CN115433341A - Hydrophilic urethane acrylate, hydrophilic trifunctional acrylate, and preparation methods and applications thereof - Google Patents
Hydrophilic urethane acrylate, hydrophilic trifunctional acrylate, and preparation methods and applications thereof Download PDFInfo
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- CN115433341A CN115433341A CN202211094731.8A CN202211094731A CN115433341A CN 115433341 A CN115433341 A CN 115433341A CN 202211094731 A CN202211094731 A CN 202211094731A CN 115433341 A CN115433341 A CN 115433341A
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- acrylate
- catalyst
- polymerization inhibitor
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- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title claims abstract description 44
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 title claims description 9
- 238000002360 preparation method Methods 0.000 title abstract description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000011347 resin Substances 0.000 claims abstract description 20
- 229920005989 resin Polymers 0.000 claims abstract description 20
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 229920005906 polyester polyol Polymers 0.000 claims abstract description 17
- 239000004814 polyurethane Substances 0.000 claims abstract description 16
- 229920002635 polyurethane Polymers 0.000 claims abstract description 16
- 239000003112 inhibitor Substances 0.000 claims abstract description 14
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 14
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000000694 effects Effects 0.000 claims abstract description 11
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 9
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 9
- 239000012948 isocyanate Substances 0.000 claims abstract description 9
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 9
- 239000004970 Chain extender Substances 0.000 claims abstract description 7
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims abstract description 6
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims abstract description 6
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 6
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000000576 coating method Methods 0.000 claims description 34
- 239000011248 coating agent Substances 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 12
- 238000007599 discharging Methods 0.000 claims description 10
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 8
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 6
- CIICLJLSRUHUBY-UHFFFAOYSA-N 4-[(2-methylpropan-2-yl)oxy]phenol Chemical compound CC(C)(C)OC1=CC=C(O)C=C1 CIICLJLSRUHUBY-UHFFFAOYSA-N 0.000 claims description 5
- KCLIFOXATBWLMW-UHFFFAOYSA-M sodium;ethane-1,2-diamine;ethanesulfonate Chemical compound [Na+].NCCN.CCS([O-])(=O)=O KCLIFOXATBWLMW-UHFFFAOYSA-M 0.000 claims description 5
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-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
- 235000010354 butylated hydroxytoluene Nutrition 0.000 claims description 4
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- 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
- 150000003863 ammonium salts Chemical class 0.000 claims description 3
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 claims description 3
- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 3
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 3
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 150000004985 diamines Chemical class 0.000 claims description 2
- MLZPVQRJNQJFRY-UHFFFAOYSA-M sodium 2-[bis(2-hydroxyethyl)amino]propane-1-sulfonate Chemical compound OCCN(C(CS(=O)(=O)[O-])C)CCO.[Na+] MLZPVQRJNQJFRY-UHFFFAOYSA-M 0.000 claims description 2
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 150000002009 diols Chemical class 0.000 claims 1
- 238000002834 transmittance Methods 0.000 abstract description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000758 substrate Substances 0.000 abstract description 2
- -1 acrylic ester Chemical class 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 238000012544 monitoring process Methods 0.000 description 12
- 238000005070 sampling Methods 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 9
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 9
- 238000005303 weighing Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 238000001723 curing Methods 0.000 description 6
- 238000000016 photochemical curing Methods 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 150000002433 hydrophilic molecules Chemical class 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical group NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 238000007766 curtain coating Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 230000002045 lasting effect Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000002103 nanocoating Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- QGTHRCDTVFFPBQ-UHFFFAOYSA-N C(C(=C)C)(=O)OCCCO.[Na] Chemical compound C(C(=C)C)(=O)OCCCO.[Na] QGTHRCDTVFFPBQ-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- WBULSJOMJYJKQX-UHFFFAOYSA-N N.OCCN(C)CCO Chemical compound N.OCCN(C)CCO WBULSJOMJYJKQX-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- YXTFRJVQOWZDPP-UHFFFAOYSA-M sodium;3,5-dicarboxybenzenesulfonate Chemical compound [Na+].OC(=O)C1=CC(C(O)=O)=CC(S([O-])(=O)=O)=C1 YXTFRJVQOWZDPP-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 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
