CN108003320A - 一种高耐水性侧链含氟-硅uv固化水性聚氨酯树脂的制备方法 - Google Patents
一种高耐水性侧链含氟-硅uv固化水性聚氨酯树脂的制备方法 Download PDFInfo
- Publication number
- CN108003320A CN108003320A CN201711370251.9A CN201711370251A CN108003320A CN 108003320 A CN108003320 A CN 108003320A CN 201711370251 A CN201711370251 A CN 201711370251A CN 108003320 A CN108003320 A CN 108003320A
- Authority
- CN
- China
- Prior art keywords
- side chain
- preparation
- silicon
- nco
- polyurethane
- 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.)
- Granted
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 30
- ZHPNWZCWUUJAJC-UHFFFAOYSA-N fluorosilicon Chemical compound [Si]F ZHPNWZCWUUJAJC-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229920005749 polyurethane resin Polymers 0.000 title claims abstract description 8
- 229920002635 polyurethane Polymers 0.000 claims abstract description 27
- 239000004814 polyurethane Substances 0.000 claims abstract description 27
- 229920000642 polymer Polymers 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 229920000728 polyester Polymers 0.000 claims abstract description 6
- 239000000839 emulsion Substances 0.000 claims abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- 229910052731 fluorine Inorganic materials 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- -1 silicon acrylic ester Chemical class 0.000 claims description 12
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 11
- 239000011737 fluorine Substances 0.000 claims description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000010792 warming Methods 0.000 claims description 9
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 7
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- 238000009835 boiling Methods 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- YXRKNIZYMIXSAD-UHFFFAOYSA-N 1,6-diisocyanatohexane Chemical compound O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O YXRKNIZYMIXSAD-UHFFFAOYSA-N 0.000 claims description 5
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 4
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 4
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 4
- 239000004970 Chain extender Substances 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 4
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 claims description 4
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- 150000002009 diols Chemical class 0.000 claims description 4
- 238000004945 emulsification Methods 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 4
- 239000003999 initiator Substances 0.000 claims description 4
- 238000009413 insulation Methods 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims 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 claims description 3
