereof.
Background
The water-based polyurethane acrylate (WPUA) has the advantages of polyurethane and polyacrylate at the same time. Polyacrylate has the advantages of high hardness, corrosion resistance, light resistance, low production cost, yellowing resistance and the like, and excellent wear resistance, weather resistance and elasticity are excellent properties possessed by polyurethane, so that WPUA is widely used in various industries of people living and industrial production. However, WPUA introduces a certain number of hydrophilic groups or atoms or groups with strong hydrophilic ability on the molecular structure, so that the WPUA has poor hydrophobic and oleophobic ability, solvent erosion resistance and mechanical properties. The organic siloxane and organic fluorine groups are introduced into polyurethane acrylic acid dispersoid, and the chemical modification effect of the organic siloxane and the organic fluorine groups on polyurethane acrylic ester polymer is achieved by utilizing the synergistic effect of the organic siloxane and the organic fluorine groups, so that the modified resin has special functions of high temperature resistance, stain resistance, solvent resistance, water resistance and the like, can be applied to water-based woodware, glass paint and metal, can completely reach the standard and the requirement of the same type of solvent type polyurethane coating on the construction performance and the paint film performance, can replace the similar solvent type polyurethane coating, has the characteristics of environmental protection and safety, and meets the development requirement of environmental protection of the current coating.
Disclosure of Invention
The invention aims to provide a preparation method of a fluorosilicone synergistic modified waterborne polyurethane-acrylate emulsion, which is used for preparing a triblock waterborne polyurethane-acrylate emulsion by synergistic modification of polyacrylate and fluorine-containing acrylate modified by double-end vinyl siloxane so as to improve the hydrophobic and oleophobic capacity, the solvent erosion resistance and the mechanical property of a common waterborne polyurethane-acrylate system.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: a triblock fluorosilicone acrylate modified polyurethane emulsion is prepared from polyurethane, wherein one end of the polyurethane is connected with an organosilicon modified polyacrylate segment, and the other end of the polyurethane is connected with an organofluorine modified polyacrylate segment.
A preparation method of triblock fluorosilicone acrylate modified polyurethane emulsion comprises the following steps:
preparation of organosilicon modified waterborne polyurethane-acrylic ester: mixing 5-20 parts of vinyl-terminated siloxane, 10-30 parts of acrylate monomer, 3-7 parts of solvent, 1-3 parts of emulsifier, 1-3 parts of surfactant, 1-3 parts of cross-linking agent and 100-300 parts of deionized water, and performing ultrasonic emulsification for 30-50 min to obtain pre-emulsion; adding a part of pre-emulsion into a reaction container, stirring and heating to 60-85 ℃ and adding 0.1-0.3 part of initiator, continuously stirring until the emulsion is blue light and the temperature is stable, continuously dripping the rest of pre-emulsion and 0.2-0.6 part of initiator, continuously dripping 100-200 parts of aqueous polyurethane prepolymer and 0.5-1.5 part of initiator after heat preservation reaction for 1-3 hours, and performing heat preservation reaction for 1-3 hours to obtain diblock organosilicon modified aqueous polyurethane-acrylate emulsion;
preparation of triblock fluorosilicone modified waterborne polyurethane-acrylic ester: 10-25 parts of fluorine-containing acrylic ester and 10-50 parts of other acrylic ester monomers are mixed to obtain monomer mixed solution; and continuously dropwise adding 0.3-1.5 parts of monomer mixed solution and initiator into the organosilicon modified waterborne polyurethane-acrylic ester system, keeping the temperature after the dropwise adding is completed for 1-2 hours, completely reacting, naturally cooling, and regulating the pH value to be neutral by ammonia water to obtain the triblock fluorine-silicon modified waterborne polyurethane-acrylic ester.
Further preferably, the vinyl-terminated siloxane is any one of vinyl-terminated dimethylpolysiloxane, 1, 3-divinyl tetramethyldisiloxane, 2,4, 6-trivinyl-2, 4, 6-trimethylcyclotrisiloxane, 2,4,6, 8-tetramethyl-2, 4,6, 8-tetravinyl cyclotrisiloxane.