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5072—Polyethers having heteroatoms other than oxygen containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/26—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfonic acids
- C07C303/28—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfonic acids by reaction of hydroxy compounds with sulfonic acids or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/24—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran
-
- 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
-
- 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
- C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
-
- 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
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
-
- 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
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/775—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur sulfur
-
- 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
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses hydrophilic polyurethane acrylate, hydrophilic trifunctional acrylate, and a preparation method and application thereof, wherein the hydrophilic polyurethane acrylate comprises the following raw materials in parts by weight: 100-200 parts of sulfonate polyester polyol, 100-200 parts of acetone, 240-350 parts of isocyanate, 0.01-0.3 part of catalyst A, 3-15 parts of chain extender, 35-60 parts of hydroxyethyl (meth) acrylate and 0.3-0.6 part of polymerization inhibitor A; the hydrophilic trifunctional acrylate comprises the following raw materials in parts by weight: 200 parts of trimethylolpropane glycidyl ether, 70-180 parts of maleic anhydride and/or propane sultone, 0.5-2 parts of catalyst B, 0.3-0.6 part of polymerization inhibitor B, 0.5-2 parts of antioxidant and 175-220 parts of (methyl) acrylic acid. The UV-cured super-hydrophilic antifogging resin is prepared by taking self-made super-hydrophilic polyurethane acrylic acid and hydrophilic trifunctional acrylic ester as main raw materials; after the system is cured into a film, the excellent adhesion, hardness and light transmittance are ensured, and meanwhile, the system has excellent hydrophilicity and a good anti-fogging effect on a transparent substrate.
Description
Technical Field
The invention belongs to the field of ultraviolet light curing, and particularly relates to hydrophilic polyurethane acrylate, hydrophilic trifunctional acrylate, and preparation methods and applications thereof.
Background
The anti-fog method is mainly divided into an electrothermal method and a method using an anti-fog functional coating. The former has good effect, but the cost is high, and the cost is needed to consume extra energy, which is deviated from the current environmental protection trend. The antifogging functional coating is divided into a hydrophobic coating and a hydrophilic coating. The hydrophobic antifogging coating still stays in the concept stage, has high cost and complex process and is difficult to be applied to actual life. The research on hydrophilic antifogging coatings is very numerous and, in principle, includes two types: a surfactant method; and (3) coating hydrophilic molecules. Surfactant methods, which cannot provide a lasting antifog effect with the constant dissolution of the surfactant; the hydrophilic molecular coating realizes the spreading of surface condensed water by improving the surface energy of the hydrophilic molecular coating, enables water drops to be converted into a water film, provides a lasting antifogging effect, and is also concerned and researched.
Hydrophilic molecules can be generally classified into inorganic hydrophilic molecules, organic macromolecules and organic-inorganic hybrid hydrophilic molecules. Currently, in the field of antifogging functional coatings, most researches are conducted on hydrophilic high molecular polymers, and the polymers usually contain some hydrophilic groups.
CN106752857A discloses a preparation method of a dual-curing acrylate super-hydrophilic antifogging coating. According to the preparation method, acrylate monomers are used as main raw materials, a silane coupling agent, hydroxyethyl acrylate and a sulfonic acrylamide monomer are introduced by adopting free radical polymerization, and double bonds are introduced by adopting half-terminated polyurethane and hydroxyl in a main chain to react. Wherein the sulfonic acid group on the main chain can endow the coating film with good hydrophilicity; the silane coupling agent and the tetraethoxysilane can be hydrolyzed and cured to form a coating, and meanwhile, the non-condensed silicon hydroxyl can further improve the hydrophilicity of the coating and endow the coating with good antifogging performance; the introduction of double bonds enables photocuring of acrylates. The coating prepared by the technical scheme has good hydrophilicity and antifogging property, but the coating has low hardness.
Patent CN103881434B reports a preparation method of an antifogging coating composition, which uses photosensitive acrylate oligomer and nano SiO 2 Modified hydroxyethyl acrylate, butyl methacrylate, acrylamide and sodium hydroxypropyl methacrylate are used as main bodies, then a small amount of reactive diluent and various auxiliary agents of a photoinitiator are added, and the antifogging coating with excellent antifogging performance and mechanical performance is obtained through UV curing, but the coating has low crosslinking degree, poor water resistance and low light transmittance.