- 238000010521 absorption reaction Methods 0.000 claims description 3
- 239000003112 inhibitor Substances 0.000 claims description 3
- 239000006210 lotion Substances 0.000 claims description 3
- 229920000515 polycarbonate Polymers 0.000 claims description 3
- 239000004417 polycarbonate Substances 0.000 claims description 3
- 235000019260 propionic acid Nutrition 0.000 claims description 3
- 238000004448 titration Methods 0.000 claims description 3
- QTKPMCIBUROOGY-UHFFFAOYSA-N 2,2,2-trifluoroethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)F QTKPMCIBUROOGY-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
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 2
- ARSRBNBHOADGJU-UHFFFAOYSA-N 7,12-dimethyltetraphene Chemical compound C1=CC2=CC=CC=C2C2=C1C(C)=C(C=CC=C1)C1=C2C ARSRBNBHOADGJU-UHFFFAOYSA-N 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- VFZRZRDOXPRTSC-UHFFFAOYSA-N DMBA Natural products COC1=CC(OC)=CC(C=O)=C1 VFZRZRDOXPRTSC-UHFFFAOYSA-N 0.000 claims description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N acrylic acid methyl ester Natural products COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 2
- 229920003054 adipate polyester Polymers 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 2
- 229920001610 polycaprolactone Polymers 0.000 claims description 2
- 239000004632 polycaprolactone Substances 0.000 claims 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 claims 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 claims description 2
- ZGYICYBLPGRURT-UHFFFAOYSA-N tri(propan-2-yl)silicon Chemical compound CC(C)[Si](C(C)C)C(C)C ZGYICYBLPGRURT-UHFFFAOYSA-N 0.000 claims description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims 2
- 238000012512 characterization method Methods 0.000 claims 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 claims 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 abstract description 6
- 229920001296 polysiloxane Polymers 0.000 abstract description 3
- 239000000853 adhesive Substances 0.000 abstract description 2
- 230000001070 adhesive effect Effects 0.000 abstract description 2
- 238000004220 aggregation Methods 0.000 abstract description 2
- 230000002776 aggregation Effects 0.000 abstract description 2
- 229920002521 macromolecule Polymers 0.000 abstract description 2
- 229920006254 polymer film Polymers 0.000 abstract description 2
- 229920006264 polyurethane film Polymers 0.000 abstract description 2
- 238000007711 solidification Methods 0.000 abstract description 2
- 230000008023 solidification Effects 0.000 abstract description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229910018557 Si O Inorganic materials 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000003848 UV Light-Curing Methods 0.000 description 2
