CN116041709A - Preparation method and application of photo-curing phenyl fluorosilicone modified epoxy paint and coating - Google Patents
Preparation method and application of photo-curing phenyl fluorosilicone modified epoxy paint and coating Download PDFInfo
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- CN116041709A CN116041709A CN202310059910.6A CN202310059910A CN116041709A CN 116041709 A CN116041709 A CN 116041709A CN 202310059910 A CN202310059910 A CN 202310059910A CN 116041709 A CN116041709 A CN 116041709A
- Authority
- CN
- China
- Prior art keywords
- epoxy
- phenyl
- fluorosilicone
- oligomer
- siloxane
- Prior art date
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- Granted
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- 239000004593 Epoxy Substances 0.000 title claims abstract description 113
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 title claims abstract description 98
- 238000000576 coating method Methods 0.000 title claims abstract description 93
- 239000011248 coating agent Substances 0.000 title claims abstract description 88
- 238000000016 photochemical curing Methods 0.000 title claims abstract description 41
- 239000003973 paint Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000003822 epoxy resin Substances 0.000 claims abstract description 101
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 101
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910000077 silane Inorganic materials 0.000 claims abstract description 24
- NOKUWSXLHXMAOM-UHFFFAOYSA-N hydroxy(phenyl)silicon Chemical compound O[Si]C1=CC=CC=C1 NOKUWSXLHXMAOM-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000012952 cationic photoinitiator Substances 0.000 claims abstract description 20
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 19
- 239000003085 diluting agent Substances 0.000 claims abstract description 16
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002318 adhesion promoter Substances 0.000 claims abstract description 14
- 230000003373 anti-fouling effect Effects 0.000 claims abstract description 13
- 239000000758 substrate Substances 0.000 claims abstract description 13
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims abstract description 12
- PARWUHTVGZSQPD-UHFFFAOYSA-N phenylsilane Chemical compound [SiH3]C1=CC=CC=C1 PARWUHTVGZSQPD-UHFFFAOYSA-N 0.000 claims abstract description 7
- -1 3-glycidoxypropyl Chemical group 0.000 claims description 106
- 229920005989 resin Polymers 0.000 claims description 53
- 239000011347 resin Substances 0.000 claims description 53
- 239000007787 solid Substances 0.000 claims description 38
- 239000000203 mixture Substances 0.000 claims description 31
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 30
- 239000003054 catalyst Substances 0.000 claims description 25
- 125000003545 alkoxy group Chemical group 0.000 claims description 22
- 239000010703 silicon Substances 0.000 claims description 19
- 229910052710 silicon Inorganic materials 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 19
- 239000002904 solvent Substances 0.000 claims description 17
- 125000003700 epoxy group Chemical group 0.000 claims description 16
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 238000001723 curing Methods 0.000 claims description 14
- 230000007062 hydrolysis Effects 0.000 claims description 14
- 238000006460 hydrolysis reaction Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000007865 diluting Methods 0.000 claims description 12
- 239000010702 perfluoropolyether Substances 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- 229910001868 water Inorganic materials 0.000 claims description 10
- 229920006334 epoxy coating Polymers 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 7
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 7
- 229920001451 polypropylene glycol Polymers 0.000 claims description 7
- 238000009835 boiling Methods 0.000 claims description 6
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical group [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 5
- 230000009471 action Effects 0.000 claims description 4
- 125000004122 cyclic group Chemical group 0.000 claims description 4
- 125000001033 ether group Chemical group 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 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
- 238000005260 corrosion Methods 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- KZMAWJRXKGLWGS-UHFFFAOYSA-N 2-chloro-n-[4-(4-methoxyphenyl)-1,3-thiazol-2-yl]-n-(3-methoxypropyl)acetamide Chemical compound S1C(N(C(=O)CCl)CCCOC)=NC(C=2C=CC(OC)=CC=2)=C1 KZMAWJRXKGLWGS-UHFFFAOYSA-N 0.000 claims description 2
- 230000000844 anti-bacterial effect Effects 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 230000000977 initiatory effect Effects 0.000 claims description 2
- 238000004806 packaging method and process Methods 0.000 claims description 2
- 238000007142 ring opening reaction Methods 0.000 claims description 2
- 238000007334 copolymerization reaction Methods 0.000 claims 2
- 125000006353 oxyethylene group Chemical group 0.000 claims 1
- 238000004382 potting Methods 0.000 claims 1
- 239000012974 tin catalyst Substances 0.000 claims 1
- 230000032683 aging Effects 0.000 abstract description 10
- 150000003839 salts Chemical class 0.000 abstract description 9
- 239000000853 adhesive Substances 0.000 abstract description 8
- 230000001070 adhesive effect Effects 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 6
- 229910008051 Si-OH Inorganic materials 0.000 abstract 1
- 229910006358 Si—OH Inorganic materials 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 38
- 239000004721 Polyphenylene oxide Substances 0.000 description 16
- 229920000570 polyether Polymers 0.000 description 16
- 239000012046 mixed solvent Substances 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- 238000005507 spraying Methods 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 10
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 239000012224 working solution Substances 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 238000010992 reflux Methods 0.000 description 9
- 239000007921 spray Substances 0.000 description 8
- 239000011521 glass Substances 0.000 description 7
- 239000005871 repellent Substances 0.000 description 7
- 239000007983 Tris buffer Substances 0.000 description 6
- 239000012530 fluid Substances 0.000 description 6
- 239000005028 tinplate Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- SPVOIFZJQGFWGU-UHFFFAOYSA-N fluoro(phenyl)silicon Chemical compound F[Si]C1=CC=CC=C1 SPVOIFZJQGFWGU-UHFFFAOYSA-N 0.000 description 5
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 5
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 5
- DBKIEXOOUXQPGC-UHFFFAOYSA-N 2-[2-(trifluoromethyl)phenyl]ethanol Chemical compound OCCC1=CC=CC=C1C(F)(F)F DBKIEXOOUXQPGC-UHFFFAOYSA-N 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- PKTOVQRKCNPVKY-UHFFFAOYSA-N dimethoxy(methyl)silicon Chemical compound CO[Si](C)OC PKTOVQRKCNPVKY-UHFFFAOYSA-N 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 125000002524 organometallic group Chemical group 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000005538 encapsulation Methods 0.000 description 3
- DRRZZMBHJXLZRS-UHFFFAOYSA-N n-[3-[dimethoxy(methyl)silyl]propyl]cyclohexanamine Chemical compound CO[Si](C)(OC)CCCNC1CCCCC1 DRRZZMBHJXLZRS-UHFFFAOYSA-N 0.000 description 3
- 238000005191 phase separation Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- MMZYCBHLNZVROM-UHFFFAOYSA-N 1-fluoro-2-methylbenzene Chemical compound CC1=CC=CC=C1F MMZYCBHLNZVROM-UHFFFAOYSA-N 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 2
- XQBCVRSTVUHIGH-UHFFFAOYSA-L [dodecanoyloxy(dioctyl)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCCCCCC)(CCCCCCCC)OC(=O)CCCCCCCCCCC XQBCVRSTVUHIGH-UHFFFAOYSA-L 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- GAURFLBIDLSLQU-UHFFFAOYSA-N diethoxy(methyl)silicon Chemical compound CCO[Si](C)OCC GAURFLBIDLSLQU-UHFFFAOYSA-N 0.000 description 2
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- QTECILHCKMCIFT-UHFFFAOYSA-N ethyl-(2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-heptadecafluorononoxy)-dimethoxysilane Chemical compound CC[Si](OC)(OC)OCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F QTECILHCKMCIFT-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 239000005543 nano-size silicon particle Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 2
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- QALDFNLNVLQDSP-UHFFFAOYSA-N triethoxy-(2,3,4,5,6-pentafluorophenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=C(F)C(F)=C(F)C(F)=C1F QALDFNLNVLQDSP-UHFFFAOYSA-N 0.000 description 2
- JLGNHOJUQFHYEZ-UHFFFAOYSA-N trimethoxy(3,3,3-trifluoropropyl)silane Chemical compound CO[Si](OC)(OC)CCC(F)(F)F JLGNHOJUQFHYEZ-UHFFFAOYSA-N 0.000 description 2