More preferably, the fluorinated acrylate is any one of perfluoroalkyl ethyl acrylate, tridecyl methacrylate, tridecyl acrylate, hexafluorobutyl methacrylate, hexafluorobutyl acrylate, dodecafluoro heptyl methacrylate, dodecafluoro heptyl acrylate, ethyl trifluoromethyl acrylate, and ethyl trifluoroacrylate.
Further preferably, the acrylic acid ester monomer is any one of butyl acrylate, methyl methacrylate, and isobutyl methacrylate.
Further preferably, the solvent is n-hexane or n-hexadecane.
Further preferably, the emulsifier is any one of sodium dodecyl benzene sulfonate, ammonium dodecyl sulfate and sodium hexadecyl benzene sulfonate
Further preferably, the surfactant is any one of polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene alkyl allyl ether, and octylphenol polyoxyethylene.
Further preferably, the cross-linking agent is any one of N-methylolacrylamide, acid diacyl well and zinc o-methoxybenzoate
Further preferably, the initiator is any one of ammonium persulfate, sodium persulfate and potassium persulfate.
Further preferably, the preparation process of the aqueous polyurethane prepolymer comprises the following steps: 5-20 parts of oligomer polyol and 7-25 parts of polyisocyanate are added into a reaction vessel, and the temperature is raised to 70-90 ℃ under the protection of nitrogen. Detecting the NCO content in the system after 3-5 hours of reaction; when the NCO content reaches the theoretical value, the temperature is reduced to 50-60 ℃, 0.5-2 parts of hydrophilic chain extender and 0.2-0.5 part of polyol are added, then the mixture is stirred and heated to 60-85 ℃, and 0.5-2 parts of catalyst and 7-12 parts of acetone or butanone are added dropwise to adjust the viscosity of the prepolymer. Cooling to room temperature after reacting for 1-3 h, adding 0.5-2 parts of triethylamine for neutralization reaction for 15min, adding 10-20 parts of deionized water, emulsifying for 15-30 min by high-speed shearing, and distilling under reduced pressure to remove the solvent, thus obtaining the waterborne polyurethane prepolymer.
Further preferably, the oligomer polyol is any one of polypropylene glycol, polycaprolactone diol, polycarbonate diol, and polytetrahydrofuran ether diol.
Further preferably, the polyisocyanate is any one of 2, 4-toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate.
Further preferably, the hydrophilic chain extender is any one of dimethylolpropionic acid and diaminobenzoic acid.
Further preferably, the polyol is any one of 1, 4-butanediol, ethylene glycol, diethylene glycol and hexanediol.
Further preferably, the catalyst is any one of dibutyl tin dilaurate, stannous octoate and methyl diethanolamine.
The beneficial effects of the invention are as follows: the preparation method comprises the steps of preparing aqueous polyurethane-acrylic ester emulsion with a triblock structure by utilizing double-end vinyl siloxane modified polyacrylate and fluorine-containing acrylic ester to synergistically modify polyurethane for the first time and adopting a segmented polymerization method. Introducing organic fluorine and organic silicon groups at the same time of introducing polyacrylate chain segments. Not only is the polyacrylate segment beneficial to improving the hardness, corrosion resistance, light resistance and yellowing resistance of the aqueous polyurethane emulsion, but also the organic fluorine silicon group greatly improves the high temperature resistance, stain resistance, solvent resistance, water resistance and the like of the traditional WPUA. The structure and the composition of the organic silicon modified acrylic ester-polyurethane-organic fluorine modified acrylic ester triblock are regulated, so that the performance advantages of polyurethane and polyacrylate can be retained to the maximum extent, the compatibility and emulsion stability between an organic fluorine silicon group and a polyurethane chain segment can be improved, and the formation of the fluorine silicon modified WPUA emulsion with excellent and stable performance is facilitated.