- 231100001244 hazardous air pollutant Toxicity 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- DSCZKKBQLCGKDI-UHFFFAOYSA-N NC(=O)OCC.[Si].[F] Chemical compound NC(=O)OCC.[Si].[F] DSCZKKBQLCGKDI-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- PYBNTRWJKQJDRE-UHFFFAOYSA-L dodecanoate;tin(2+) Chemical class [Sn+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O PYBNTRWJKQJDRE-UHFFFAOYSA-L 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical class COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000004672 propanoic acids Chemical class 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 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
- 230000001681 protective effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 229920006009 resin backbone Polymers 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 229920006313 waterborne resin Polymers 0.000 description 1
- 239000013035 waterborne resin Substances 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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
-
- 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
- C08G18/34—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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
-
- 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
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
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)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
本发明涉及一种高耐水性侧链含氟‑硅UV固化水性聚氨酯树脂的制备方法。本发明的目的在于提供一种利用高分子有机氟和有机硅进行改性制备高耐水、耐候、耐溶剂性可UV固化水性聚氨酯乳液及其制备方法。本发明的水性聚氨酯经有机氟和有机硅改性得到侧链含有机氟硅的水性聚氨酯,该聚合物成膜后,聚合物侧链的有机氟和有机硅链段更倾向于表面聚集取向,而聚氨酯链段朝向内层。这样既能在保证聚酯型聚氨酯树脂优良的附着力、硬度、固化速率等的同时又赋予改性聚氨酯涂膜优良的耐水性、耐溶剂性和耐候性。
Description
技术领域
本发明属于高分子材料技术领域,具体涉及一种高耐水性侧链含氟-硅UV固化水性聚氨酯树脂的制备方法。
背景介绍
紫外光固化水性树脂继承和发展了传统UV固化技术和水性涂料技术的许多优点,如低成本、低粘度、良好的涂布适应性、设备简单、无毒性、无刺激性、不燃性等。由于UV固化水性树脂的优点突出,近年来得到较快的发展,其产品已被众多领域应用。
目前大量被使用的聚氨酯以溶剂型为主,但随着人们环保意识的增强和环保法规的确立,传统的溶剂型化学品的挥发性有机化合物(VOC)和有害空气污染物(HAP)的排放愈来愈受到严格限制。制备聚氨酯的水性化技术,以水代替有机溶剂,不仅提高了生产和施工的安全性,避免了有机溶剂的可燃性和毒性,而且能减少或消除聚氨酯固化过程中有机溶剂发带来的环境问题。同时,由于水性聚氨酯以水为介质,气味小、节能、操作加工方便等优点。但聚氨酯水性化后其耐水性、物理力学性能等都会有一定程度的下降,制约了水性聚氨酯材料的应用。
有机硅是一类以重复单元Si-O键为主链,且有机基团直接连接在Si原子上的聚合物。它是半有机、半无机结构的高分子化合物,兼具有机和无机化合物的特性,具有良好的耐低温、耐候性、疏水性、生理惰性以及电绝缘等许多优异的性能。将其用于水性聚氨酯的改性,能有效的提高涂膜的耐水性、耐候型、耐溶剂性和滑爽性。通过在聚酯型水性聚氨酯树脂主链中引入Si-O键得到有机硅改性水性聚氨酯,以提高涂层的耐水性、耐溶剂性、耐候性和抗污性。
含氟聚氨酯以其独有的性能,受到广泛关注。氟原子半径小、电负性强、碳氟键键能高,因此赋予了聚氨酯材料极好的耐紫外线和核辐射性、优良耐磨性,低表面能和高耐候性等性能。与含氟主链型聚氨酯相比,侧链含氟型聚氨酯在自身表面张力的驱动下成膜时,分布于侧链的含氟链段更易于向表面迁移和富集,形成对聚氨酯表面进行有效保护。通常由侧链含氟聚醚多元醇制备的含氟聚氨酯材料,可实现只在表面结构中含氟,体相可少氟或无氟,在不降低材料的力学性能、粘结性和防护性的同时,可实现低氟含量、低成本、高耐水性。
发明内容