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 2
- UHUUYVZLXJHWDV-UHFFFAOYSA-N trimethyl(methylsilyloxy)silane Chemical compound C[SiH2]O[Si](C)(C)C UHUUYVZLXJHWDV-UHFFFAOYSA-N 0.000 description 2
- BBSJGZAOMVKHHF-UHFFFAOYSA-N trimethyl-[methyl-[2-(7-oxabicyclo[4.1.0]heptan-3-yl)ethyl]silyl]oxysilane Chemical compound C[SiH](CCC1CCC2OC2C1)O[Si](C)(C)C BBSJGZAOMVKHHF-UHFFFAOYSA-N 0.000 description 2
- FODCFYIWOJIZQL-UHFFFAOYSA-N 1-methylsulfanyl-3,5-bis(trifluoromethyl)benzene Chemical compound CSC1=CC(C(F)(F)F)=CC(C(F)(F)F)=C1 FODCFYIWOJIZQL-UHFFFAOYSA-N 0.000 description 1
- VSIKJPJINIDELZ-UHFFFAOYSA-N 2,2,4,4,6,6,8,8-octakis-phenyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound O1[Si](C=2C=CC=CC=2)(C=2C=CC=CC=2)O[Si](C=2C=CC=CC=2)(C=2C=CC=CC=2)O[Si](C=2C=CC=CC=2)(C=2C=CC=CC=2)O[Si]1(C=1C=CC=CC=1)C1=CC=CC=C1 VSIKJPJINIDELZ-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- TVBHYYFJOKDTPF-UHFFFAOYSA-N 3-(1,1,1,2,3,3,3-heptafluoropropan-2-yloxy)propyl-trimethoxysilane Chemical compound CO[Si](OC)(OC)CCCOC(F)(C(F)(F)F)C(F)(F)F TVBHYYFJOKDTPF-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910014033 C-OH Inorganic materials 0.000 description 1
- 229910014570 C—OH Inorganic materials 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910018540 Si C Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- RHQDFWAXVIIEBN-UHFFFAOYSA-N Trifluoroethanol Chemical compound OCC(F)(F)F RHQDFWAXVIIEBN-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000005410 aryl sulfonium group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 239000004842 bisphenol F epoxy resin Substances 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- ZZNQQQWFKKTOSD-UHFFFAOYSA-N diethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OCC)(OCC)C1=CC=CC=C1 ZZNQQQWFKKTOSD-UHFFFAOYSA-N 0.000 description 1
- LCKPYBMEBRESRM-UHFFFAOYSA-N diethoxy-ethyl-(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecan-2-yloxy)silane Chemical compound FC(C(C(C(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)C(C)O[Si](OCC)(OCC)CC LCKPYBMEBRESRM-UHFFFAOYSA-N 0.000 description 1
- VJYNTADJZPKUAF-UHFFFAOYSA-N diethoxy-methyl-(3,3,3-trifluoropropyl)silane Chemical compound CCO[Si](C)(OCC)CCC(F)(F)F VJYNTADJZPKUAF-UHFFFAOYSA-N 0.000 description 1
- UJTGYJODGVUOGO-UHFFFAOYSA-N diethoxy-methyl-propylsilane Chemical compound CCC[Si](C)(OCC)OCC UJTGYJODGVUOGO-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- DIJRHOZMLZRNLM-UHFFFAOYSA-N dimethoxy-methyl-(3,3,3-trifluoropropyl)silane Chemical compound CO[Si](C)(OC)CCC(F)(F)F DIJRHOZMLZRNLM-UHFFFAOYSA-N 0.000 description 1
- HURAXYIBQPNMKB-UHFFFAOYSA-N dimethoxy-methyl-(oxiran-2-ylmethoxy)silane Chemical compound CO[Si](C)(OC)OCC1CO1 HURAXYIBQPNMKB-UHFFFAOYSA-N 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- VBZWSGALLODQNC-UHFFFAOYSA-N hexafluoroacetone Chemical compound FC(F)(F)C(=O)C(F)(F)F VBZWSGALLODQNC-UHFFFAOYSA-N 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- NYMPGSQKHIOWIO-UHFFFAOYSA-N hydroxy(diphenyl)silicon Chemical class C=1C=CC=CC=1[Si](O)C1=CC=CC=C1 NYMPGSQKHIOWIO-UHFFFAOYSA-N 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229940089951 perfluorooctyl triethoxysilane Drugs 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 239000012994 photoredox catalyst Substances 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- RSNQKPMXXVDJFG-UHFFFAOYSA-N tetrasiloxane Chemical compound [SiH3]O[SiH2]O[SiH2]O[SiH3] RSNQKPMXXVDJFG-UHFFFAOYSA-N 0.000 description 1
- 125000005409 triarylsulfonium group Chemical group 0.000 description 1
- ZLGWXNBXAXOQBG-UHFFFAOYSA-N triethoxy(3,3,3-trifluoropropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCC(F)(F)F ZLGWXNBXAXOQBG-UHFFFAOYSA-N 0.000 description 1
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 description 1
- 125000000725 trifluoropropyl group Chemical group [H]C([H])(*)C([H])([H])C(F)(F)F 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- XFFHTZIRHGKTBQ-UHFFFAOYSA-N trimethoxy-(2,3,4,5,6-pentafluorophenyl)silane Chemical compound CO[Si](OC)(OC)C1=C(F)C(F)=C(F)C(F)=C1F XFFHTZIRHGKTBQ-UHFFFAOYSA-N 0.000 description 1
- XFVUECRWXACELC-UHFFFAOYSA-N trimethyl oxiran-2-ylmethyl silicate Chemical compound CO[Si](OC)(OC)OCC1CO1 XFVUECRWXACELC-UHFFFAOYSA-N 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
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- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
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- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
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- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
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- 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
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/10—Block or graft copolymers containing polysiloxane sequences
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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Abstract
The invention discloses a preparation method and application of a photo-curing phenyl fluorosilicone modified epoxy paint and a coating. The coating consists of 65-95 parts of epoxy phenyl fluorosilicone oligomer-g-epoxy resin, 5-30 parts of 2-4 functional epoxy oligosiloxane reactive diluent, 0-5 parts of adhesion promoter, 0-50% of nano silica sol based on the total mass of the materials and 1-6% of cationic photoinitiator; wherein, the epoxy phenyl fluorosilicone oligomer-g-epoxy resin is prepared by preparing an epoxy phenyl fluorosilicone oligomer intermediate containing Si-OH in the structure by the polycondensation reaction of epoxy silane, fluorocarbon silane and phenyl silane/phenyl siloxane oligomer, and then bonding the oligomer intermediate with the epoxy resin. The coating is coated on the surface of a substrate, and the prepared photo-curing coating is good in salt fog resistance and adhesive force, waterproof, antifouling, ageing resistance and impact resistance after being irradiated by ultraviolet light.
Description
Technical Field
The invention belongs to the field of functional resin, paint and coating, and relates to a preparation method and application of ultraviolet light curing paint and coating containing epoxy phenyl fluorosilicone oligomer chemical grafting modified (-g-) epoxy resin and epoxy oligosiloxane reactive diluent.
Background
The epoxy resin has good adhesive force, strong adhesion, chemical corrosion resistance and good electrical insulation, so the epoxy resin has wide application in the aspects of circuit board encapsulation, electronic component encapsulation, insulation, corrosion resistance, moisture resistance, functional coating preparation and the like. However, coatings prepared based on conventional epoxy resins are hard and brittle, and poor in weather and ageing resistance and impact resistance; the performances of weather resistance, ageing resistance, flexibility and the like of the epoxy resin coating which is physically or chemically modified by the organic silicon can be improved, but the waterproof and antifouling performances of the organic silicon modified epoxy resin coating are not ideal under the influence of the organic silicon structure and the surface energy.
The modification of epoxy resins with polyorganosiloxanes, silicones has been one of the focus of research in the fields of functional resins, coatings and coatings in the literature, see CN104293267, CN103173175, CN109851759, CN106349460, j.mat.sci., materials in Electronics,2017,28 (19): 14522-14535, etc.; however, chemical modification of epoxy resins with fluorosilicone resins having higher water and oil repellency has been recently reported because of the great difference in structure and solubility parameters between the two resins, which tends to result in the incompatibility of the two resins and the extremely easy occurrence of phase separation and delamination.
It is well known that introducing water-repellent and oil-repellent fluorocarbon groups into the structure of silicone resin helps to improve the water-repellent and anti-fouling properties and anti-aging effects of the silicone resin; if phenyl groups are further introduced into the structure, it is expected to improve the miscibility of the fluorosilicone resin with aromatic epoxy resins such as bisphenol A epoxy resin, bisphenol F epoxy resin, and the like. However, the coating formed by the fluorosilicone resin has poor adhesive force, and the epoxy resin is easy to cause the modified resin to be sticky, so that a large amount of solvent is required to dilute the coating in use, and the advantages of the epoxy resin in the aspects of improving the coating adhesion and adhesive force and the like are further weakened.