CN 114058199A reports a UV-cured super-hydrophilic antifogging coating and a preparation method and application thereof. The UV-cured super-hydrophilic antifogging coating takes commercially available UV resin oligomer, acrylic monomers, a surfactant and a modified two-dimensional nano material as main raw materials, and a cured coating has good hydrophilicity and mechanical properties, good water resistance and long-term antifogging property, but the surfactant is dissolved out in the using process.
Hydrophilic photocuring antifogging coatings have been reported, and the reported antifogging coatings have a certain antifogging effect but have defects, such as poor antifogging durability, low hardness of antifogging films, low light transmittance and the like. Among them, the surface with high surface energy formed by using hydrophilic polymers has two contradictory surfaces of hydrophilicity and hardness, which is the reason why many reports and researches on hydrophilic antifogging coatings cannot be carried out on market at present.
Disclosure of Invention
In order to solve the problems in the prior art, the hydrophilic polyurethane acrylate is prepared by adopting the sulfonate polyester polyol and the sulfonate modified diisocyanate, the hydrophilic trifunctional acrylate is prepared by adopting the trimethylolpropane glycidyl ether as a raw material, and the antifogging coating with good strength and antifogging effect can be prepared by adopting the hydrophilic polyurethane acrylate and the hydrophilic trifunctional acrylate as photocuring resins.
The invention provides a hydrophilic polyurethane acrylate, which comprises the following raw materials in parts by weight:
100-200 parts of sulfonate polyester polyol, 100-200 parts of acetone, 240-350 parts of isocyanate, 0.01-0.3 part of catalyst A, 3-15 parts of chain extender, 35-60 parts of hydroxyethyl (meth) acrylate and 0.3-0.6 part of polymerization inhibitor A.
Further, it is preferable that the sulfonate type polyester polyol has a molecular weight of 400 to 1000, and it is further preferable that sodium 5-sulfoisophthalate is prepared by condensing ethylene glycol, diethylene glycol or triethylene glycol.
Further, the isocyanate is preferably a sulfonate-modified isocyanate, and further preferably one or a combination of at least two of WHDI, WIPDI, and WTDI.
Further, the chain extender is selected from hydrophilic diamine or dihydric alcohol containing carboxyl, sulfonate and ammonium salt, and is further preferably one or more of dimethylolpropionic acid (DMPA), dimethylolbutyric acid (DMBA), ethylenediamine ethanesulfonic acid sodium salt (A95), N-methyldiethanolamine ammonium salt and N, N-bis (2-hydroxyethyl) -2-aminopropanesulfonic acid sodium salt.
Further, the catalyst a is preferably one or a combination of at least two of a high-activity bismuth-based catalyst, dibutyltin dilaurate and stannous octoate.
Further, the polymerization inhibitor A is preferably one of p-hydroxyanisole, p-diphenol, p-tert-butoxyphenol, 2, 6-di-tert-butyl-4-methylphenol, or a combination of at least two of them.
The second aspect of the present invention provides a method for preparing the hydrophilic urethane acrylate, comprising the steps of:
(1) Adding acetone into sulfonate polyester polyol, uniformly mixing, and then adding isocyanate and a catalyst A for reaction;
(2) Adding a chain extender for reaction;
(3) Adding hydroxyethyl (meth) acrylate and a polymerization inhibitor A for reaction, and discharging when the NCO% is less than 0.2%.
Further, in the step (1), the sulfonate polyester polyol is dehydrated before use until the water content is less than 500 ppm, and the dehydration process specifically comprises the steps of heating to 100-110 ℃ under stirring and heating conditions, starting a vacuum pump, and dehydrating for 2-3h.
Further, in the step (1), the reaction temperature is preferably 60-70 ℃, and the reaction time is preferably 2-3h.
Further, in the step (2), the reaction temperature is preferably 60-70 ℃, and the reaction time is preferably 4-5 h.
Further, in the step (3), the reaction temperature is preferably 60-70 ℃, and the reaction time is preferably 4-5 h.
The third aspect of the invention provides a hydrophilic trifunctional acrylate which comprises the following raw materials in parts by mass:
200 parts of trimethylolpropane glycidyl ether, 70-180 parts of maleic anhydride and/or propane sultone, 0.5-2 parts of catalyst B, 0.3-0.6 part of polymerization inhibitor B, 0.5-2 parts of antioxidant and 175-220 parts of (methyl) acrylic acid.