本发明的目的在于提供一种利用高分子有机氟和有机硅进行改性制备高耐水、耐候、耐溶剂性可UV固化水性聚氨酯乳液及其制备方法。本发明的水性聚氨酯经有机氟和有机硅改性得到侧链含有机氟硅的水性聚氨酯,该聚合物成膜后,聚合物侧链的有机氟和有机硅链段更倾向于表面聚集取向,而聚氨酯链段朝向内层。这样既能在保证聚酯型聚氨酯树脂优良的附着力、硬度、固化速率等的同时又赋予改性聚氨酯涂膜优良的耐水性、耐溶剂性和耐候性。
本发明的技术方案是:
一种高耐水性侧链含氟-硅UV固化水性聚氨酯树脂的制备方法,包括如下步骤:
(1)侧链含氟硅预聚体的制备:将计量含氟丙烯酸酯、有机硅丙烯酸酯、甲基丙烯酸羟乙酯、N,N-二甲基甲酰胺和引发剂加入装有冷凝管、氮气导管、搅拌棒和温度计的四口烧瓶中,通入氮气保护,升温至75-80℃反应7-8小时,得到侧链含氟硅预聚体;
(2)NCO半封端聚氨酯预聚物的制备:将计量HDI三聚体(HDT)、催化剂和丙酮加入装有冷凝管、氮气导管、搅拌棒和温度计的四口烧瓶中,升温至50-55℃滴加一定量的聚酯二元醇,反应3-4h,采用二正丁胺法滴定体系中游离的-NCO含量,当-NCO达到理论值时,升温至78-80℃,加入扩链剂反应2-3小时当NCO达到理论值后降温到60-65℃加入活性封端剂、阻聚剂、丙酮保温反应3小时,NCO达到理论值,反应停止,得到NCO半封端聚氨酯预聚物;
(3)侧链含氟硅水性聚氨酯乳液的制备:将计量侧链含氟硅预聚体、NCO半封端聚氨酯预聚物、催化剂、丙酮加入装有冷凝管、氮气导管、搅拌棒和温度计的四口烧瓶中,升温至60℃反应4h,当-NCO红外吸收峰完全消失时终止反应,将反应温度降至20-25℃,加入一定量的三乙胺,高速剪切30min,再加入去离子水,剪切乳化30min,减压旋蒸除去溶剂,即得侧链含氟水性聚氨酯乳液。
步骤(1)中所述含氟丙烯酸酯为甲基丙烯酸三氟乙酯、甲基丙烯酸六氟丁酯、丙烯酸六氟丁酯、甲基丙烯酸八氟戊酯、丙烯酸十二氟庚酯、甲基丙烯酸十二氟庚酯、甲基丙烯酸十三氟辛酯中的至少一种;
步骤(1)中所述有机硅丙烯酸酯为3-(三甲氧基甲硅烷基)丙基-2-甲基-2-丙烯酸酯、三异丙基硅烷基甲基丙烯酸酯中的至少一种;
步骤(1)中所述引发剂为偶氮二异丁腈、过氧化二苯甲酰中的至少一种;
步骤(2)和(3)中所述催化剂为二月桂酸二丁基锡、辛酸亚锡中的至少一种;
步骤(2)中所述阻聚剂为对苯二酚、对甲氧基苯酚中的至少一种;
步骤(2)中所述聚酯二元醇为聚碳酸酯二元醇、聚己内酯二元醇、己二酸聚酯二元醇中的至少一种;
步骤(2)中所述扩链剂为二羟甲基丙酸(DMPA)、二羟甲基丁酸(DMBA)中的至少一种;
步骤(3)中所述活性封端剂为丙烯酸羟乙酯(HEA)、甲基丙烯酸羟乙酯(HEMA)、丙烯酸羟丙酯(HPA)、甲基丙烯酸羟丙酯(HPMA)、季戊四醇三丙烯酸酯(PETA)中的至少一种。
本发明的有益效果是:通过以上反应,合成得到高耐水性侧链含氟-硅可UV固化水性聚氨酯树脂涂料用树脂。该树脂可用于提高涂料的耐水性、耐候性、防污性、耐热性,可广泛用于塑料、薄膜、门窗等具有耐水、耐候、防污要求的表面。
具体实施方式
实施例1
侧链含氟硅预聚体的制备:将1.5g甲基丙烯酸十二氟庚酯、2g 3-(三甲氧基甲硅烷基)丙基-2-甲基-2-丙烯酸酯、6.5g甲基丙烯酸羟乙酯、20ml N,N-二甲基甲酰胺和0.25g偶氮二异丁腈加入装有冷凝管、氮气导管、搅拌棒的100ml的三口烧瓶中,通入氮气保护,升温至80℃反应8小时,得到侧链含氟硅预聚体;
NCO半封端聚氨酯预聚物的制备:将10.08g HDI三聚体(HDT)、0.05g二月桂酸二丁基锡和15ml丙酮加入装有冷凝管、氮气导管、搅拌棒100ml三口烧瓶中,升温至55℃滴加12g日本旭化成的聚碳酸酯二醇,反应4h,采用二正丁胺法滴定体系中游离的-NCO含量,当-NCO达到理论值时,升温至80℃,加入1.34g二羟甲基丙酸(DMPA)反应3小时当NCO达到理论值后降温到60℃加入1.30g甲基丙烯酸羟乙酯(HEMA)、0.01g对甲氧基苯酚、5ml丙酮保温反应3小时,NCO达到理论值,反应停止,得到NCO半封端聚氨酯预聚物;
侧链含氟硅水性聚氨酯乳液的制备:将第一步合成的侧链含氟硅预聚体、第二步合成的NCO半封端聚氨酯预聚物、0.05g二月桂酸二丁基锡、10ml丙酮加入装有冷凝管、氮气导管、搅拌棒和温度计250ml四口烧瓶中,升温至60℃反应4h,当-NCO红外吸收峰完全消失时终止反应,将反应温度降至25℃,加入1.15g的三乙胺,转速800rpm高速剪切30min,再加入去55g离子水,转速1200rpm剪切乳化30min,减压旋蒸除去溶剂,即得侧链含氟硅水性聚氨酯乳液。
Claims (2)
1.一种高耐水性侧链含氟-硅UV固化水性聚氨酯树脂的制备方法,其特征步骤为:
(1)侧链含氟硅预聚体的制备:将计量含氟丙烯酸酯、有机硅丙烯酸酯、甲基丙烯酸羟乙酯、N,N-二甲基甲酰胺和引发剂加入装有冷凝管、氮气导管、搅拌棒和温度计的四口烧瓶中,通入氮气保护,升温至75-80℃反应7-8小时,得到侧链含氟硅预聚体;
(2)NCO半封端聚氨酯预聚物的制备:将计量HDI三聚体(HDT)、催化剂和丙酮加入装有冷凝管、氮气导管、搅拌棒和温度计的四口烧瓶中,升温至50-55℃滴加一定量的聚酯二元醇,反应3-4h,采用二正丁胺法滴定体系中游离的-NCO含量,当-NCO达到理论值时,升温至78-80℃,加入扩链剂反应2-3小时当NCO达到理论值后降温到60-65℃加入活性封端剂、阻聚剂、丙酮保温反应3小时,NCO达到理论值,反应停止,得到NCO半封端聚氨酯预聚物;
(3)侧链含氟硅水性聚氨酯乳液的制备:将计量侧链含氟硅预聚体、NCO半封端聚氨酯预聚物、催化剂、丙酮加入装有冷凝管、氮气导管、搅拌棒和温度计的四口烧瓶中,升温至60℃反应4h,当-NCO红外吸收峰完全消失时终止反应,将反应温度降至20-25℃,加入一定量的三乙胺,高速剪切30min,再加入去离子水,剪切乳化30min,减压旋蒸除去溶剂,即得侧链含氟水性聚氨酯乳液。
2.如权利要求1所述的一种高耐水性侧链含氟-硅UV固化水性聚氨酯树脂的制备方法,其特征在于:
步骤(1)中所述含氟丙烯酸酯为甲基丙烯酸三氟乙酯、甲基丙烯酸六氟丁酯、丙烯酸六氟丁酯、甲基丙烯酸八氟戊酯、丙烯酸十二氟庚酯、甲基丙烯酸十二氟庚酯、甲基丙烯酸十三氟辛酯中的至少一种;
步骤(1)中所述有机硅丙烯酸酯为3-(三甲氧基甲硅烷基)丙基-2-甲基-2-丙烯酸酯、三异丙基硅烷基甲基丙烯酸酯中的至少一种;