Disclosure of Invention
The invention provides a photo-curing phenyl fluorosilicone modified epoxy paint, a preparation method and application of the coating, and aims to solve the defect that fluorosilicone resin and epoxy resin are not mutually soluble and improve the performances of waterproof, antifouling and the like of a modified epoxy resin coating.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the photo-curing phenyl fluorosilicone modified epoxy paint consists of a resin component, a silica sol component accounting for 0-50% of the resin component in mass and a cationic photoinitiator accounting for 1-6% of the resin component in mass, wherein the resin component consists of 65-95 parts of photo-curing phenyl fluorosilicone modified epoxy resin, 5-30 parts of 2-4 functional epoxy oligosiloxane reactive diluent (ESi) and 0-5 parts of epoxy Adhesion Promoter (AP) by mass; the silica sol component is nano silica sol or modified nano silica sol; the main component of the photo-curing phenyl fluorosilicone modified epoxy resin is epoxy phenyl fluorosilicone oligomer-g-ring Oxygen resin (PF/ER), PF/ER is a copolymer of (epoxysiloxane-co-fluorocarbon-based siloxane-co-phenyl siloxane) -g-epoxy resin containing D, T units in the structure, or a copolymer of (epoxysiloxane-co-fluorocarbon-based siloxane-co-phenyl siloxane oligomer) -g-epoxy resin containing D, T units in the structure; in PF/ER, the epoxy group is 2, 3-glycidoxypropyl, 3, 4-cyclohexylethyl or (2, 3-glycidoxypolyoxypropylene ether propyl (wherein the polyoxyethylene polyoxypropylene ether group is- (C) 2 H 4 O) a (C 3 H 6 O) b -, wherein a=0 to 6, b=3 to 6, and a+b=3 to 6), and the fluorocarbon group is C 1 ～C 8 One of perfluoroalkyl group, perfluoroaryl group or perfluoropolyether group, etc., the phenyl siloxane oligomer is D, T phenyl siloxane oligomer or phenyl siloxane-co-alkyl siloxane copolymer oligomer, and alkyl group contained in the phenyl siloxane-co-alkyl siloxane copolymer oligomer is-CH 3 ～-C 18 H 37 。
Preferably, the preparation of the photo-curing phenyl fluorosilicone modified epoxy resin comprises the following steps:
(1) precursor-Synthesis of epoxy phenyl fluorosilicone oligomer (EPFS) containing silicon hydroxyl groups in the Structure
Uniformly stirring and mixing 10-25 parts by mass of epoxy silane, 10-45 parts by mass of fluorocarbon silane and 30-80 parts by mass of phenylsilane or phenylsiloxane oligomer to obtain a mixture A; uniformly stirring and mixing the mixture A with 100-300% of organic solvent by mass of the mixture A, 1-2% of hydrolysis catalyst by mass of the mixture A and water with the same molar quantity as alkoxy in silane contained in the mixture A, heating to 60-80 ℃ for hydrolysis polycondensation reaction for 1-3 h to obtain epoxy phenyl fluorosilicone oligomer solution containing silicon hydroxyl in the structure for later use;
(2) Synthesis of epoxy phenyl fluorosilicone oligomer-g-epoxy resin (PF/ER)
Taking an EPFS solution (the solid content is 20-50wt%), adding a metering polycondensation reaction organic metal catalyst and Epoxy Resin (ER), heating to 80-120 ℃ under stirring to perform polycondensation reaction for 1-3 h, wherein the polycondensation reaction organic metal catalyst accounts for 0.5-2% of the mass of the EPFS contained in the EPFS solution, the mass ratio of the EPFS contained in the EPFS solution to the Epoxy Resin (ER) is 1:9-2:1, evaporating the solvent after the reaction is finished, removing low-boiling-point substances, and obtaining semitransparent-transparent viscous liquid, namely epoxy phenyl fluorosilicone oligomer-g-epoxy resin, which is named as PF/ER;
(3) And (3) dissolving and diluting the epoxy phenyl fluorosilicone oligomer-g-epoxy resin with an organic solvent until the solid content is 50-80 wt% for later use.
Preferably, the epoxy silane is silane containing one epoxy group and 2-3 alkoxy groups in the molecule, the alkoxy groups are methoxy or ethoxy, and the epoxy group is one of 2, 3-glycidoxypropyl, 3, 4-cyclohexylethyl or (2, 3-glycidoxypolyoxypolyoxypropylene ether propyl; the epoxysilane is specifically selected from (3, 4-epoxycyclohexyl) ethyl trialkoxysilane [ e.g., (3, 4-epoxycyclohexyl) ethyl trimethoxysilane, (3, 4-epoxycyclohexyl) ethyl triethoxysilane ] ](2, 3-glycidoxypropyl) methyldialkoxysilane [ e.g., (2, 3-glycidoxypropyl) methyldimethoxysilane, (2, 3-glycidoxypropyl) methyldiethoxysilane ]](2, 3-glycidoxypropyl) trialkoxysilane [ e.g., (2, 3-glycidoxypropyl) trimethoxysilane, (2, 3-glycidoxypropyl) triethoxysilane](2, 3-epoxypropoxy) polyoxyethylene polyoxypropylene ether propyl trialkoxysilane [ such as (2, 3-epoxypropoxy) polyoxyethylene polyoxypropylene ether propyl trimethoxysilane, (2, 3-epoxypropoxy) polyoxyethylene polyoxypropylene ether propyl triethoxysilane ]](2, 3-epoxypropoxy) polyoxyethylene polyoxypropylene ether propyl methyl dialkoxysilane [ such as (2, 3-epoxypropoxy) polyoxyethylene polyoxypropylene ether propyl methyl dimethoxy silane, (2, 3-epoxypropoxy) polyoxyethylene polyoxypropylene ether propyl methyl diethoxy silane)]The structure of the polyoxyethylene polyoxypropylene ether group contained in the (2, 3-glycidoxy) polyoxyethylene polyoxypropylene ether propyl group in the (2, 3-glycidoxy) polyoxyethylene polyoxypropylene ether propyl trialkoxysilane or the (2, 3-glycidoxy) polyoxyethylene polyoxypropylene ether propyl methyl dialkoxysilane is- (C) 2 H 4 O) a (C 3 H 6 O) b In the formula, a=0 to 6, b=3 to 6, and a+b=3 to 6.
Preferably, the fluorocarbon silane contains C in the molecule 1 ～C 8 Perfluoroalkyl (e.g. 3-heptafluoroisopropyl propyl, C 1 ～C 8 A perfluoroalkylethyl) ethyl group, a perfluoroaryl group (e.g., pentafluorophenyl) or a perfluoropolyether group, and containing 2 to 3 alkoxy groups, which are methoxy or ethoxy groups; the fluorocarbon silane is specifically selected from heptadecafluorooctyl ethyl trialkoxysilane [ such as heptadecafluorooctyl ethyl trimethoxysilane (also known as 1H, 2H-perfluorodecyl trimethoxysilane), heptadecafluorooctyl ethyl triethoxysilane (also known as 1H, 2H-perfluorodecyl triethoxysilane)]Tridecyl ethyl trialkoxysilane [ e.g. tridecyl ethyl trimethoxysilane (also known as 1H, 2H-perfluorooctyl trimethoxysilane), tridecyl ethyl triethoxysilane (also known as 1H, 2H-perfluorooctyl triethoxysilane)]Nine-fluoro-butyl ethyl trialkoxysilane [ e.g., nine-fluoro-butyl ethyl trimethoxysilane (also known as 1H, 2H-perfluorohexyl trimethoxysilane), nine-fluoro-butyl ethyl triethoxysilane (also known as 1H, 2H-perfluorohexyl triethoxysilane)]3-heptafluoroisopropoxypropyl trialkoxysilane (such as 3-heptafluoroisopropoxypropyl trimethoxysilane, 3-heptafluoroisopropoxypropyl triethoxysilane), trifluoropropyl trialkoxysilane (such as trifluoropropyl trimethoxysilane, trifluoropropyl triethoxysilane), trifluoropropyl methyl dialkoxysilane (such as trifluoropropyl methyl dimethoxy silane, trifluoropropyl methyl diethoxy silane), pentafluorophenyl trialkoxysilane (such as pentafluorophenyl trimethoxysilane, pentafluorophenyl triethoxysilane), perfluoropolyether-based trialkoxysilane (such as perfluoropolyether trimethoxysilane having an average molecular weight of Mn=1000 to 3000, mn=1000 to 3000 perfluoropolyether triethoxysilane), perfluoropolyether-based methyl dialkoxysilane, and the like, or a mixture of 2 to 3 thereof.
Preferably, the phenylsilane is silane containing 1-2 phenyl groups and 2-3 alkoxy groups in the molecule, and the alkoxy groups are methoxy or ethoxy; the phenylsilane is specifically selected from one of phenyltrialkoxysilane (such as phenyltrimethoxysilane and phenyltriethoxysilane) or diphenyldialkoxysilane (such as diphenyldimethoxy silane and diphenyldiethoxy silane), or a mixture of one of diphenyldialkoxysilane and one of phenyltrialkoxysilane in any proportion.
Preferably, the phenyl siloxane oligomer (phenyl siloxane self oligomer or phenyl siloxane-co-alkyl siloxane copolymer oligomer) has a selected polymerization degree<10. Siloxane oligomer which contains silicon hydroxyl or silicon alkoxy in the molecule and D, T phenyl siloxane chain or phenyl siloxane oligomer chain and has a linear, cyclic, dendritic or semi-closed cage structure; the phenyl siloxane oligomer is specifically selected from one of semi-closed cage phenyl heptapolysiloxane trisilyl alcohol, cyclic 1,3,5, 7-tetramethyl-1, 3,5, 7-tetraphenyl cyclotetrasiloxane, cyclic octaphenyl cyclotetrasiloxane, hydroxyl or alkoxy end-capped polydiphenyl siloxane, hydroxyl or alkoxy end-capped diphenylsiloxane-co-phenyl siloxane, hydroxyl or alkoxy end-capped diphenylsiloxane-co-dialkyl siloxane, hydroxyl or alkoxy end-capped diphenylsiloxane-co-alkyl siloxane, hydroxyl or alkoxy end-capped phenylsiloxane-co-dialkyl siloxane and the like, the alkoxy is methoxy or ethoxy, and the alkyl is-CH 3 ～-C 18 H 37 。
Preferably, in the preparation step of the photo-curing phenyl fluorosilicone modified epoxy resin, the organic solvent is one or a mixture of more solvents of alcohols, fluoroalcohols, alcohol ethers, ketones, alcohol ether esters, aromatic hydrocarbons, fluoroaromatics and the like which have good intersolubility to fluorocarbon silane, phenylsilane, epoxysilane and the like, such as Ethanol (EA), acetone, toluene (MB), fluorotoluene (FT), benzotrifluoride (TFT), xylene, trifluoroethanol, hexafluoroacetone, butanone, cyclohexanone, methyl isobutyl ketone (MIBK), ethyl acetate (EAc), butyl Acetate (BA), ethylene glycol methyl ether, propylene glycol methyl ether, ethylene glycol methyl ether acetate, propylene glycol methyl ether acetate (PMA) and the like.