Drawings
FIG. 1 is a flow chart of a preparation process of triblock fluorine-silicon synergistic modified waterborne polyurethane-acrylic ester.
FIG. 2 is a block diagram of a three-block fluorosilicone synergistic modified waterborne polyurethane-acrylate.
In the figure: 100-polyurethane, 200-organosilicon modified polyacrylate segment, 300-organofluorine modified polyacrylate segment
Detailed Description
The present invention will be described in further detail with reference to fig. 1 and examples, but the experimental embodiment is not limited thereto.
The parts mentioned in the following examples of the present invention are all parts by mass.
Example 1
Step 1: 10 parts of polypropylene glycol and 12 parts of 2, 4-toluene diisocyanate are added into a reaction vessel, and the temperature is raised to 80 ℃ under the protection of nitrogen; detecting the NCO content in the system after 3 hours of reaction; when the NCO content reaches the theoretical value (namely, the polypropylene glycol is completely reacted), the temperature is reduced to 50 ℃,1 part of dimethylolpropionic acid and 0.3 part of 1, 4-butanediol are added, then the mixture is stirred and heated to 80 ℃, and 1.5 parts of dibutyltin dilaurate and 8 parts of acetone are added dropwise to adjust the viscosity of the prepolymer. Cooling to room temperature after reacting for 3 hours, adding 1.5 parts of triethylamine for neutralization reaction for 15 minutes, adding 15 parts of deionized water, and carrying out high-speed shearing emulsification for 20 minutes and reduced pressure distillation to remove a solvent to obtain the waterborne polyurethane prepolymer WPU.
Step 2: 10 parts of vinyl-terminated dimethylpolysiloxane, 10 parts of butyl acrylate, 10 parts of methyl methacrylate, 5 parts of N-hexane, 1 part of sodium dodecyl benzene sulfonate, 1 part of polyoxyethylene alkyl ether, 1 part of N-methylolacrylamide and 100 parts of deionized water are mixed, and the mixture is subjected to ultrasonic emulsification for 30 minutes to obtain a pre-emulsion. Adding 1/3 of the pre-emulsion into a reaction vessel, stirring and heating to 80 ℃, adding 0.1 part of potassium persulfate, continuously stirring until the emulsion is blue light and the temperature is stable, continuously dripping the rest 2/3 of the pre-emulsion and 0.2 part of potassium persulfate within 2 hours, continuously dripping 100 parts of WPU prepolymer and 0.5 part of initiator after heat preservation reaction for 1 hour, and performing heat preservation reaction for 2 hours to obtain the diblock organosilicon modified waterborne polyurethane-acrylic ester emulsion.
Step 3: 10 parts of perfluoroalkyl ethyl acrylate, 10 parts of butyl acrylate and 10 parts of methyl methacrylate are mixed to obtain a monomer mixed solution; and (3) continuously dropwise adding 0.2 part of monomer mixed solution and potassium persulfate into the diblock organosilicon modified waterborne polyurethane-acrylic ester system obtained in the second step, carrying out heat preservation reaction for 1h after the dropwise adding is finished within 2h, naturally cooling, and regulating the pH value to be neutral by ammonia water to obtain the triblock fluorosilicone modified waterborne polyurethane-acrylic ester.
Example 2
Step 1: 7 parts of polycarbonate diol and 10 parts of isophorone diisocyanate were added to a reaction vessel, and the temperature was raised to 85℃under nitrogen protection. Detecting the NCO content in the system after 3.5 hours of reaction; when the NCO content reaches the theoretical value (namely the polycarbonate diol is completely reacted), the temperature is reduced to 50 ℃,2 parts of dimethylolpropionic acid and 0.2 part of ethylene glycol are added, then the mixture is stirred and heated to 85 ℃, and 2 parts of dibutyltin dilaurate and 10 parts of acetone are added dropwise to adjust the viscosity of the prepolymer. Cooling to room temperature after reacting for 3 hours, adding 2 parts of triethylamine for neutralization reaction for 15 minutes, adding 15 parts of deionized water, and removing the solvent through high-speed shearing and emulsification for 20 minutes and reduced pressure distillation to obtain the waterborne polyurethane prepolymer WPU.