Further, it is preferable that the catalyst B is one of tetraethylammonium bromide, benzyltrimethylammonium chloride, tetrabutylammonium bromide or a combination of at least two thereof.
Further, it is preferable that the polymerization inhibitor B is one of p-hydroxyanisole, p-diphenol, p-tert-butoxyphenol, 2, 6-di-tert-butyl-4-methylphenol or a combination of at least two thereof.
Further, the antioxidant is preferably one or a combination of at least two of antioxidant 1010, antioxidant 626, antioxidant 168 and hypophosphorous acid.
The fourth aspect of the present invention provides a method for preparing the hydrophilic trifunctional acrylate, including the steps of:
(1) Taking trimethylolpropane glycidyl ether, adding a catalyst B, a polymerization inhibitor B and an antioxidant, adding (methyl) acrylic acid, and reacting until the acid value is less than 5mgKOH/g;
(2) Adding maleic anhydride and/or propane sultone, continuing to react, and discharging for later use after the acid value is qualified.
Further, the reaction temperature of the step (1) is preferably 90-110 ℃, and the reaction time is preferably 5-7h.
Further, the reaction temperature of the step (2) is preferably 110-120 ℃, and the reaction time is preferably 2-3h.
The fifth aspect of the invention provides an application of the hydrophilic polyurethane acrylate and the hydrophilic trifunctional acrylate in hydrophilic antifogging photocuring resin.
Further, the hydrophilic urethane acrylate and the hydrophilic trifunctional acrylate can be used as hydrophilic anti-fog photocuring resin to prepare a hydrophilic anti-fog photocuring coating together with a solvent, a photoinitiator and the like commonly used in the field, wherein the coating comprises the following raw materials in parts by mass:
25 parts of hydrophilic polyurethane acrylate, 5-8 parts of hydrophilic trifunctional acrylate, 30-80 parts of solvent and 0.6-1.3 parts of photoinitiator.
Further, the solvent is selected from one or a combination of at least two of methyl isobutyl ketone, butanone, acetone, ethyl acetate, cyclohexanone and toluene.
Further, the photoinitiator is selected from one or a combination of at least two of 1173, 184, TPO and 1700.
The preparation method of the hydrophilic antifogging photocureable coating can be as follows: uniformly mixing hydrophilic polyurethane acrylate, hydrophilic trifunctional acrylate, a solvent and a photoinitiator, curtain coating on a transparent PC board, drying the solvent, and forming a film through ultraviolet curing.
Compared with the prior art, the invention has the beneficial effects that: the technical scheme of the invention breakthroughs the preparation of the UV-cured super-hydrophilic antifogging resin by using self-made super-hydrophilic polyurethane acrylic acid and hydrophilic trifunctional acrylate as main raw materials; after the system is cured into a film, the excellent adhesion, hardness and light transmittance are ensured, and meanwhile, the system has excellent hydrophilicity and a good anti-fogging effect on a transparent substrate.
Detailed Description
The present invention is further described with reference to the following examples, which are not intended to limit the invention, and it should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Example 1
Weighing 100 g of sulfonate polyester polyol BY3306, adding the sulfonate polyester polyol BY3306 into a three-neck flask with a mechanical stirrer and a thermometer, heating and melting, controlling the temperature and dehydrating for 2-3h until the water content is less than 500 ppm, cooling, adding 100 g of acetone, uniformly mixing, then adding 350 g of WIPDI and 0.05 g of dibutyltin dilaurate, controlling the temperature and reacting for 2 h, sampling and monitoring NCO, adding 3.5 g of dimethylolpropionic acid (DMPA) after the NCO% reaches a theoretical value, continuing to react for 4-5 h, sampling and monitoring NCO, adding 53 g of hydroxyethyl methacrylate and 0.3 g of p-methoxyphenol after the NCO% reaches the theoretical value, continuing to react for 4-5 h, sampling and monitoring NCO, discharging when the NCO% is less than 0.2, and marking as resin 1;
weighing 200 g of glycidyl ether (with the epoxy value = 0.72), adding the glycidyl ether into a three-neck flask provided with a dropping funnel and a thermometer, then adding p-methoxyphenol (0.6 g), tetrabutylammonium bromide (1.7 g) and an aqueous hypophosphorous acid solution (1.2 g), uniformly mixing, dropwise adding acrylic acid (176.9 g), after completing dropwise adding within 30 min, controlling the temperature to be 90-110 ℃ for reaction for 5-7h and controlling the acid value to be less than 5mgKOH/g, adding maleic anhydride (140 g), controlling the temperature to be 110-120 ℃ for reaction for 2-3h, discharging for later use after the acid value is qualified, and naming the glycidyl ether as XSJ-1;
weighing 25 g of resin 1,5.6 g of XSJ-1, 50 g of methyl isobutyl ketone and 0.9 g of photoinitiator (1173), uniformly mixing, spraying on a transparent PC board, drying a solvent, and forming a film through ultraviolet curing.