Preferably, the organic solvent is a mixed solvent such as arene-alcohol, fluoroarene-alcohol, arene-ester, fluoroarene-ester, arene-ether ester, fluoroarene-ether ester, arene-alcohol-ether ester, fluoroarene-alcohol-ether ester, and the like, such as one of fluorotoluene-ethanol, fluorotoluene-butyl acetate, benzotrifluoride-ethanol-butyl acetate, butyl acetate-pentafluoropentanol, PMA-propylene glycol methyl ether, fluorotoluene-ethyl acetate, and the like.
Preferably, the hydrolysis catalyst is one of inorganic acid (such as concentrated hydrochloric acid), organic acid (such as citric acid, glacial acetic acid), etc.
Preferably, the organometallic catalyst for polycondensation reaction is an organotin catalyst, an organobismuth catalyst or an organozinc catalyst; the organic metal catalyst for the polycondensation reaction is specifically selected from one of dioctyltin dilaurate, dibutyl tin diacetate, bismuth diisooctoate, zinc diisooctoate and the like.
Preferably, the Epoxy Resin (ER) is one of epoxy resins containing C-hydroxyl groups in the structure of bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin and the like, the epoxy value (the mole number of epoxy groups contained in 100g of resin) is 0.2-0.59, and the viscosity is about 1000-20000 mPa.s.
Preferably, the 2-4 functional epoxy oligosiloxane reactive diluent is a mixture of one or two of linear or cyclic siloxane oligomers with 2-4 epoxy groups and polymerization degree of 2-4 in the molecule [ structures shown as formulas (A) - (E) ]:
R＝CH 3 or C 2 H 5 X=0 to 3, y=0 to 6 and x+y=3 to 9
The polyoxyethylene polyoxypropylene ether group contained in the 2-4 functional epoxy oligosiloxane reactive diluent has the structure of- (C) 2 H 4 O) x (C 3 H 6 O) y Wherein x and y may be the same or different from a and b, x=0 to 3, y=0 to 6 and x+y=3 to 9, and may be directly ordered from the manufacturer or synthesized by hydrosilylation And (3) forming the finished product.
Preferably, the 2-4 functional epoxy oligosiloxane reactive diluent is specifically selected from the group consisting of α, ω -bis (2, 3-glycidoxypropyl) tetramethyldisiloxane, α, ω -bis [ (2, 3-glycidoxypropyl) polyoxypropylene ether propyl ] tetramethyldisiloxane, α, ω -bis (3, 4-epoxycyclohexylethyl) tetramethyldisiloxane, 1-trialkoxysilyleth-3, 5, 7-tris (2, 3-glycidoxypropyl) -1,3,5, 7-tetramethylcyclotetrasiloxane [ such as 1-trimethoxysilyleth-3, 5, 7-tris (2, 3-glycidoxypropyl) -1,3,5, 7-tetramethylcyclotetrasiloxane, 1-triethoxysilylethyl-3, 5, 7-tris (2, 3-glycidoxypropyl) -1,3,5, 7-trimethylcyclotetrasiloxane ], 1-trialkoxysilylethyl-3, 5, 7-tris [ (3, 3-glycidoxypropyl) poly (1, 3-glycidoxypropyl) -1,3,5, 7-tetramethylcyclotetrasiloxane [ such as 1-trimethoxysilylethyl-3, 5, 7-tris (2, 3-glycidoxypropyl) tetramethyl-1, 3,5, 7-tetramethylcyclotetrasiloxane ], 1-triethoxysilylpropyl ] -1, 5, 7-tris (2, 3, 7-epoxypropyl) polyoxyethylsiloxane, 1, 7-trimethylcyclopropylethyl) tetrasiloxane 1, 3-bis (trialkoxysilylethyl) -5, 7-bis (2, 3-epoxypropoxypropyl) -1,3,5, 7-tetramethylcyclotetrasiloxane [ e.g., 1, 3-bis (trimethoxysilylethyl) -5, 7-bis (2, 3-epoxypropoxypropyl) -1,3,5, 7-tetramethylcyclotetrasiloxane, 1, 3-bis (triethoxysilylethyl) -5, 7-bis (2, 3-epoxypropoxypropyl) -1,3,5, 7-tetramethylcyclotetrasiloxane ] and 1, 5-bis (trialkoxysilylethyl) -3, 7-bis (2, 3-epoxypropoxypropyl) -1,3,5, 7-tetramethylcyclotetrasiloxane [ e.g., 1, 5-bis (trimethoxysilylethyl) -3, 7-bis (2, 3-epoxypropoxypropyl) -1,3,5, 7-tetramethylcyclotetrasiloxane mixtures of 1, 5-bis (triethoxysilylethyl) -3, 7-bis (2, 3-epoxypropoxypropyl) -1,3,5, 7-tetramethylcyclotetrasiloxane ], mixtures of 1, 3-bis (trialkoxysilylethyl) -5, 7-bis (3, 4-epoxycyclohexylethyl) -1,3,5, 7-tetramethylcyclotetrasiloxane with 1, 5-bis (trialkoxysilylethyl) -3, 7-bis (3, 4-epoxycyclohexylethyl) -1,3,5, 7-tetramethylcyclotetrasiloxane, wherein the alkoxy groups are methoxy or ethoxy, 1,3,5, 7-tetrakis (2, 3-epoxypropoxypropyl) -1,3,5, 7-tetramethylcyclotetrasiloxane, 1,3,5, 7-tetra (3, 4-epoxycyclohexylethyl) -1,3,5, 7-tetramethyl cyclotetrasiloxane, 1,3,5, 7-tetra [ (2, 3-epoxypropoxy) polyoxyethylene polyoxypropylene ether propyl ] -1,3,5, 7-tetramethyl cyclotetrasiloxane, and the like.
Preferably, the epoxy Adhesion Promoter (AP) is a substance which contains an epoxy group and a siloxy group, and can participate in a photo-curing reaction of a resin or a paint and can increase adhesion between a substrate and an organic coating formed by the photo-curing reaction; the epoxy adhesion promoter is specifically selected from (2, 3-epoxypropoxy) methyldialkoxysilane [ such as (2, 3-epoxypropoxy) methyldimethoxysilane, (2, 3-epoxypropoxy) methyldiethoxysilane ], (2, 3-epoxypropoxy) trialkoxysilane [ such as (2, 3-epoxypropoxy) trimethoxysilane, (2, 3-epoxypropoxy) triethoxysilane ], mn=300-600 (2, 3-epoxypropoxy polyoxypropylene ether propyl) methyldialkoxysilane [ such as (2, 3-epoxypropoxy polyoxypropylene ether propyl) methyldimethoxysilane of Mn=300-600 ], (2, 3-epoxypropoxy) polyether propylmethyldialkoxysilane of Mn=300-600 [ such as (2, 3-epoxypropoxy) polyether propylmethyldimethoxysilane of Mn=300-600, (2, 3-epoxypropoxy) polyether propylmethyldiethoxysilane of Mn=300-600 ], polyether (2, 3-epoxypropoxy) polyether of Mn=300-600 [ such as polyether with Mn=300-3-epoxypropoxy ] polyether of the polyether (2, 3-epoxypropoxy) polyether of Mn=300-600, and the like, the polyether (3-epoxypropoxy polyether) of which the polyether has a polyoxyethylene structure of Mn=300-600 is represented by the following polyether (2, 3-epoxypropoxy) and the like, the polyether (3-epoxypropoxy) and the polyether (3-epoxypropoxy) has the polyether structure:
-(C 2 H 4 O) a1 (C 3 H 6 O) b1
Wherein a is 1 、b 1 A may be the same as or different from a, b, x, y 1 ＝0～3、b 1 =0 to 6 and a 1 +b 1 ＝0～6。
Preferably, the cationic photoinitiator is aryl sulfonium salt, onium salt and other substances capable of initiating epoxy group cationic ring-opening reaction under the ultraviolet irradiation condition (namely under the action of ultraviolet light); the cationic photoinitiator is specifically selected from one of cationic diphenyl- (4-phenylthio) phenylsulfonium hexafluoroantimonate (cationic photoinitiator 6976), 4-phenylthio) phenyldiphenylsulfonium hexafluorophosphate (cationic photoinitiator 6992), bis (4-tert-butylphenyl) iodonium hexafluorophosphate (cationic photoinitiator PI 9388), 4-isobutylphenyl-4' -methylphenyl iodohexafluorophosphate (cationic photoinitiator 250), triaryl sulfonium hexafluorophosphate (cationic photoinitiator 1176), η6-isopropylferrocene (II) hexafluorophosphate (cationic photoinitiator 261) and the like.