Step 2: 15 parts of vinyl-terminated dimethylpolysiloxane, 5 parts of butyl acrylate, 10 parts of methyl methacrylate, 5 parts of N-hexane, 1 part of sodium dodecyl benzene sulfonate, 1 part of polyoxyethylene alkyl ether, 1 part of N-methylolacrylamide and 80 parts of deionized water are mixed, and the mixture is subjected to ultrasonic emulsification for 40 minutes to obtain a pre-emulsion. Adding 1/3 of the pre-emulsion into a reaction vessel, stirring and heating to 85 ℃, adding 0.15 part of potassium persulfate, continuously stirring until the emulsion is blue light and the temperature is stable, continuously dripping the rest 2/3 of the pre-emulsion and 0.3 part of potassium persulfate within 2 hours, continuously dripping 120 parts of WPU prepolymer and 0.9 part of initiator after heat preservation reaction for 1 hour, and carrying out heat preservation reaction for 3 hours to obtain the diblock organosilicon modified waterborne polyurethane-acrylic ester emulsion.
Step 3: 15 parts of tridecafluorooctyl methacrylate and 20 parts of butyl acrylate and 10 parts of isobutyl methacrylate are mixed to obtain a monomer mixed solution; and (3) continuously dropwise adding 0.3 part of monomer mixed solution and 0.3 part of potassium persulfate into the diblock organosilicon modified waterborne polyurethane-acrylic ester system obtained in the second step, carrying out heat preservation reaction for 1.5 hours after dropwise adding is completed, naturally cooling, and regulating the pH value to be neutral by ammonia water to obtain the triblock fluorosilicone modified waterborne polyurethane-acrylic ester.
Example 3
Step 1: 10 parts of polytetrahydrofuran ether glycol and 13 parts of isophorone diisocyanate are added into a reaction vessel, and the temperature is raised to 85 ℃ under the protection of nitrogen. Detecting the NCO content in the system after 3 hours of reaction; when the NCO content reaches the theoretical value (namely, the polytetrahydrofuran ether dihydric alcohol is completely reacted), the temperature is reduced to 50 ℃,2 parts of diaminobenzoic acid and 0.5 part of diethylene glycol are added, then the mixture is stirred and heated to 70 ℃, and 2 parts of stannous octoate and 10 parts of acetone are added dropwise to adjust the viscosity of the prepolymer. Cooling to room temperature after reacting for 3 hours, adding 2 parts of triethylamine for neutralization reaction for 15 minutes, adding 20 parts of deionized water, and removing the solvent through high-speed shearing and emulsification for 30 minutes and reduced pressure distillation to obtain the waterborne polyurethane prepolymer WPU.
Step 2: 10 parts of 1, 3-divinyl tetramethyl disiloxane, 10 parts of butyl acrylate, 5 parts of isobutyl methacrylate, 7 parts of n-hexadecane, 2 parts of sodium hexadecyl benzene sulfonate, 1 part of polyoxyethylene alkylphenyl ether, 1 part of zinc o-methoxybenzoate and 120 parts of deionized water are mixed, and the mixture is subjected to ultrasonic emulsification for 50 minutes to obtain a pre-emulsion. Adding 1/3 of the pre-emulsion into a reaction vessel, stirring and heating to 85 ℃, adding 0.2 part of ammonium persulfate, continuously stirring until the emulsion is blue light and the temperature is stable, continuously dripping the rest 2/3 of the pre-emulsion and 0.4 part of ammonium persulfate in 2h, continuously dripping 200 parts of WPU (polyurethane-polyurethane) prepolymer and 1.2 parts of an initiator after heat preservation reaction for 1h, and performing heat preservation reaction for 3h to obtain the diblock organosilicon modified waterborne polyurethane-acrylate emulsion.