Example 2
Urethane acrylate is resin 1 synthesized in example 1;
weighing 200 g of glycidyl ether (epoxy value = 0.72), adding the glycidyl ether into a three-neck flask provided with a dropping funnel and a thermometer, then adding p-tert-butoxyphenol (0.6 g), benzyltrimethylammonium chloride (1.7 g) and an aqueous solution of hypophosphorous acid (1.2 g), uniformly mixing, dropwise adding acrylic acid (176.9 g), after finishing dropwise adding within 30 min, controlling the temperature to be 90-110 ℃ for reaction for 5-7h and the acid value to be less than 5mgKOH/g, adding propane sultone (175 g), controlling the temperature to be 110-120 ℃ for reaction for 2-3h, discharging for later use after the acid value is qualified, and naming the glycidyl ether as XSJ-2;
weighing 25 g of resin 1,5.6 g of XSJ-2, 50 g of methyl isobutyl ketone and 0.9 g of photoinitiator (1173), uniformly mixing, curtain-coating on a transparent PC plate, drying a solvent, and forming a film through ultraviolet curing.
Example 3
Weighing 100 g of sulfonate polyester polyol BY3306, adding the sulfonate polyester polyol BY3306 into a three-neck flask with a mechanical stirrer and a thermometer, heating and melting, controlling the temperature and dehydrating for 2-3h until the water content is less than 500 ppm, cooling, adding 100 g of acetone, uniformly mixing, then adding 350 g of WIPDI and 0.05 g of stannous octoate, controlling the temperature and reacting for 2 h, sampling and monitoring NCO, adding 12.2 g of dimethylolpropionic acid (DMPA) after the NCO% reaches a theoretical value, continuing to react for 4-5 h, sampling and monitoring NCO, adding 36 g of hydroxyethyl acrylate and 0.3 g of p-2, 6-di-tert-butyl-4-methylphenol after the NCO% reaches the theoretical value, continuing to react for 4-5 h, sampling and monitoring the NCO, and discharging and marking as resin 2 when the NCO% is less than 0.2;
the trifunctional acrylate was XSJ-2 as synthesized in example 2;
25 g of resin 2,5.6 g of XSJ-2, 50 g of methyl isobutyl ketone and 0.9 g of photoinitiator (1173) are weighed, evenly mixed, sprayed and coated on a transparent PC board, and after a solvent is dried, the mixture is cured by ultraviolet light to form a film.
Example 4
Weighing 100 g of sulfonate polyester polyol BY3306, adding the sulfonate polyester polyol BY3306 into a three-neck flask with a mechanical stirrer and a thermometer, heating and melting, controlling the temperature and dehydrating for 2-3h until the water content is less than 500 ppm, cooling, adding 100 g of acetone, uniformly mixing, then adding 240 g of WHDI and 0.05 g of stannous octoate, controlling the temperature and reacting for 2 h, sampling and monitoring NCO, adding 7.7 g of dimethylolbutyric acid (DMBA) after the NCO% reaches a theoretical value, continuing to react for 4-5 h, sampling and monitoring NCO, adding 46.7 g of hydroxyethyl methacrylate and 0.4 g of p-methoxyphenol after the NCO% reaches the theoretical value, continuing to react for 4-5 h, sampling and monitoring NCO, and discharging and marking as resin 3 when the NCO% is less than 0.2;
the trifunctional acrylate was XSJ-2 as synthesized in example 2;
weighing 25 g of resin 3,5.6 g of XSJ-2, 50 g of methyl isobutyl ketone and 0.9 g of photoinitiator (1173), uniformly mixing, spraying on a transparent PC board, drying a solvent, and forming a film through ultraviolet curing.