Preferably, the modified nanosilicon sol is nanosilicon (SiO 2 ) Silica sol prepared by modifying the sol with phenyl or perfluoroalkyl has a solid content of 20-35 wt%, an average particle size of 20-30 nm and a ph=6-7, and can be prepared by the method in literature (CN 106927690) or ordered from the manufacturer.
A preparation method of a photo-curing phenyl fluorosilicone modified epoxy coating comprises the following steps:
(1) Preparing a coating: stirring and dispersing the photo-curing phenyl fluorosilicone modified epoxy resin (namely diluted epoxy phenyl fluorosilicone oligomer-g-epoxy resin, wherein the solid content is 50-80 wt%), 2-4 functional epoxy oligosiloxane reactive diluent (ESi) and epoxy Adhesion Promoter (AP), and 0-50% of modified nano silica sol (or nano silica sol) and 1-6% of cationic photoinitiator by the total mass of the photo-curing phenyl fluorosilicone modified epoxy resin+ESi+AP for 20-30 min to obtain uniform fluid, namely photo-curing phenyl fluorosilicone modified epoxy paint (UVPF);
(2) And (3) preparing a coating: and (3) taking a clean substrate, diluting the photocuring UVPF coating with the solvent which is the same as the diluted epoxy phenyl fluorosilicone oligomer-g-epoxy resin to a solid content of 40-45 wt%, uniformly coating the substrate on the surface of the clean substrate, firstly leveling the substrate at 20-35 ℃ for 20-30 min, then pre-drying the substrate at 100-120 ℃ for 3-10 min, and then placing the substrate in an Ultraviolet (UV) curing machine for ultraviolet curing for 2-4 min to obtain the photocuring UVPF coating on the surface of the substrate.
Preferably, the substrate is selected from one of tin plate, aluminum alloy, steel plate, copper-clad circuit board, glass, ceramic, PC circuit board and the like; the coating mode is one of spraying, brushing, wire rod coating, spin coating, rolling coating and the like.
The application of the photo-curing phenyl fluorosilicone modified epoxy paint comprises the application of the paint in the fields of packaging and encapsulation of circuit boards and electronic components, preparation of metal antibacterial, anticorrosion and antifouling functional coatings and the like.
The beneficial effects of the invention are as follows:
according to the invention, through the designed and synthesized water-repellent oil-repellent epoxy phenyl fluorosilicone resin oligomer containing silicon hydroxyl (Si-OH) and the chemical bonding with epoxy resin, the epoxy phenyl fluorosilicone resin oligomer-g-epoxy resin (PF/ER) is obtained, the problem that the fluorosilicone resin and the epoxy resin are not easy to dissolve in each other is solved, and the experimental result shows that the waterproof and antifouling effects, ageing resistance, impact resistance and other performances of the epoxy coating modified by taking the epoxy resin as a resin component can be effectively improved, the surface of the coating is smooth, and the purpose of prolonging the service life of the functional coating is further achieved.
The invention takes 2-4 functional epoxy oligosiloxane (ESi) as a reactive diluent of PF/ER resin, and is compounded with a silica sol hardening component, a cationic photoinitiator and the like to prepare the photo-curing resin coating, and the coating can be rapidly cured into a desired coating under the action of ultraviolet irradiation, and the coating has excellent waterproof, antifouling and anticorrosion (relating to salt fog resistance and alkali resistance) performance and good adhesive force and impact resistance performance.
Furthermore, the epoxy phenyl fluorosilicone resin oligomer is chemically condensed with the epoxy resin containing C-OH in the structure, the obtained epoxy phenyl fluorosilicone resin oligomer-g-epoxy resin (PF/ER) has the dual functions of fluorosilicone resin and epoxy resin (not only can provide the special water and oil repellency of the modified resin coating by the fluorosilicone resin, but also can enable the target coating to have good adhesion and adhesive force of the epoxy resin), thereby not only fundamentally solving the problems of immiscibility, easy layering and the like of the physically blended fluorosilicone resin and the epoxy resin, but also facilitating the use of newly developed viscous resin.
Detailed Description
The present invention is described in further detail below with reference to examples, which are only for the purpose of illustrating the present invention, but are not to be construed as limiting the scope of the present invention.
In order to overcome the defects of poor intersolubility and easy phase separation of fluorosilicone resin and epoxy resin, the epoxy phenyl fluorosilicone resin oligomer containing silicon hydroxyl in the structure is synthesized by hydrolysis and polycondensation of epoxy silane and fluorocarbon silane, phenyl silane or phenyl siloxane oligomer, and then the epoxy phenyl fluorosilicone resin oligomer is grafted and chemically bonded with the epoxy resin, so that epoxy phenyl fluorosilicone oligomer-g-epoxy resin (PF/ER), namely oligomeric (epoxy siloxane-co-fluorocarbon siloxane-co-phenyl siloxane/phenyl siloxane oligomer) -g-epoxy resin, is prepared, has the dual functions of the fluorosilicone resin and the epoxy resin, and can effectively realize compatibility and homogeneous phase in a system; then PF/ER resin is used as a water-repellent oil-repellent film-forming component, and the resin is combined with 2-4 functional epoxy oligosiloxane reactive diluents, cationic photoinitiators and the like to prepare the photo-curing coating, under the action of ultraviolet light, the coating not only can realize rapid photo-curing (due to homogeneous phase), but also utilizes the advantages of large bond energy and good ultraviolet aging resistance of C-F bonds (bond energy 485 kJ/mol), si-O bonds (422.5 kJ/mol) and Si-C bonds (334.7 kJ/mol) in a fluorosilicone oligomeric resin structure, and the epoxy resin chain segment with strong adhesiveness is enriched towards the surface of the coating (enriched towards the interface of a substrate) by virtue of the surface orientation of the fluorosilicone chain segment with low surface energy in the resin, so that the fluorosilicone modified epoxy coating obtained after photo-curing has good adhesive force and also has excellent waterproof, antifouling, ageing resistance and salt fog resistance effects.
Example 1
(1) Synthesis of epoxy phenyl fluorosilicone oligomer EPFS-1 containing silicon hydroxyl group in the structure
10.0g of (2, 3-glycidoxypropyl) trimethoxysilane (KH 560), 10.0g of heptadecafluorooctyl ethyl trimethoxysilane, 80.0g of methoxy-terminated diphenylsiloxane (n) -co-hexadecylsiloxane (m) trimer (chain unit ratio n: m=2:1, mol/mol) were successively added to a three-necked flask equipped with a thermometer, reflux condenser and stirrer, and stirred and mixed to give a total of 100.0g of mixture A; then 100 percent (100.0 g) of mixed solvent of benzotrifluoride-ethanol (TFT: EA=1:1, w/w) and 1 percent (1.0 g) of hydrolysis catalyst (concentrated hydrochloric acid with the mass concentration of 36.5 percent) calculated by the mass of the mixture A are added, deionized water with the same molar quantity as alkoxy in silane is added dropwise under stirring, and then the temperature is raised to 80 ℃ for hydrolysis polycondensation reaction for 1h, thus obtaining transparent liquid, namely the epoxy phenyl fluorosilicone oligomer EPFS-1-2, 3-epoxypropoxypropyl siloxane-co-heptadecafluorooctyl ethyl siloxane-co- (diphenyl siloxane-co-hexadecyl siloxane) oligomer solution with the silicon hydroxyl in the structure, wherein the epoxy group content (the same applies based on the molar quantity of epoxy groups contained in 100g of resin) is about 0.0442, and the solid content is about 48.18 percent for standby.
(2) Synthesis of epoxy phenyl fluorosilicone oligomer-g-epoxy resin PF/ER-1
100.0g of EPFS-1 solution was put into a three-necked flask equipped with a thermometer, a reflux condenser and a stirrer, 1% (about 0.48 g) of dioctyl tin dilaurate as an organometallic catalyst and 24.09g of bisphenol A type epoxy resin E44 having an epoxy value of about 0.44 and a viscosity of about 16500 mPa.s were further added in accordance with the mass of EPFS-1 contained (about 48.18 g), the mixture was heated to 80℃under stirring to carry out polycondensation reaction for 3 hours, and after the reaction was completed, the solvent was distilled off and the reaction was carried out at 80℃and P was carried out Watch (watch) Decompression and low boiling under the pressure of 0.85MPa are carried out to obtain transparent viscous liquid, namely epoxy phenyl fluorosilicone oligomer-g-epoxy resin, (2, 3-glycidoxypropyl siloxane-co-heptadecafluorooctyl ethyl siloxane-co-diphenyl siloxane-co-hexadecyl siloxane oligomer) -g-epoxy resin is named PF/ER-1.
(3) The PF/ER-1 resin synthesized in step 2 was diluted with a mixed solvent of benzotrifluoride-ethyl acetate (TFT: EAc=1:2, w/w) to a solid content of about 50wt% for use.