Step 3: 20 parts of hexafluorobutyl acrylate and 10 parts of butyl acrylate and 30 parts of methyl methacrylate are mixed to obtain a monomer mixed solution; and (3) continuously dropwise adding 0.6 part of monomer mixed solution and ammonium persulfate into the diblock organosilicon modified waterborne polyurethane-acrylic ester system obtained in the second step, carrying out heat preservation reaction for 1h after the dropwise adding is finished within 2h, naturally cooling, and regulating the pH value to be neutral by ammonia water to obtain the triblock fluorosilicone modified waterborne polyurethane-acrylic ester.
As shown in FIG. 2, the three-block fluorosilicone acrylate modified polyurethane emulsion is polyurethane 100 in the middle, one end of the polyurethane 100 is connected with an organosilicon modified polyacrylate segment 200, and the other end of the polyurethane 100 is connected with an organofluorine modified polyacrylate segment 300.
Comparative example 1
The other steps are the same as in example 1 except that no vinyl-terminated dimethylpolysiloxane is added in step 2 and no perfluoroalkyl ethyl acrylate is added in step 3.
Comparative example 2
The other steps are the same as in example 2 except that no vinyl-terminated dimethylpolysiloxane is added in step 2 and tridecafluorooctyl methacrylate is not added in step 3.
Comparative example 3
The other steps are the same as in example 3, except that no terminal 1, 3-divinyl tetramethyl disiloxane is added in step 2 and no hexafluorobutyl acrylate is added in step 3.
TABLE 1 test results of the three-block fluorosilicone modified waterborne polyurethane-acrylate coatings of the invention
As can be seen from the above table, the present invention utilizes a co-modified polyurethane of a double-ended vinyl siloxane modified polyacrylate and a fluoroacrylate. Under the action of an initiator, through the segmented polymerization reaction of the polyurethane prepolymer and acrylic ester, an organosilicon modified polyacrylate segment and an organofluorine modified polyacrylate segment are respectively introduced at two ends of the polyurethane. Because the organic fluorine silicon modified polyacrylate chain segment and the polyurethane chain segment have better compatibility, the problem of poor compatibility caused by directly introducing the organic fluorine silicon group is avoided, and the obtained emulsion has good storage stability and freeze thawing stability. Meanwhile, due to the introduction of organosilicon and organic fluorine groups, a large number of C-F, si-O bonds exist in a molecular chain, so that the hydrophobicity, the water resistance and the mechanical property of the coating can be effectively improved.
The embodiments of the invention are not limited to the examples described above, but all modifications and variants based on the description described above fall within the scope of protection of the appended claims, without being limited to specific details.
Claims (11)
1. A triblock fluorosilicone acrylate modified polyurethane emulsion is characterized in that polyurethane is arranged in the middle, one end of the polyurethane is connected with an organosilicon modified polyacrylate segment, and the other end of the polyurethane is connected with an organofluorine modified polyacrylate segment.
2. A preparation method of triblock fluorosilicone acrylate modified polyurethane emulsion is characterized by comprising the following steps:
preparation of organosilicon modified waterborne polyurethane-acrylic ester: mixing 5-20 parts of vinyl-terminated siloxane, 10-30 parts of acrylate monomer, 3-7 parts of solvent, 1-3 parts of emulsifier, 1-3 parts of surfactant, 1-3 parts of cross-linking agent and 100-300 parts of deionized water, and performing ultrasonic emulsification for 30-50 min to obtain pre-emulsion; adding a part of pre-emulsion into a reaction container, stirring and heating to 60-85 ℃, adding 0.1-0.3 part of initiator, continuously stirring until the emulsion is blue light and the temperature is stable, continuously dripping the rest of pre-emulsion and 0.2-0.6 part of initiator, carrying out heat preservation reaction for 1-3 hours, continuously dripping 100-200 parts of aqueous polyurethane prepolymer and 0.5-1.5 part of initiator, and carrying out heat preservation reaction for 1-3 hours to obtain diblock organosilicon modified aqueous polyurethane-acrylate emulsion;
preparation of triblock fluorosilicone modified waterborne polyurethane-acrylic ester: 10-25 parts of fluorine-containing acrylic ester and 10-50 parts of other acrylic ester monomers are mixed to obtain monomer mixed solution; and continuously dropwise adding 0.3-1.5 parts of monomer mixed solution and initiator into the organosilicon modified waterborne polyurethane-acrylic ester system, keeping the temperature after the dropwise adding is completed for 1-2 hours, performing complete reaction, naturally cooling, and regulating the pH value to be neutral by ammonia water to obtain the triblock fluorine-silicon modified waterborne polyurethane-acrylic ester.