步骤(1)中所述引发剂为偶氮二异丁腈、过氧化二苯甲酰中的至少一种;
步骤(2)和(3)中所述催化剂为二月桂酸二丁基锡、辛酸亚锡中的至少一种;
步骤(2)中所述阻聚剂为对苯二酚、对甲氧基苯酚中的至少一种;
步骤(2)中所述聚酯二元醇为聚碳酸酯二元醇、聚己内酯二元醇、己二酸聚酯二元醇中的至少一种;
步骤(2)中所述扩链剂为二羟甲基丙酸(DMPA)、二羟甲基丁酸(DMBA)中的至少一种;
步骤(3)中所述活性封端剂为丙烯酸羟乙酯(HEA)、甲基丙烯酸羟乙酯(HEMA)、丙烯酸羟丙酯(HPA)、甲基丙烯酸羟丙酯(HPMA)、季戊四醇三丙烯酸酯(PETA)中的至少一种。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201711370251.9A CN108003320B (zh) | 2017-12-19 | 2017-12-19 | 一种高耐水性侧链含氟-硅uv固化水性聚氨酯树脂的制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201711370251.9A CN108003320B (zh) | 2017-12-19 | 2017-12-19 | 一种高耐水性侧链含氟-硅uv固化水性聚氨酯树脂的制备方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN108003320A true CN108003320A (zh) | 2018-05-08 |
CN108003320B CN108003320B (zh) | 2020-08-11 |
Family
ID=62059915
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201711370251.9A Expired - Fee Related CN108003320B (zh) | 2017-12-19 | 2017-12-19 | 一种高耐水性侧链含氟-硅uv固化水性聚氨酯树脂的制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN108003320B (zh) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109824849A (zh) * | 2019-02-19 | 2019-05-31 | 四川尤博瑞新材料有限公司 | 一种低氟硅水性聚氨酯乳液及其弹性薄膜制品 |
CN109851752A (zh) * | 2018-12-13 | 2019-06-07 | 江南大学 | 一种侧链氟硅改性可uv固化水性聚氨酯树脂的制备方法 |
CN111518255A (zh) * | 2020-04-01 | 2020-08-11 | 华东师范大学 | 一种透明疏水含硅氟聚氨酯涂层及其制备方法 |
CN112724768A (zh) * | 2019-10-14 | 2021-04-30 | 上海飞凯光电材料股份有限公司 | 封边材料、制备方法及其应用 |
CN115505096A (zh) * | 2022-09-26 | 2022-12-23 | 三晃树脂(佛山)有限公司 | 一种耐候能力强的聚氨酯及其制备方法 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20060235138A1 (en) * | 2005-04-19 | 2006-10-19 | Dpi Co., Ltd. | Method of preparing self-emulsified urethane aqueous dispersion and method of preparing core-shell emulsion resin composition using the same |
CN102875765A (zh) * | 2012-08-31 | 2013-01-16 | 江苏创基新材料有限公司 | 具有纳米微结构的有机硅氟低表面能防污涂层剂制备方法 |
CN103059706A (zh) * | 2012-12-31 | 2013-04-24 | 广东工业大学 | 一种高固体份光固化含氟聚氨酯-丙烯酸酯涂料(pfua)及其制备方法 |
CN103305112A (zh) * | 2013-06-27 | 2013-09-18 | 浙江大学 | 一种具有防覆冰功能的环保涂料及其制备方法 |
-
2017
- 2017-12-19 CN CN201711370251.9A patent/CN108003320B/zh not_active Expired - Fee Related
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20060235138A1 (en) * | 2005-04-19 | 2006-10-19 | Dpi Co., Ltd. | Method of preparing self-emulsified urethane aqueous dispersion and method of preparing core-shell emulsion resin composition using the same |
CN102875765A (zh) * | 2012-08-31 | 2013-01-16 | 江苏创基新材料有限公司 | 具有纳米微结构的有机硅氟低表面能防污涂层剂制备方法 |
CN103059706A (zh) * | 2012-12-31 | 2013-04-24 | 广东工业大学 | 一种高固体份光固化含氟聚氨酯-丙烯酸酯涂料(pfua)及其制备方法 |
CN103305112A (zh) * | 2013-06-27 | 2013-09-18 | 浙江大学 | 一种具有防覆冰功能的环保涂料及其制备方法 |
Non-Patent Citations (1)
Title |
---|
徐文总等: "含氟、硅丙烯酸酯改性水性聚氨酯乳液的制备与性能研究", 《化工新型材料》 * |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109851752A (zh) * | 2018-12-13 | 2019-06-07 | 江南大学 | 一种侧链氟硅改性可uv固化水性聚氨酯树脂的制备方法 |