Example 5
Weighing 100 g of sulfonate polyester polyol BY3306, adding the sulfonate polyester polyol BY3306 into a three-neck flask with a mechanical stirrer and a thermometer, heating and melting, controlling the temperature and dehydrating for 2-3h until the water content is less than 500 ppm, cooling, adding 100 g of acetone, uniformly mixing, then adding 350 g of WIPDI and 0.5 g of high-activity bismuth catalyst, controlling the temperature and reacting for 2 h, sampling and monitoring NCO, adding 6.8 g of ethylenediamine ethanesulfonic acid sodium salt (A95) after the NCO% reaches a theoretical value, continuing to react for 4-5 h, sampling and monitoring NCO, adding 35 g of hydroxyethyl methacrylate and 0.3 g of p-methoxyphenol after the NCO% reaches the theoretical value, continuing to react for 4-5 h, sampling and monitoring NCO, and marking as a resin 4 when the NCO% is less than 0.2, discharging;
the trifunctional acrylate was XSJ-2 as synthesized in example 2;
25 g of resin 4,5.6 g of XSJ-2, 50 g of methyl isobutyl ketone and 0.9 g of photoinitiator (1173) are weighed, evenly mixed, sprayed and coated on a transparent PC board, and after a solvent is dried, the mixture is cured by ultraviolet light to form a film.
Comparative example 1
30.6 g of resin 1, 50 g of methyl isobutyl ketone and 0.9 g of photoinitiator (1173) are weighed, evenly mixed, sprayed on a transparent PC plate, dried by a solvent and cured by ultraviolet light to form a film.
Comparative example 2
30.6 g of XSJ-2, 50 g of methyl isobutyl ketone and 0.9 g of photoinitiator (1173) are weighed, evenly mixed, sprayed and coated on a transparent PC plate, dried by solvent and solidified into a film by ultraviolet light.
Comparative example 3
25 g of resin 1,5.6 g of TMPTA (trimethylolpropane triacrylate), 50 g of methyl isobutyl ketone and 0.9 g of photoinitiator (1173) are weighed, evenly mixed, sprayed and coated on a transparent PC plate, and after a solvent is dried, the mixture is cured by ultraviolet light to form a film.
The hardness, hydrophilicity, adhesion, light transmittance and antifogging property of the examples and comparative examples were tested as follows:
hardness: measuring the coating hardness according to the national standard GB/T6739-2006, and using a film coating pencil scratch hardness tester (QHQ type);
testing the hydrophilic anti-fog coating by adopting an SDC-100S contact angle measuring instrument, and observing the hydrophilic effect of the anti-fog coating under different experimental conditions;
adhesion force: the adhesion of the coating is measured according to the national Standard method GB/T9286-1998, using a paint film ruling instrument (QFH type);
light transmittance: testing the cured coating using a light transmittance haze meter;
the antifogging time is tested by a self-made device, and the specific method comprises the following steps: and (3) placing the glass sheet above a constant-temperature water bath, heating the water to 100 ℃, wherein the distance between the glass sheet and the water surface is 5 cm, and if the glass sheet does not fog in 5 min, determining that the glass sheet is qualified.
The specific test results are as follows:
| numbering | Hardness of pencil | Contact angle/degree of water | Adhesion force | Light transmittance | Antifogging time/min |
| Example 1 | 4H | 8.3 | 0 | 96% | Qualified |
| Example 2 | 4H | 7.1 | 0 | 96% | Qualified |
| Example 3 | 4H | 9.8 | 0 | 96% | Qualified |
| Example 4 | 4H | 7.3 | 0 | 96% | Qualified |
| Example 5 | 4H | 6.1 | 0 | 96% | Qualified |
| Comparative example 1 | 2H | 2.9 | 0 | 96% | Qualified |
| Comparative example 2 | 6H | 20 | 0 | 96% | Fail to be qualified |
| Comparative example 3 | 4 H | 34 | 1 | 96% | Fail to be qualified |
The test data show that the hydrophilic urethane acrylate and the trifunctional acrylate are compounded, so that the cured film has good hydrophilicity, high hardness, good antifogging property and good application value.
Claims (10)
1. The hydrophilic polyurethane acrylate comprises the following raw materials in parts by weight:
100-200 parts of sulfonate polyester polyol, 100-200 parts of acetone, 240-350 parts of isocyanate, 0.01-0.3 part of catalyst A, 3-15 parts of chain extender, 35-60 parts of hydroxyethyl (meth) acrylate and 0.3-0.6 part of polymerization inhibitor A.
2. The hydrophilic urethane acrylate according to claim 1, wherein the molecular weight of the sulfonate type polyester polyol is preferably 400 to 1000, and more preferably the molecular weight is prepared by condensing 5-sodium isophthalate with ethylene glycol, diethylene glycol or triethylene glycol; preferably, the isocyanate is a sulfonate-modified isocyanate, and more preferably one or a combination of at least two of WHDI, WIPDI, and WTDI.
3. The hydrophilic polyurethane acrylate according to claim 1, wherein the chain extender is selected from the group consisting of hydrophilic diamines or diols containing carboxyl, sulfonate, ammonium salts, preferably one or more of dimethylolpropionic acid (DMPA), dimethylolbutyric acid (DMBA), sodium ethylenediamine ethanesulfonate (A95) N-methyldiethanol ammonium salt, and sodium N, N-bis (2-hydroxyethyl) -2-aminopropanesulfonate.
4. The hydrophilic urethane acrylate according to claim 1, wherein the preferred catalyst A is one or a combination of at least two of a high-activity bismuth-based catalyst, dibutyltin dilaurate and stannous octoate; preferably, polymerization inhibitor A is selected from one or a combination of at least two of p-hydroxyanisole, p-diphenol, p-tert-butoxyphenol and 2, 6-di-tert-butyl-4-methylphenol.
5. A process for preparing the hydrophilic urethane acrylates of any one of claims 1 to 4, comprising the steps of:
(1) Adding acetone into sulfonate polyester polyol, uniformly mixing, and then adding isocyanate and a catalyst A for reaction;
(2) Adding a chain extender for reaction;
(3) Adding hydroxyethyl (meth) acrylate and a polymerization inhibitor A for reaction, and discharging when the NCO% is less than 0.2%.
6. A hydrophilic trifunctional acrylate comprises the following raw materials in parts by weight:
200 parts of trimethylolpropane glycidyl ether, 70-180 parts of maleic anhydride and/or propane sultone, 0.5-2 parts of catalyst B, 0.3-0.6 part of polymerization inhibitor B, 0.5-2 parts of antioxidant and 175-220 parts of (methyl) acrylic acid.
7. The hydrophilic trifunctional acrylate according to claim 6, wherein the catalyst B is preferably one of tetraethylammonium bromide, benzyltrimethylammonium chloride, tetrabutylammonium bromide or a combination of at least two thereof; the polymerization inhibitor B is preferably one or the combination of at least two of p-hydroxyanisole, p-diphenol, p-tert-butoxyphenol and 2, 6-di-tert-butyl-4-methylphenol; preferably, the antioxidant is one or a combination of at least two of antioxidant 1010, antioxidant 626, antioxidant 168 and hypophosphorous acid.
8. A process for preparing the hydrophilic trifunctional acrylate of claim 6 or 7, comprising the steps of:
taking trimethylolpropane glycidyl ether, adding a catalyst B, a polymerization inhibitor B and an antioxidant, adding (methyl) acrylic acid, and reacting until the acid value is less than 5mgKOH/g;
adding maleic anhydride and/or propane sultone, continuing to react, and discharging for later use after the acid value is qualified.
9. Use of the hydrophilic urethane acrylate according to any one of claims 1 to 5 and the hydrophilic trifunctional acrylate according to any one of claims 6 to 8 in a hydrophilic antifogging photocurable resin.
10. The application of claim 9, wherein the hydrophilic anti-fog light-cured resin is used for preparing a coating, and the coating comprises the following raw materials in parts by mass:
25 parts of hydrophilic polyurethane acrylate, 5-8 parts of hydrophilic trifunctional acrylate, 30-80 parts of solvent and 0.6-1.3 parts of photoinitiator.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116004111A (en) * | 2023-02-07 | 2023-04-25 | 泉州师范学院 | Preparation method of bionic super-hydrophilic coating, coating and application thereof |
| CN116376424A (en) * | 2023-03-07 | 2023-07-04 | 广东希贵光固化材料有限公司 | UV anti-fog coating for solar cell light-transmitting sheet |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106752857A (en) * | 2016-11-28 | 2017-05-31 | 江南大学 | A kind of preparation method of the super hydrophilic antifogging coating of dual cure acrylate |
| CN107254250A (en) * | 2017-07-10 | 2017-10-17 | 湖南邦弗特新材料技术有限公司 | A kind of aqueous UV urethane acrylate dispersoids of high glaze and preparation method thereof |
| CN108503792A (en) * | 2018-03-22 | 2018-09-07 | 深圳市姿彩科技有限公司 | Aqueous polyurethane acrylate resin and preparation method |
| CN109320687A (en) * | 2018-09-28 | 2019-02-12 | 合众（佛山）化工有限公司 | A kind of anionic isocyanate trimer waterborne curing agent |
| CN111253547A (en) * | 2020-01-21 | 2020-06-09 | 武汉工程大学 | Sulfonate type ultraviolet-curing waterborne polyurethane and preparation method thereof |
| CN111423343A (en) * | 2020-03-20 | 2020-07-17 | 佛山市精信汇明科技有限公司 | Hydrophilic diisocyanate and preparation method and application thereof |
| US20210071031A1 (en) * | 2018-12-25 | 2021-03-11 | Hunan Sokan New Materials Co., Ltd. | An aqueous antifogging resin, aqueous antifogging coating composition and preparation method thereof |
| CN112794982A (en) * | 2021-01-18 | 2021-05-14 | 广东工业大学 | Polyurethane acrylate and preparation method and application thereof |
-
2022
- 2022-09-08 CN CN202211094731.8A patent/CN115433341B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106752857A (en) * | 2016-11-28 | 2017-05-31 | 江南大学 | A kind of preparation method of the super hydrophilic antifogging coating of dual cure acrylate |
| CN107254250A (en) * | 2017-07-10 | 2017-10-17 | 湖南邦弗特新材料技术有限公司 | A kind of aqueous UV urethane acrylate dispersoids of high glaze and preparation method thereof |
| CN108503792A (en) * | 2018-03-22 | 2018-09-07 | 深圳市姿彩科技有限公司 | Aqueous polyurethane acrylate resin and preparation method |
| CN109320687A (en) * | 2018-09-28 | 2019-02-12 | 合众（佛山）化工有限公司 | A kind of anionic isocyanate trimer waterborne curing agent |
| US20210071031A1 (en) * | 2018-12-25 | 2021-03-11 | Hunan Sokan New Materials Co., Ltd. | An aqueous antifogging resin, aqueous antifogging coating composition and preparation method thereof |
| CN111253547A (en) * | 2020-01-21 | 2020-06-09 | 武汉工程大学 | Sulfonate type ultraviolet-curing waterborne polyurethane and preparation method thereof |
| CN111423343A (en) * | 2020-03-20 | 2020-07-17 | 佛山市精信汇明科技有限公司 | Hydrophilic diisocyanate and preparation method and application thereof |
| CN112794982A (en) * | 2021-01-18 | 2021-05-14 | 广东工业大学 | Polyurethane acrylate and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 刘卫清: ""UV固化水性环氧丙締酸树脂合成及其乳化的研究"", 《中国优秀硕士学位论文全文数据库（工程科技Ⅰ辑）》, pages 018 - 53 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116004111A (en) * | 2023-02-07 | 2023-04-25 | 泉州师范学院 | Preparation method of bionic super-hydrophilic coating, coating and application thereof |
| CN116376424A (en) * | 2023-03-07 | 2023-07-04 | 广东希贵光固化材料有限公司 | UV anti-fog coating for solar cell light-transmitting sheet |
| CN116376424B (en) * | 2023-03-07 | 2024-01-26 | 广东希贵光固化材料有限公司 | UV anti-fog coating for solar cell light-transmitting sheet |
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|---|---|
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