3. The method for preparing the triblock fluorosilicone acrylate modified polyurethane emulsion according to claim 2, wherein the vinyl-terminated siloxane is any one of vinyl-terminated dimethylpolysiloxane, 1, 3-divinyl tetramethyl disiloxane, 2,4, 6-trivinyl-2, 4, 6-trimethyl cyclotrisiloxane and 2,4,6, 8-tetramethyl-2, 4,6, 8-tetravinyl cyclotrisiloxane.
4. The method for preparing the triblock fluorosilicone acrylate modified polyurethane emulsion according to claim 2, wherein the fluorinated acrylate is any one of perfluoroalkyl ethyl acrylate, tridecyl fluorooctyl methacrylate, tridecyl fluorooctyl acrylate, hexafluorobutyl methacrylate, hexafluorobutyl acrylate, dodecafluoroheptyl methacrylate, dodecafluoroheptyl acrylate, ethyl trifluormethacrylate and ethyl trifluoracetate.
5. The method for preparing the triblock fluorosilicone acrylate modified polyurethane emulsion according to claim 2, wherein the acrylate monomer is any one of butyl acrylate, methyl methacrylate and isobutyl methacrylate.
6. The method for preparing the triblock fluorosilicone acrylate modified polyurethane emulsion according to claim 2, wherein the solvent is n-hexane or n-hexadecane.
7. The method for preparing the triblock fluorosilicone acrylate modified polyurethane emulsion according to claim 2, wherein the emulsifier is any one of sodium dodecyl benzene sulfonate, ammonium dodecyl sulfate and sodium hexadecyl benzene sulfonate.
8. The method for preparing the triblock fluorosilicone acrylate modified polyurethane emulsion according to claim 2, wherein the surfactant is any one of polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene alkyl allyl ether and octyl phenol polyoxyethylene.
9. The preparation method of the triblock fluorosilicone acrylate modified polyurethane emulsion according to claim 2, wherein the cross-linking agent is any one of N-methylolacrylamide, acid diacyl well and zinc o-methoxybenzoate.
10. The method for preparing the triblock fluorosilicone acrylate modified polyurethane emulsion according to claim 2, wherein the initiator is any one of ammonium persulfate, sodium persulfate and potassium persulfate.