(4) Preparation of photo-curing phenyl fluorosilicone modified epoxy paint UVPF-1
65.0g of PF/ER-1 resin with the solid content of about 50wt%, 30.0g of difunctional epoxy oligosiloxane reactive diluent alpha, omega-bis (3, 4-epoxycyclohexylethyl) tetramethyl disiloxane with the structure shown in the formula (A), 5.0g of adhesion promoter Mn=400, (2, 3-epoxypropoxypolyoxypropylene ether propyl) methyldimethoxy silane and a cationic photoinitiator 6976 with the mass of 1 percent (1.0 g) based on the total mass of the materials are stirred and dispersed for 30min to obtain uniform fluid, namely the photo-curing phenyl fluorosilicone modified epoxy paint with the solid content of about 67.82wt%, and the photo-curing phenyl fluorosilicone modified epoxy paint is marked as UVPF-1.
(5) Coating preparation
And (3) diluting the UVPF-1 coating with a mixed solvent of benzotrifluoride and ethyl acetate (1:2, W/W) until the solid content is about 40wt%, obtaining a UVPF-1 working solution, uniformly spraying the UVPF-1 working solution on the surface of clean tinplate or glass by using a spray gun with the caliber of about 0.8mm (the spraying amount is controlled so that the thickness of the dried coating is about 20 mu m), leveling for 30min at room temperature (about 25 ℃), baking for 3min at 100 ℃, and finally curing for 2min by using an ultraviolet curing machine with the power of 1000W, thus obtaining the coating sample of the UVPF-1.
Example 2
(1) Synthesis of epoxy phenyl fluorosilicone oligomer EPFS-2 containing silicon hydroxyl group in the structure
20.0g of (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 35.0g of pentafluorophenyl triethoxysilane and 45.0g of diphenyldimethoxysilane are sequentially added into a three-necked flask equipped with a thermometer, a reflux condenser and a stirrer, and stirred and mixed uniformly to obtain a total of 100.0g of mixture A; then adding 300% (300.0 g) of mixed solvent of benzotrifluoride-ethanol (1:1, w/w) and 1% (1.0 g) of hydrolysis catalyst (concentrated hydrochloric acid with the mass concentration of 36.5%) based on the mass of the mixture A, dropwise adding deionized water with the same molar quantity as alkoxy in silane under stirring, heating to 60 ℃ for hydrolysis polycondensation reaction for 3 hours to obtain transparent liquid, namely the solution of epoxy phenyl fluorosilicone oligomer EPFS-2-3, 4-cyclohexyl ethyl siloxane-co-pentafluorophenyl siloxane-co-diphenyl siloxane containing silicon hydroxyl in the structure, wherein the epoxy group content is about 0.1085, volatilizing part of the solvent, and then enabling the solid content to be increased to about 20.83 weight percent for later use.
(2) Synthesis of epoxy phenyl fluorosilicone oligomer-g-epoxy resin PF/ER-2
50.0g of EPFS-2 solution was charged into a three-necked flask equipped with a thermometer, reflux condenser and stirrer, and 2% (about 0.20 g) of bismuth diisooctoate, an organometallic catalyst, and 93.78g of a catalyst having an epoxy value of about 0.51, were further added in accordance with the mass of EPFS-2 contained (about 10.42 g),Bisphenol A type epoxy resin E51 with the viscosity of about 20000 mPas (the mass ratio of EPFS-2 to the epoxy resin E51 is controlled to be about 1:9), and then stirring and heating to 120 ℃ for polycondensation reaction for 1h; after the reaction, the solvent was distilled off, followed by reaction at P Watch (watch) The low boiling point is removed under reduced pressure under about 0.9MPa to obtain transparent viscous liquid, namely epoxy phenyl fluorosilicone oligomer-g-epoxy resin, (3, 4-cyclohexyl ethyl siloxane-co-pentafluorophenyl siloxane-co-diphenyl siloxane) -g-epoxy resin, which is named PF/ER-2.
(3) Diluting the PF/ER-2 resin synthesized in the step 2 with a mixed solvent of benzotrifluoride and ethyl acetate (1:2, w/w) until the solid content is about 60wt% for later use.
(4) Preparation of photo-curing phenyl fluorosilicone modified epoxy paint UVPF-2
95.0g of PF/ER-2 resin with the solid content of about 60wt%, 5.0g of trifunctional epoxy oligosiloxane reactive diluent 1-trimethoxy silicon ethyl-3, 5, 7-tri (2, 3-glycidoxypropyl) -1,3,5, 7-tetramethyl cyclo-tetrasiloxane with the solid content of 30wt% based on 50 percent of the total mass of the materials, 6 percent of cationic photoinitiator 6992 with the average particle size of about 20nm and 6 percent (6.0 g) are taken, stirred and dispersed for 20 minutes to obtain uniform fluid, namely the photo-curing phenyl fluorosilicon modified epoxy paint with the solid content of about 53.21wt%, and the photo-curing phenyl fluorosilicon modified epoxy paint is marked as UVPF-2.
(5) Coating preparation
And (3) diluting the UVPF-2 coating with a mixed solvent of benzotrifluoride and ethyl acetate (1:2, W/W) until the solid content is about 45wt%, obtaining UVPF-2 working solution, uniformly spraying the UVPF-2 working solution on the surface of clean tinplate or glass by using a spray gun with the caliber of about 0.8mm (the spraying amount is controlled so that the thickness of the dried coating is about 25 mu m), leveling for 30min at room temperature (about 25 ℃), drying for 10min at 100 ℃, and curing for 4min by using an ultraviolet curing machine with the power of 1000W, thus obtaining the coating sample of the UVPF-2.
Example 3
(1) Synthesis of epoxy phenyl fluorosilicone oligomer EPFS-3 containing silicon hydroxyl group in the structure
Into a three-necked flask equipped with a thermometer, reflux condenser and stirrer, 25 were sequentially added.0g a =0, b=3 2, 3-glycidoxypropyl polyoxypropylene ether propyl methyl dimethoxy silane, 45.0g fluorocarbon base silane mixture of perfluoropolyether trimethoxy silane (15.0 g) with trifluoropropyl trimethoxy silane (30.0 g) with mn=1500, 30.0g methoxy end-capped phenyl siloxane (n) 1 ) Dimethylsiloxane (m) 1 ) Tetramer (n) 1 :m 1 Chain link ratio=1:1, mol/mol), stirring and mixing well to obtain a total of 100.0g of mixture a; then adding 200% (200.0 g) of mixed solvent of benzotrifluoride-ethanol (2:1, w/w) and 1% (1.0 g) of hydrolysis catalyst (concentrated hydrochloric acid with the mass concentration of 36.5%) by mass of the mixture A, dropwise adding deionized water with the same molar quantity as alkoxy in silane under stirring, heating to 70 ℃ for hydrolysis polycondensation reaction for 2 hours to obtain transparent liquid, namely the epoxy phenyl fluorosilicon oligomer EPFS-3-2, 3-glycidoxypropyl polyoxypropylene ether propyl methyl siloxane-co-perfluoro polyether siloxane-co-trifluoropropyl siloxane-co- (phenyl siloxane-co-dimethyl siloxane) oligomer solution containing silicon hydroxyl groups in the structure, wherein the epoxy group content is about 0.0975, and volatilizing part of the solvent to ensure that the solid content is increased to about 50wt% for later use.
(2) Synthesis of epoxy phenyl fluorosilicone oligomer-g-epoxy resin PF/ER-3
Adding 100.0g of EPFS-3 solution into a three-necked flask with a thermometer, a reflux condenser and a stirrer, adding 1% (about 0.5 g) of organic metal catalyst dibutyltin diacetate and 50.0g of hydrogenated bisphenol A epoxy resin HE44 with an epoxy value of about 0.44 and a viscosity of about 4300 mPa.s (controlling the mass ratio of the EPFS-3 to the epoxy resin HE44 to be about 1:1) according to the mass (about 50.0 g) of the EPFS-3, stirring and heating to 100 ℃, and carrying out polycondensation reaction for 2 hours; after the reaction, the solvent was distilled off, followed by reaction at P Watch (watch) The low boiling point was removed under reduced pressure at about 0.85MPa to obtain a clear viscous liquid, namely epoxy phenyl fluorosilicone oligomer-g-epoxy resin, (2, 3-glycidoxypropyl polyoxypropylene ether propyl methyl siloxane-co-perfluoropolyether siloxane-co-trifluoropropyl siloxane-co-phenyl siloxane-co-dimethylsiloxane oligomer) -g-epoxy resin, designated PF/ER-3.
(3) Diluting the PF/ER-3 resin synthesized in the step 2 by using a mixed solvent of benzotrifluoride and ethyl acetate (1:1, w/w) until the solid content is about 60wt% for later use.
(4) Preparation of photo-curing phenyl fluorosilicone modified epoxy paint UVPF-3
84.0g of PF/ER-3 resin with the solid content of about 60wt%, 15.0g of tetrafunctional epoxy oligosiloxane reactive diluent 1,3,5, 7-tetra (2, 3-glycidoxypropyl) -1,3,5, 7-tetramethyl cyclotetrasiloxane with the structure shown in the formula (C), 1.0g of adhesion promoter KH-560, 30 percent (30.0 g) of phenyl modified nano silica sol with the solid content of 20wt% and the average grain diameter of about 30nm and 3 percent (3.0 g) of cationic photoinitiator 1176 based on the total mass of the materials, and stirring and dispersing for 25min to obtain uniform fluid, namely the photo-curing phenyl fluorosilicone modified epoxy paint with the solid content of about 56.69wt%, and is marked as UVPF-3.