CN109824849A (zh) * | 2019-02-19 | 2019-05-31 | 四川尤博瑞新材料有限公司 | 一种低氟硅水性聚氨酯乳液及其弹性薄膜制品 |
CN109824849B (zh) * | 2019-02-19 | 2021-05-11 | 四川尤博瑞新材料有限公司 | 一种低氟硅水性聚氨酯乳液及其弹性薄膜制品 |
CN112724768A (zh) * | 2019-10-14 | 2021-04-30 | 上海飞凯光电材料股份有限公司 | 封边材料、制备方法及其应用 |
CN111518255A (zh) * | 2020-04-01 | 2020-08-11 | 华东师范大学 | 一种透明疏水含硅氟聚氨酯涂层及其制备方法 |
CN111518255B (zh) * | 2020-04-01 | 2022-04-05 | 华东师范大学 | 一种透明疏水含硅氟聚氨酯涂层及其制备方法 |
CN115505096A (zh) * | 2022-09-26 | 2022-12-23 | 三晃树脂(佛山)有限公司 | 一种耐候能力强的聚氨酯及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
CN108003320B (zh) | 2020-08-11 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN108003320A (zh) | 一种高耐水性侧链含氟-硅uv固化水性聚氨酯树脂的制备方法 | |
CN105086916B (zh) | 一种高透光uv‑湿气双固化胶黏剂 | |
Zhang et al. | Synthesis and properties of UV-curable polyester-based waterborne polyurethane/functionalized silica composites and morphology of their nanostructured films | |
Kahraman et al. | The novel use of organo alkoxy silane for the synthesis of organic–inorganic hybrid coatings | |
CN108456290A (zh) | 一种双重固化聚氨酯丙烯酸酯树脂及其制备方法 | |
CN104448211A (zh) | 一种uv固化含氟超支化水性聚氨酯树脂的制备方法 | |
CN104448235A (zh) | 一种耐水、耐候可uv固化超支化水性聚氨酯树脂的制备方法 | |
JP6465316B2 (ja) | 硬化型組成物 | |
CN104558501A (zh) | 一种紫外线和湿气双重固化型改性聚氨酯及其制备方法 | |
CN107880235A (zh) | 一种高耐候性氟改性uv固化多臂型水性聚氨酯树脂的制备方法 | |
CN105440260B (zh) | 紫外光固化聚氨酯丙烯酸酯及其制备方法 | |
Zhang et al. | Synthesis and characterization of waterborne UV-curable polyurethane modified with side-chain triethoxysilane and colloidal silica | |
CN107880236A (zh) | 一种高性能可uv固化超支化水性含氟聚氨酯树脂的制备方法 | |
Mishra et al. | High-performance waterborne UV-curable polyurethane dispersion based on thiol–acrylate/thiol–epoxy hybrid networks | |
CN109851752A (zh) | 一种侧链氟硅改性可uv固化水性聚氨酯树脂的制备方法 | |
CN106632968A (zh) | 一种氟硅改性水性uv固化超支化刷状聚氨酯的制备方法 | |
CN109575222A (zh) | 一种氟-硫复合改性uv固化多臂型水性聚氨酯的制备方法 | |
Chen et al. | UV-curable PDMS-containing PU system for hydrophobic textile surface treatment | |
Liu et al. | Synthesis of fluorinated polycarbonate-based polyurethane acrylate for UV-curable coatings | |
Ali et al. | Bio‐based photo‐curable polyurethane composites | |
JP2013018848A (ja) | 活性エネルギー線硬化性組成物、及び塗装物品 | |
CN105542121B (zh) | 紫外光固化聚氨酯丙烯酸酯及其制备方法 | |
CN105399913B (zh) | 紫外光固化聚氨酯丙烯酸酯及其制备方法 | |
CN109666105A (zh) | 一种可uv固化水性聚氨酯高隔热涂料的制备方法 | |
Nebioglu et al. | Optimization of UV curable acrylated polyester-polyurethane/polysiloxane ceramer coatings using a response surface methodology |
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 | ||
GR01 | Patent grant | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20200811 |
|
CF01 | Termination of patent right due to non-payment of annual fee |