11. The preparation method of the triblock fluorosilicone acrylate modified polyurethane emulsion according to claim 2, wherein the preparation process of the aqueous polyurethane prepolymer is as follows: 5-20 parts of oligomer polyol and 7-25 parts of polyisocyanate are added into a reaction container, and the temperature is raised to 70-90 ℃ under the protection of nitrogen. Detecting the NCO content in the system after 3-5 hours of reaction; and when the NCO content reaches a theoretical value, cooling to 50-60 ℃, adding 0.5-2 parts of hydrophilic chain extender and 0.2-0.5 part of polyalcohol, stirring, heating to 60-85 ℃, and dropwise adding 0.5-2 parts of catalyst and 7-12 parts of acetone or butanone to adjust the viscosity of the prepolymer. And (3) after reacting for 1-3 hours, cooling to room temperature, adding 0.5-2 parts of triethylamine for neutralization reaction for 15 minutes, adding 10-20 parts of deionized water, emulsifying for 15-30 minutes by high-speed shearing, and removing the solvent by reduced pressure distillation to obtain the waterborne polyurethane prepolymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211649424.1A CN116041713A (en) | 2022-12-21 | 2022-12-21 | Triblock fluorine-silicon synergistic modified waterborne polyurethane-acrylate emulsion and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211649424.1A CN116041713A (en) | 2022-12-21 | 2022-12-21 | Triblock fluorine-silicon synergistic modified waterborne polyurethane-acrylate emulsion and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116041713A true CN116041713A (en) | 2023-05-02 |
Family
ID=86113895
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211649424.1A Pending CN116041713A (en) | 2022-12-21 | 2022-12-21 | Triblock fluorine-silicon synergistic modified waterborne polyurethane-acrylate emulsion and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116041713A (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060167206A1 (en) * | 2003-07-11 | 2006-07-27 | Alois Maier | Fluorine-modified polyurethane resins containing one or two constituents, method for the production thereof, and use of the same |
| CN1951968A (en) * | 2006-10-09 | 2007-04-25 | 中国科学技术大学 | Fluorin-silicon modified core-shell structure polyurethane-acrylate emulsion preparation method |
| CN102432768A (en) * | 2011-10-10 | 2012-05-02 | 嘉兴禾欣化学工业有限公司 | Method for preparing fluorine-silicon containing polyurethane and acrylate emulsion |
| CN103059210A (en) * | 2013-01-30 | 2013-04-24 | 广东银洋树脂有限公司 | Modified hydroxyacrylate emulsion and preparation method thereof |
| CN103804613A (en) * | 2014-02-20 | 2014-05-21 | 江西省科学院应用化学研究所 | Preparation method of organic silicon modified cationic waterborne antibacterial polyurethane emulsion |
| CN105348449A (en) * | 2015-12-16 | 2016-02-24 | 江南大学 | Preparation method of fluorine-silicone modified polyurethane-acrylate composite emulsion |
| KR20170061334A (en) * | 2015-11-26 | 2017-06-05 | 공주대학교 산학협력단 | Silicone-fluorine urethane acrylate resin for forming aqueous adhesive and composition of adhesive comprising the same |
| CN109608974A (en) * | 2018-10-26 | 2019-04-12 | 合肥科天水性科技有限责任公司 | A kind of fluoridation aquosity polyurethane and its preparation method and application |
| CN111849298A (en) * | 2020-07-03 | 2020-10-30 | 安徽朗凯奇建材有限公司 | Organic fluorine-silicon/fluorine-containing acrylate modified polyurethane waterproof coating and preparation method thereof |
-
2022
- 2022-12-21 CN CN202211649424.1A patent/CN116041713A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060167206A1 (en) * | 2003-07-11 | 2006-07-27 | Alois Maier | Fluorine-modified polyurethane resins containing one or two constituents, method for the production thereof, and use of the same |
| CN1951968A (en) * | 2006-10-09 | 2007-04-25 | 中国科学技术大学 | Fluorin-silicon modified core-shell structure polyurethane-acrylate emulsion preparation method |
| CN102432768A (en) * | 2011-10-10 | 2012-05-02 | 嘉兴禾欣化学工业有限公司 | Method for preparing fluorine-silicon containing polyurethane and acrylate emulsion |
| CN103059210A (en) * | 2013-01-30 | 2013-04-24 | 广东银洋树脂有限公司 | Modified hydroxyacrylate emulsion and preparation method thereof |