(5) Coating preparation
And (3) diluting the UVPF-3 coating with a mixed solvent of benzotrifluoride and ethyl acetate (1:1, W/W) until the solid content is about 40wt%, obtaining UVPF-3 working solution, uniformly spraying the UVPF-3 working solution on the surface of clean tinplate or glass by using a spray gun with the caliber of about 0.8mm (the spraying amount is controlled so that the thickness of the dried coating is about 21.5 mu m), leveling for 30min at room temperature (about 25 ℃), drying for 5min at 100 ℃, and curing for 2min by using an ultraviolet curing machine with the power of 1000W, thus obtaining the coating sample of the UVPF-3.
Example 4
(1) Synthesis of epoxy phenyl fluorosilicone oligomer EPFS-4 containing silicon hydroxyl group in the structure
Into a three-necked flask equipped with a thermometer, reflux condenser and stirrer, 20.0g of (2, 3-glycidoxypropyl) methyldimethoxysilane (KH 781), 33.0g of tridecyl fluorohexylethyltrimethoxysilane and 47.0g of hydroxy-terminated phenylsiloxane (n) 2 ) -co-diethyl siloxane (m) 2 ) Dimer (mer ratio n) 2 :m 2 =1:1, mol/mol), stirring and mixing to obtain a total of 100.0g of mixture a; then 150% (150.0 g) of mixed benzotrifluoride-ethanol (1:1, w/w) solvent and 1% (1.0 g) of hydrolysis catalyst (36.5% by mass concentrated hydrochloric acid) were added thereto based on the mass of the mixture A, and the mixture was added dropwise with stirring to form an alkoxy group with silane And heating deionized water with equal molar weight to 75 ℃ for hydrolysis polycondensation reaction for 2.5 hours to obtain transparent liquid, namely the epoxy phenyl fluorosilicone oligomer EPFS-4-2, 3-glycidoxypropyl methyl siloxane-co-tridecyfluorohexyl ethyl siloxane-co- (phenyl siloxane-co-diethyl siloxane) oligomer solution containing silicon hydroxyl groups in the structure, wherein the epoxy group content is about 0.1001, and the solid content is increased to about 50wt% after part of solvent is volatilized for standby.
(2) Synthesis of epoxy phenyl fluorosilicone oligomer-g-epoxy resin PF/ER-4
Adding 90.0g of EPFS-4 solution into a three-necked flask provided with a thermometer, a reflux condenser and a stirrer, adding 1.45% (about 0.65 g) of organic metal catalyst zinc diisooctoate and 55.0g of bisphenol F type epoxy resin F170 with an epoxy value of about 0.59 and a viscosity of about 2500 mPas according to the mass (about 45.0 g) of the EPFS-4, stirring and heating to 100 ℃ for polycondensation reaction for 1.5h; after the reaction, the solvent was distilled off, followed by reaction at P Watch (watch) The mixture is decompressed and low boiling under the pressure of about 0.83MPa to obtain transparent viscous liquid, namely epoxy phenyl fluorosilicone oligomer-g-epoxy resin (2, 3-glycidoxypropyl methyl siloxane-co-tridecyfluorohexyl ethyl siloxane-co-phenyl siloxane-co-diethyl siloxane oligomer) -g-epoxy resin containing silicon hydroxyl in the structure is named as PF/ER-4.
(3) Diluting the PF/ER-4 resin synthesized in the step 2 with a mixed solvent of benzotrifluoride and ethyl acetate (1:2, w/w) until the solid content is about 80wt% for later use.
(4) Preparation of photo-curing phenyl fluorosilicone modified epoxy paint UVPF-4
78.5g of PF/ER-4 resin with a solid content of about 80wt%, 20.0g of trifunctional epoxy oligosiloxane reactive diluent with a structure shown as formulas (D) and (E), 1, 3-bis (trimethoxysilylethyl) -5, 7-bis (2, 3-glycidoxypropyl) -1,3,5, 7-tetramethyl cyclotetrasiloxane, a mixture of 1, 5-bis (trimethoxysilylethyl) -3, 7-bis (2, 3-glycidoxypropyl) -1,3,5, 7-tetramethyl cyclotetrasiloxane (the mass ratio of the two components in the mixture is about 1:1), 1.5g of adhesion promoter (2, 3-glycidoxypropyl) triethoxysilane, trideoxyethyl modified nano silica sol with a solid content of 25wt% and an average particle size of about 20nm and 3.8% (3.8 g) of cationic photoinitiator 6976 are taken, and dispersed for 25min to obtain a uniform fluid, namely, the photo-modified epoxy phenyl epoxy resin with a solid content of about 68 wt% as the UVLF-4.
(5) Coating preparation
And (3) diluting the UVPF-4 coating with a mixed solvent of benzotrifluoride and ethyl acetate (1:2, W/W) until the solid content is about 40wt%, obtaining UVPF-4 working solution, uniformly spraying the UVPF-4 working solution on the surface of clean tinplate or glass by using a spray gun with the caliber of about 0.8mm (the spraying amount is controlled so that the thickness of the dried coating is about 22.5 mu m), leveling for 20min at room temperature (about 25 ℃), drying for 6min at 100 ℃, and curing for 2min by using an ultraviolet curing machine with the power of 1000W, thus obtaining the coating sample of the UVPF-4.
Example 5
(1) Synthesis of epoxy phenyl fluorosilicone oligomer-g-epoxy resin PF/ER-5
100.0g of the EPFS-2 solution prepared in example 2 (solid content: about 20.83wt%, epoxy group content: about 0.1085) was charged into a three-necked flask equipped with a thermometer, reflux condenser and stirrer, 2% (about 0.42 g) of dibutyltin dilaurate as an organometallic catalyst and 31.26g of bisphenol A type epoxy resin E20 having an epoxy value of about 0.20 were further added in terms of mass (about 20.83 g) of EPFS-2 contained therein (the mass ratio of EPFS-2 to epoxy resin E20 was controlled: about 2:3), and then heated to 110℃with stirring to conduct polycondensation for 2.5 hours; after the reaction, the solvent was distilled off, followed by reaction at P Watch (watch) The low boiling point is removed under reduced pressure under about 0.9MPa to obtain transparent viscous liquid, namely epoxy phenyl fluorosilicone oligomer-g-epoxy resin, (3, 4-cyclohexyl ethyl siloxane-co-pentafluorophenyl siloxane-co-diphenyl siloxane) -g-epoxy resin, which is named PF/ER-5.
(2) Diluting the PF/ER-5 resin synthesized in the step 1 with a mixed solvent of benzotrifluoride and ethyl acetate (1:2, w/w) until the solid content is about 60wt% for later use.
(3) Preparation of photo-curing phenyl fluorosilicone modified epoxy paint UVPF-5
88.0g of PF/ER-5 resin with a solid content of about 60wt%, 10.0g of trifunctional epoxy oligosiloxane reactive diluent 1-trimethoxy silicon ethyl-3, 5, 7-tri (2, 3-glycidoxypropyl) -1,3,5, 7-tetramethyl cyclo-tetrasiloxane with a solid content of about 60wt%, 2.0g of adhesion promoter (2, 3-glycidoxypropyl) trimethoxy silane with a solid content of about 30wt% based on the total mass of the materials (35.0 g) and an average particle diameter of about 20nm, and 4.5g of cationic photoinitiator 6992 with a solid content of about 57.20wt% of the photo-cured phenyl fluorosilicon modified epoxy paint were taken, and stirred and dispersed for 20min to obtain a uniform fluid, namely the photo-cured phenyl fluorosilicon modified epoxy paint, which is named UVPF-5.
(4) Coating preparation
And (3) diluting the UVPF-5 coating with a mixed solvent of benzotrifluoride and ethyl acetate (1:2, W/W) until the solid content is about 43wt%, obtaining a UVPF-5 working solution, uniformly spraying the UVPF-5 working solution on the surface of clean tinplate or glass by using a spray gun with the caliber of about 0.8mm (the spraying amount is controlled so that the thickness of the dried coating is about 20 mu m), leveling for 30min at room temperature (about 25 ℃), drying for 5min at 100 ℃, and curing for 2min by using an ultraviolet curing machine with the power of 1000W, thus obtaining the coating sample of the UVPF-5.
Example 6
A photocurable epoxy coating was formulated with 95.0g of an epoxy E51-ethyl acetate solution having a solids content of about 60% by weight, and the like, in place of 95.0g of the diluted PF/ER-2 resin used in example 2 (having a solids content of about 60% by weight), and was designated CB-1 and used as a reference for the photocurable phenyl fluorosilicone-modified epoxy coating formulated in the other examples. The preparation procedure of CB-1 coating and the preparation of the coating are described in example 2.
The photo-cured phenyl fluorosilicone modified epoxy coating (UVPF-1-5 coating) samples and CB-1 coating samples prepared in the above examples were equilibrated at room temperature (25.+ -. 2 ℃) and Relative Humidity (RH) of 48% for 24 hours, and then subjected to performance test:
Coating light transmittance (T%): using glass as a coating substrate, and measuring by using a Cary 5000 type ultraviolet-visible spectrophotometer;
ageing resistance of the coating (1000 h×85 ℃ C. ×RH 85%): with reference to GB/T2423.24-1995 standard, the test is carried out by using a KK-SN-150 xenon lamp aging resistance test box;
waterproof performance of the coating: with the static contact angle (theta) of the water drop on the surface of the coating H2O ) The water drop size was 5. Mu.L as measured with JC-2000C1 static contact angle measuring instrument at room temperature (25.+ -. 2 ℃); θ H2O The larger the coating surface, the better the water repellency;
salt spray resistance of the coating: referring to GB/T10125-1997 standard, 5wt% NaCl aqueous solution (simulated saline) is used as a test solution, the coating is sealed by wax-rosin, and the coating is measured by a YWX/Q-150 salt spray resistance tester;
coating adhesion: with reference to HGT3792-2014 standard, the electric adhesion tester is used for measurement, and the grade 0 is best;
impact resistance of the coating: with reference to GB/T1732-1993 standard, with an impact resistor;
coating flexibility: reference is made to the GB/T1731-1993 method, measured with a paint film elasticity tester;
coating hardness: reference to GB/T6739-93 method, measured with a pencil durometer of type QHQ-A;
antifouling properties of the coating: the fly ash is classified into 5 grades, preferably 0 grade, as measured by the method specified in GB/T9780-1988.
Alkali resistance of the coating: the coating is firstly edge-sealed by wax-rosin, then is soaked in 5 percent NaOH aqueous solution for standing for 186 hours, is taken out, and is observed whether the coating is foamed, wrinkled, fallen, discolored and the like.
The experimental test results are shown in table 1.
TABLE 1 comparison of Properties of photo-cured UVPF coatings
* -a coating sample; no change in the surface of the coating for 1000 hours at 85 ℃ x RH 85%; and & -no obvious change in the surface of the coating
Slave watch1, it can be seen that the coating UVPF-1-5 prepared by the embodiment of the invention has the surface theta H2O The salt fog resistance reaches 108.2-120.6 degrees, the salt fog resistance reaches 1000-1200H, the hardness reaches 2H-4H, the impact resistance reaches 55-80 cm, and the antifouling grade reaches 0-1 grade; compared with a reference CB-1 coating, the waterproof, antifouling and impact resistance of the surface of the coating are obviously improved, the salt spray resistance and the ageing resistance are enhanced, and the adhesion and the light transmittance are not greatly different; in addition, the UVPF-1-5 coating prepared by the embodiment of the invention is homogeneous, does not have layering or phase separation phenomenon, and has a smooth surface after photo-curing. The UVPF-1-5 coating prepared by the invention has good adhesive force, excellent waterproof, antifouling, anticorrosive, aging-resistant and impact-resistant properties, and the coating has excellent application effect as a whole.
Claims (10)
1. A photo-curing phenyl fluorosilicone modified epoxy resin is characterized in that: comprises epoxy phenyl fluorosilicone oligomer-g-epoxy resin, wherein the epoxy phenyl fluorosilicone oligomer-g-epoxy resin is a copolymer of (epoxy siloxane-co-fluorocarbon-base siloxane-co-phenyl siloxane) -g-epoxy resin or a copolymer of (epoxy siloxane-co-fluorocarbon-base siloxane-co-phenyl siloxane oligomer) -g-epoxy resin; in the epoxy phenyl fluorosilicone oligomer-g-epoxy resin, the epoxy group is one of 2, 3-glycidoxypropyl, 3, 4-cyclohexylethyl or (2, 3-glycidoxypolyoxypolyoxypropylene ether propyl, and the fluorocarbon group is C 1 ～C 8 One of perfluoroalkyl group, perfluoroaryl group and perfluoropolyether group, the phenyl siloxane oligomer is the oligomer of phenyl siloxane itself or the oligomer formed by copolymerization of phenyl siloxane-co-alkyl siloxane, and the alkyl group in the oligomer formed by copolymerization of phenyl siloxane-co-alkyl siloxane is-CH 3 ～-C 18 H 37 。
2. A photo-curing phenyl fluorosilicone modified epoxy paint is characterized in that: the coating consists of a resin component, a silica sol component accounting for 0-50% of the mass of the resin component and a cationic photoinitiator accounting for 1-6% of the mass of the resin component, wherein the resin component consists of 65-95 parts by mass of the photo-curing phenyl fluorosilicone modified epoxy resin as defined in claim 1, 5-30 parts by mass of 2-4 functional epoxy oligosiloxane reactive diluent and 0-5 parts by mass of adhesion promoter, and the silica sol component is nano silica sol or modified nano silica sol.
3. The photo-curable phenyl fluorosilicone modified epoxy paint of claim 2, wherein: the preparation method of the photo-curing phenyl fluorosilicone modified epoxy resin comprises the following steps:
1) Uniformly stirring and mixing 10-25 parts by mass of epoxy silane, 10-45 parts by mass of fluorocarbon silane and 30-80 parts by mass of phenylsilane or phenylsiloxane oligomer to obtain a mixture A; uniformly stirring and mixing the mixture A with 100-300% of solvent by mass of the mixture A, 1-2% of hydrolysis catalyst by mass of the mixture A and water with the same molar quantity as alkoxy in silane contained in the mixture A, heating to 60-80 ℃ for hydrolysis polycondensation reaction for 1-3 hours to obtain epoxy phenyl fluorosilicone oligomer solution;
2) Heating the epoxy phenyl fluorosilicone oligomer solution, an organic metal catalyst and epoxy resin to 80-120 ℃ under stirring, and carrying out polycondensation reaction for 1-3 h, wherein the organic metal catalyst accounts for 0.5-2% of the mass of the epoxy phenyl fluorosilicone oligomer contained in the epoxy phenyl fluorosilicone oligomer solution, the mass ratio of the epoxy phenyl fluorosilicone oligomer to the epoxy resin contained in the epoxy phenyl fluorosilicone oligomer solution is 1:9-2:1, and evaporating the solvent after the reaction is finished, removing low-boiling substances, thereby obtaining the epoxy phenyl fluorosilicone oligomer-g-epoxy resin;
3) And dissolving and diluting the epoxy phenyl fluorosilicone oligomer-g-epoxy resin with a solvent until the solid content is 50-80%.
4. A photo-curable phenyl fluorosilicone modified epoxy paint according to claim 3, characterized in that: the epoxy silane is silane containing one epoxy group and 2-3 alkoxy groups in the molecule, the alkoxy groups are methoxy or ethoxy, and the epoxy groups are 2, 3-glycidoxypropyl, 3, 4-cyclohexylethyl or (2, 3-glycidoxypoly)One of the oxyethylene polyoxypropylene ether propyl groups, wherein the polyoxyethylene polyoxypropylene ether group contained in the (2, 3-epoxypropoxy) polyoxyethylene polyoxypropylene ether propyl group has the structure of- (C) 2 H 4 O) a (C 3 H 6 O) b -wherein a = 0 to 6, b = 3 to 6 and a + b = 3 to 6; the fluorocarbon silane contains C in molecule 1 ～C 8 Perfluoroalkyl, perfluoroaryl or perfluoropolyether groups and containing 2 to 3 alkoxy groups, wherein the alkoxy groups are methoxy or ethoxy groups.
5. A photo-curable phenyl fluorosilicone modified epoxy paint according to claim 3, characterized in that: the phenyl siloxane oligomer is a siloxane oligomer with the polymerization degree of <10, containing silicon hydroxyl or silicon alkoxy in the molecule and containing phenyl siloxane chain units or phenyl siloxane oligomer chain units and having a linear, cyclic, dendritic or semi-closed cage structure.
6. A photo-curable phenyl fluorosilicone modified epoxy paint according to claim 3, characterized in that: the organic metal catalyst is an organic tin catalyst, an organic bismuth catalyst or an organic zinc catalyst; the epoxy resin is epoxy resin containing C-hydroxyl in the structure, the epoxy value is 0.2-0.59, and the viscosity is 1000-20000 mPa.s.
7. The photo-curable phenyl fluorosilicone modified epoxy paint of claim 2, wherein: the 2-4 functional epoxy oligosiloxane reactive diluent is one or two mixture of siloxane oligomer with 2-4 epoxy groups and polymerization degree of 2-4.
8. The photo-curable phenyl fluorosilicone modified epoxy paint of claim 2, wherein: the cationic photoinitiator is a substance for initiating epoxy group cationic ring-opening reaction under the action of ultraviolet light.
9. A preparation method of a photo-curing phenyl fluorosilicone modified epoxy coating is characterized by comprising the following steps of: the method comprises the following steps:
the photo-curing phenyl fluorosilicone modified epoxy coating according to any one of claims 2-8 is diluted and then coated on the surface of a substrate, and then leveling, pre-baking to remove solvent and ultraviolet curing are sequentially carried out, so that the photo-curing phenyl fluorosilicone modified epoxy coating is obtained.
10. Use of the photo-cured phenyl fluorosilicone modified epoxy paint according to any one of claims 2-8 in packaging, potting and preparation of an antibacterial, anti-corrosion and anti-fouling functional coating.
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