| CN103804613A (en) * | 2014-02-20 | 2014-05-21 | 江西省科学院应用化学研究所 | Preparation method of organic silicon modified cationic waterborne antibacterial polyurethane emulsion |
| KR20170061334A (en) * | 2015-11-26 | 2017-06-05 | 공주대학교 산학협력단 | Silicone-fluorine urethane acrylate resin for forming aqueous adhesive and composition of adhesive comprising the same |
| CN105348449A (en) * | 2015-12-16 | 2016-02-24 | 江南大学 | Preparation method of fluorine-silicone modified polyurethane-acrylate composite emulsion |
| CN109608974A (en) * | 2018-10-26 | 2019-04-12 | 合肥科天水性科技有限责任公司 | A kind of fluoridation aquosity polyurethane and its preparation method and application |
| CN111849298A (en) * | 2020-07-03 | 2020-10-30 | 安徽朗凯奇建材有限公司 | Organic fluorine-silicon/fluorine-containing acrylate modified polyurethane waterproof coating and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 李伟;胡剑青;涂伟萍;: "有机硅改性水性聚氨酯-聚丙烯酸酯乳液的研究", 涂料工业, no. 07, pages 36 - 38 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107903357B (en) | Fluorine-containing polyurethane modified acrylic acid water-based resin and preparation method thereof | |
| US5594065A (en) | Two component waterborne crosslinkable polyurethane/acrylate-hybrid systems | |
| CN101362815B (en) | Hybrid polyurethane-polyacrylacid ester dispersion containing fluorine and/or siloxane and preparation method thereof | |
| CN109734846B (en) | Core-shell type waterborne polyurethane/acrylate composite emulsion, preparation method thereof and damping coating | |
| CN109575192B (en) | Emulsifier-free waterborne polyurethane acrylate hydrophobic emulsion and preparation method thereof | |
| CN105064036A (en) | Preparation method and application of hyperbranched polyurethane acrylate interpenetrating polymer network waterproof agent | |
| CN109608974B (en) | Fluorinated waterborne polyurethane and preparation method and application thereof | |
| CN112194772B (en) | High-solid self-repairing type waterborne polyurethane acrylate and preparation method thereof | |
| US11053336B2 (en) | High heat resistant and high scratch resistant water-based polyurethane and manufacturing method thereof | |
| CN108003314A (en) | A kind of preparation method of amphipathic free radical type polysilicone-polyurethanes prepolymer | |
| CN109293871B (en) | Self-leveling water-based fluorine-containing polyurethane acrylic resin, preparation method thereof and water-based photocureable coating | |
| CN113773436A (en) | Amphiphilic organic silicon coating and preparation method and application thereof | |
| CN108467471B (en) | Comb-shaped multi-branched aqueous polyurethane dispersion and preparation and application thereof | |
| CN108164650B (en) | Alkenyl-terminated nonionic waterborne polyurethane modified acrylate emulsion and preparation method thereof | |
| CN116875169B (en) | Waterproof corrosion-resistant water paint and preparation method thereof | |
| CN110862508B (en) | Preparation method of triazine-based fluorine-containing chain extender modified polyurethane emulsion | |
| CN116041713A (en) | Triblock fluorine-silicon synergistic modified waterborne polyurethane-acrylate emulsion and preparation method thereof | |
| CN112980376A (en) | Waterborne polyurethane adhesive and preparation method thereof | |
| US11639414B2 (en) | Water-based polyurethane resin and manufacturing method thereof | |
| CN108102349B (en) | Preparation method of organic bentonite/epoxy resin composite modified waterborne polyurethane emulsion | |
| AU2020103155A4 (en) | Non-ionic water based polyurethane and preparation method and use thereof | |
| CN114316202A (en) | Ultraviolet-curing aqueous polyurethane acrylate emulsion and preparation method thereof | |
| DE10112390A1 (en) | Polyurethane dispersion for use as binder, e.g. in paint or adhesives, contains mixture of polymeric polyol, low-mol. wt. polyol, anionically-modifiable polymeth-acrylate-diol, polyisocyanate, neutralizing agent and water | |
| CN110819197A (en) | Surface treating agent with self-cleaning performance for synthetic leather and preparation method thereof | |
| CN111303349B (en) | Carbon dioxide-based cationic waterborne polyurethane grafted polyacrylate dispersion and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |