CN103012698B - Non-toxic long-acting low-surface-energy antifouling resin and preparation method and application thereof - Google Patents
Non-toxic long-acting low-surface-energy antifouling resin and preparation method and application thereof Download PDFInfo
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- CN103012698B CN103012698B CN201210495986.5A CN201210495986A CN103012698B CN 103012698 B CN103012698 B CN 103012698B CN 201210495986 A CN201210495986 A CN 201210495986A CN 103012698 B CN103012698 B CN 103012698B
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- 229920005989 resin Polymers 0.000 title claims abstract description 71
- 239000011347 resin Substances 0.000 title claims abstract description 71
- 230000003373 anti-fouling effect Effects 0.000 title claims abstract description 66
- 231100000252 nontoxic Toxicity 0.000 title claims abstract description 30
- 230000003000 nontoxic effect Effects 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000002105 nanoparticle Substances 0.000 claims abstract description 80
- 239000007822 coupling agent Substances 0.000 claims abstract description 36
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 36
- 239000010703 silicon Substances 0.000 claims abstract description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 31
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 28
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003973 paint Substances 0.000 claims abstract description 19
- 239000003960 organic solvent Substances 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000178 monomer Substances 0.000 claims abstract description 14
- 239000003999 initiator Substances 0.000 claims abstract description 7
- 239000011259 mixed solution Substances 0.000 claims description 32
- 229920001296 polysiloxane Polymers 0.000 claims description 32
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 30
- 238000010792 warming Methods 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 29
- 238000010992 reflux Methods 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 20
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 16
- 239000005543 nano-size silicon particle Substances 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 13
- 238000002203 pretreatment Methods 0.000 claims description 13
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 10
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 9
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- 239000011521 glass Substances 0.000 claims description 9
- 239000005056 polyisocyanate Substances 0.000 claims description 9
- 229920001228 polyisocyanate Polymers 0.000 claims description 9
- 239000004576 sand Substances 0.000 claims description 9
- 239000002002 slurry Substances 0.000 claims description 9
- 229910052726 zirconium Inorganic materials 0.000 claims description 9
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 8
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 8
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 8
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 claims description 8
- 229940043265 methyl isobutyl ketone Drugs 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 5
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 claims description 4
- SYBYTAAJFKOIEJ-UHFFFAOYSA-N 3-Methylbutan-2-one Chemical compound CC(C)C(C)=O SYBYTAAJFKOIEJ-UHFFFAOYSA-N 0.000 claims description 4
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical group CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 4
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical group COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 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 4
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 4
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 claims description 3
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 claims description 3
- ZMWJQGOYIBHQJG-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propan-1-ol Chemical compound CCO[Si](C)(OCC)CCCO ZMWJQGOYIBHQJG-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 claims description 3
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 3
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 claims description 3
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 claims description 3
- IDQBJILTOGBZCR-UHFFFAOYSA-N 1-butoxypropan-1-ol Chemical compound CCCCOC(O)CC IDQBJILTOGBZCR-UHFFFAOYSA-N 0.000 claims description 2
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 claims description 2
- ZMARGGQEAJXRFP-UHFFFAOYSA-N 1-hydroxypropan-2-yl 2-methylprop-2-enoate Chemical compound OCC(C)OC(=O)C(C)=C ZMARGGQEAJXRFP-UHFFFAOYSA-N 0.000 claims description 2
- FENFUOGYJVOCRY-UHFFFAOYSA-N 1-propoxypropan-2-ol Chemical compound CCCOCC(C)O FENFUOGYJVOCRY-UHFFFAOYSA-N 0.000 claims description 2
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 claims description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 2
- NQSLZEHVGKWKAY-UHFFFAOYSA-N 6-methylheptyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C(C)=C NQSLZEHVGKWKAY-UHFFFAOYSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 2
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 2
- RSKGMYDENCAJEN-UHFFFAOYSA-N hexadecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCCCCCC[Si](OC)(OC)OC RSKGMYDENCAJEN-UHFFFAOYSA-N 0.000 claims description 2
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 2
- VLCAYQIMSMPEBW-UHFFFAOYSA-N methyl 3-hydroxy-2-methylidenebutanoate Chemical compound COC(=O)C(=C)C(C)O VLCAYQIMSMPEBW-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- MSRJTTSHWYDFIU-UHFFFAOYSA-N octyltriethoxysilane Chemical compound CCCCCCCC[Si](OCC)(OCC)OCC MSRJTTSHWYDFIU-UHFFFAOYSA-N 0.000 claims description 2
- 229960003493 octyltriethoxysilane Drugs 0.000 claims description 2
- GYDSPAVLTMAXHT-UHFFFAOYSA-N pentyl 2-methylprop-2-enoate Chemical compound CCCCCOC(=O)C(C)=C GYDSPAVLTMAXHT-UHFFFAOYSA-N 0.000 claims description 2
- ULDDEWDFUNBUCM-UHFFFAOYSA-N pentyl prop-2-enoate Chemical compound CCCCCOC(=O)C=C ULDDEWDFUNBUCM-UHFFFAOYSA-N 0.000 claims description 2
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 2
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 claims description 2
- 229910000375 tin(II) sulfate Inorganic materials 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 1
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical group CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract description 8
- 230000007062 hydrolysis Effects 0.000 abstract description 6
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 3
- 238000004140 cleaning Methods 0.000 abstract description 2
- 239000004925 Acrylic resin Substances 0.000 abstract 2
- 229920000178 Acrylic resin Polymers 0.000 abstract 2
- 231100001261 hazardous Toxicity 0.000 abstract 1
- 239000004615 ingredient Substances 0.000 abstract 1
- 231100000956 nontoxicity Toxicity 0.000 abstract 1
- 230000002265 prevention Effects 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- -1 azo compound Chemical class 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000002966 varnish Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000005498 polishing Methods 0.000 description 3
- 150000001242 acetic acid derivatives Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000002574 poison Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 230000037452 priming Effects 0.000 description 2
- 239000013535 sea water Substances 0.000 description 2
- XUIMIQQOPSSXEZ-NJFSPNSNSA-N silicon-30 atom Chemical group [30Si] XUIMIQQOPSSXEZ-NJFSPNSNSA-N 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 231100000167 toxic agent Toxicity 0.000 description 2
- 239000003440 toxic substance Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- LBJNMUFDOHXDFG-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu].[Cu] LBJNMUFDOHXDFG-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 230000000994 depressogenic effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N glycolonitrile Natural products N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 210000004400 mucous membrane Anatomy 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000005028 tinplate Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 230000002110 toxicologic effect Effects 0.000 description 1
- 231100000027 toxicology Toxicity 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Abstract
The invention relates to the field of antifouling paint, in particular relates to a non-toxic long-acting low-surface-energy antifouling resin and a preparation method and application thereof, and in particular relates to a nano particle organic modified acrylic resin which is mainly used for antifouling of ships. The resin is non-hazardous to marine organisms, and integrates properties of self-cleaning, low surface energy, hydrolysis pollution prevention and the like. The resin comprises the following ingredients in parts by mass: 10-30 parts of nano particles, 50-100 parts of ethanol, 10-50 parts of organic silicon coupling agents, 2-9 parts of water, 0.1-1.0 part of hydrochloric acid, 30-60 parts of acrylic acid monomer, 0.01-1.0 part of initiator, and 20-100 parts of organic solvent. Through the hydrolysis of the organic silicon coupling agent, the nano particles are solidly combined with the acrylic acid monomer so as to form a structure that the nano particles are used as a nuclear and the organic silicon modified acrylic resin is used as a shell. The antifouling resin has the properties of no toxicity, low surface energy and good bottom paint adhesion force, and is provided with hydrolysis groups.
Description
Technical field
The present invention relates to antifouling paint field, be specially long-acting low surface energy antifouling resin of a kind of Novel non-toxic and its preparation method and application, particularly nanoparticle organosilicon modified crylic acid resin, is mainly used in the antifouling of boats and ships.Anti-to automatically cleaning, low surface energy and the hydrolysis performance such as to stain, to marine organisms toxicological harmless, is dissolved in all over the body by this resin.
Background technology
Traditional antifouling paint owing to using the poison material such as organotin, red precipitate, DDT more, its toxicity is comparatively large, to marine organisms and ecological environmental pollution serious, directly affect the healthy of people by food chain, be prohibited from using, substantially exited the market of antifouling paint.
At present, what succeed application is tin-free self-polishing coating, and it, having hydrophilic acrylate copolymer from disappearing molten resin for base-material, coordinating low toxicity Red copper oxide and other stain control agents to make, having the effect from polishing and drag reduction, and antifouling phase effect can reach 3 years.But it in use, it can not change initial roughness, fuel-efficient effect is bad, and its maximum shortcoming is: form one deck mucous membrane in film coated surface after poison material oozes out, the adhesion problem of lower road antifouling varnish construction is had a strong impact on when depressed place is repaiied, and having research surface, the copper+auxiliary harm of toxic agent to ocean is almost equal to organotin, and such antifouling paint is finally also by disabled.
All be devoted to the research of non-toxic anti-pollution paint for sea of new generation both at home and abroad, mainly contain nontoxic self-polishing antifouling paint of new generation, bionical antifouling paint, low surface energy anti-fouling paint, nanostructured surface antifouling paint, conduction antifouling paint etc.
Wherein, low surface energy anti-fouling paint then can prevent the attachment of various marine life, what is more important, and low surface energy anti-fouling paint is the low surface energy physical action on coating based surface, plays effect antifouling for a long time, there is not the release loss problem of toxicant.Low surface energy anti-fouling paint environmental friendliness, safety non-toxic, being recognized is a kind of optimal marine antifouling coating.The subject matter of restriction low surface energy antifouling coating for seas development: one is be difficult to obtain the surfacing with more low surface energy, makes its contact angle with water more greatly, makes the more difficult adhesion of marine life; Two is that it easily reconstructs in the seawater, and its surface energy is increased in time, and reduce with water contact angle, marine life easily adheres to again.
Nanoparticle has distinctive small-size effect, surface effects, quantum effect, macro quanta tunnel effect etc., is more and more subject to the favor of investigator.Application method is the class matrix material that nanoparticle and polymkeric substance are directly carried out dispersing and mixing and obtain widely at present, the advantage of the method is simple to operate, easy industrialization, but if the nanoparticle dispersion of ecosystem is evenly more difficult, and the stability of dispersion is not good yet.
Summary of the invention
The object of the present invention is to provide a kind of non-toxic long-acting low surface energy antifouling resin and its preparation method and application, solve silicone resin and roughstuff sticking power deficiency in prior art, the nanoparticle dispersion of ecosystem is evenly more difficult, and the problem such as the stability of dispersion is not good.
Technical scheme of the present invention is:
A kind of non-toxic long-acting low surface energy antifouling resin, according to the mass fraction, the component of this resin is as follows:
Nanoparticle 10-30 part; Ethanol 50-100 part; Organo-silicon coupling agent 10-50 part; Water 2-9 part; Hydrochloric acid (concentration 37wt%) 0.1-1.0 part; Acrylic Acid Monomer 30-60 part; Initiator 0.01-1.0 part; Organic solvent 20-100 part.
Described non-toxic long-acting low surface energy antifouling resin, nanoparticle is one or more in nano silicon, nano aluminium oxide, nano titanium oxide, and the granularity of nanoparticle is 50-200nm.
Described non-toxic long-acting low surface energy antifouling resin, organo-silicon coupling agent be propyl-triethoxysilicane, propyl trimethoxy silicane, hydroxypropyl methyl diethoxy silane, dimethyldiethoxysilane, octyltri-ethoxysilane, octyl group Trimethoxy silane, hexadecyl, hexadecyl trimethoxy silane one or more.
Described non-toxic long-acting low surface energy antifouling resin, Acrylic Acid Monomer is methyl acrylate, ethyl propenoate, propyl acrylate, butyl acrylate, amyl acrylate, Ethyl acrylate, Isooctyl acrylate monomer, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, propyl methacrylate, butyl methacrylate, pentylmethacrylate, N-Hexyl methacrylate, n octyl methacrylate, Isooctyl methacrylate, vinylformic acid, methacrylic acid, Hydroxyethyl acrylate, hydroxyethyl methylacrylate, Propylene glycol monoacrylate, Rocryl 410, one or more in glycidyl methacrylate.
Described non-toxic long-acting low surface energy antifouling resin, initiator is azo compound or acetate compounds, and azo compound is azo-two isobutyl cyanogen, and acetate compounds is t-butylperoxyl benzoate or crosses octanoic acid ter-butyl ester.
Described non-toxic long-acting low surface energy antifouling resin, organic solvent is one or more in benzene,toluene,xylene, N-BUTYL ACETATE, vinyl acetic monomer, ethanol, propyl carbinol, isopropylcarbinol, sec-butyl alcohol, acetone, ethylene glycol ether acetate, 1-Methoxy-2-propyl acetate, ethylene glycol ethyl ether, ethylene glycol monobutyl ether, glycol propyl ether, propylene-glycol ethyl ether, propylene glycol propyl ether, propandiol butyl ether, pimelinketone, methyl ethyl ketone, methylethylketone, methyl iso-butyl ketone (MIBK), methyl isopropyl ketone, methyl n-butyl ketone, methyl iso-butyl ketone (MIBK), tetrahydrofuran (THF).
The preparation method of described non-toxic long-acting low surface energy antifouling resin, first nanoparticle organo-silicon coupling agent is carried out pre-treatment, then organo-silicon coupling agent is hydrolyzed, then the silicone oligomer obtained by hydrolyzate and Acrylic Acid Monomer carry out polyreaction, comprise the steps:
1) pre-treatment of nanoparticle
Nanoparticle, ethanol are poured in reactor, after stirring, start to drip organo-silicon coupling agent, formation is made to take nanoparticle as core, organo-silicon coupling agent is the mixing solutions of shell, then pour in sand mill and add zirconium pearl or granulated glass sphere grinds, finally formed with the nano slurry of the coated nanoparticle of organo-silicon coupling agent;
2) preparation of nanoparticle silicone oligomer
Above-mentioned solution is added in reactor, opens and stir; And in reactor, drip the mixing liquid be made up of deionized water, hydrochloric acid (concentration 37wt%), after dropwising, continue to stir 20-30 minute, then reflux temperature is warming up to, it is made to react 2-4 hour at reflux, then remove organic solvent under vacuum, namely obtaining take nanoparticle as the silicone oligomer of core;
3) preparation of nanoparticle organosilicon modified crylic acid resin
Get silicone oligomer 5-30 part by mass fraction, nanoparticle silicone oligomer, Acrylic Acid Monomer, initiator, organic solvent are mixed, form mixed solution; Pour the mixed solution of 1/4 quality into reactor, the mixed solution of another 3/4 quality is poured in dropping funnel; Reactor is warming up to 100 DEG C, starts to drip, be warming up to 130 DEG C after dropping, keep after 2-5 hour, be cooled to 50 DEG C with bottom discharge, obtain non-toxic long-acting low surface energy antifouling resin.
The preparation method of described non-toxic long-acting low surface energy antifouling resin, in step 1), organo-silicon coupling agent time for adding controls at 20-30 minute; Step 2) in, the mixing liquid of deionized water, hydrochloric acid composition, time for adding controls at 20-30 minute; In step 3), mixed solution time for adding controls at 1-1.5h.
The application of described non-toxic long-acting low surface energy antifouling resin, this antifouling resin in use, adds solidifying agent and catalyzer fully reacts, and forms low surface energy anti-fouling paint.
Catalyzer is the one in dibutyl tin laurate or stannous sulfate, catalyst levels is the 0.01-0.1wt% of described antifouling resin, solidifying agent is polyisocyanates compounds, and the mol ratio of polyisocyanates compounds and described antifouling resin presses NCO/OH=1.0-2.0.
In the present invention, polyisocyanates compounds can be selected from Bayer Bitterfeld GmbH (Bayer) company
iL,
n75,
n100,
n3200,
n3390,
n3300,
vPLS2010/1,
vPLS2025,
vPLS2103,
z4470; The Tolonate of sub-(Rhodia) company in France sieve ground
tMhDB-75MX, Tolonate HDT-90; CORONATE2604, CORONATEHX-T, CORONATE2384, CORONATEHK of Japanese polyurethane Co., Ltd..
Tool of the present invention has the following advantages:
1, adding by nanoparticle in resin of the present invention, other silicone resins are solved and roughstuff adheres to hypodynamic defect.Resin low surface energy and nanotechnology are melted into a whole by the present invention, for the antifouling resin of marine ship, this resin is a kind of is core with nanoparticle, take organosilicon modified crylic acid resin as nontoxic, the low surface energy of shell, with hydrolysising group, the antifouling resin good with priming paint sticking power.
2, organo-silicon coupling agent of the present invention forms a lot of Organosilicon Alcohol in Organic intermediate through hydrolysis rear surface, just because of the existence of this intermediate, nano-inorganic substance and vinylformic acid organism are very firmly coupled together, serve the effect that " bridge " is the same, make final nanoparticle organosilicon modified crylic acid resin have good stability.
3, the present invention's coating that this resin is made has very low surface energy, and marine organisms are difficult to, in film coated surface attachment, even if attachment is also insecure, be easy to come off under current or other External Force Actings.
4, organo-silicon coupling agent of the present invention and Acrylic Acid Monomer react, generate-si-o-c-key, this siloxane bond is easy to hydrolytic cleavage, thus constantly have newborn siloxanes to occur, form the coating of new low surface energy, solve the increase in time of common low surface energy coat, surface energy constantly increases, and makes the defect that marine life easily adheres to gradually.
Embodiment
The preparation method of non-toxic long-acting low surface energy antifouling resin of the present invention, first carries out pre-treatment by nanoparticle organo-silicon coupling agent, is then hydrolyzed by organo-silicon coupling agent, then the silicone oligomer obtained by hydrolyzate and Acrylic Acid Monomer carry out polyreaction.
Below by embodiment, the present invention is described in more detail.
Embodiment 1
1. the pre-treatment of nanoparticle
According to the mass fraction, nano silicon 10 parts, ethanol 60 parts are poured in reactor, after stirring, start to drip dimethyldiethoxysilane 30 parts, time for adding controls at 20-30 minute, and make formation take nanoparticle as core, organo-silicon coupling agent is the mixing solutions of shell, then pour in sand mill and add zirconium pearl or granulated glass sphere grinds, finally to be formed with the nano slurry of the coated nanoparticle of organo-silicon coupling agent.
2. the preparation of nanoparticle silicone oligomer
Above-mentioned solution is added in reactor, opens and stir.And drip by deionized water 3 parts, hydrochloric acid (concentration 37wt%) 0.4 part of mixing liquid formed in reactor, time for adding controls at 20-30 minute, after dropwising, continue stirring 20 minutes, then reflux temperature is warming up to, make it react 3 hours at reflux, then remove organic solvent under vacuum, can obtain take nano silicon as the silicone oligomer of core.
3. the preparation of nanoparticle organosilicon modified crylic acid resin
According to the mass fraction, by above-mentioned nanoparticle silicone oligomer 15 parts, methyl methacrylate 30 parts, butyl acrylate 15 parts, Hydroxyethyl acrylate 9 parts, 1 part, vinylformic acid, azo-bis-isobutyl cyanide 0.4 part, dimethylbenzene 21 parts, butyl ester 9 parts mixes, and forms mixed solution; Pour the mixed solution of 1/4 quality into reactor, the mixed solution of another 3/4 quality is poured in dropping funnel.Reactor is warming up to 100 DEG C, start to drip, time for adding controls at 1h, is warming up to 130 DEG C after dropping, keeps after 5 hours, is cooled to 50 DEG C with bottom discharge, obtains non-toxic long-acting low surface energy antifouling resin.
Embodiment 2
1. the pre-treatment of nanoparticle
According to the mass fraction, nano silicon 30 parts, ethanol 50 parts are poured in reactor, after stirring, start to drip dimethyldiethoxysilane 30 parts, time for adding controls at 20-30 minute, and make formation take nanoparticle as core, organo-silicon coupling agent is the mixing solutions of shell, then pour in sand mill and add zirconium pearl or granulated glass sphere grinds, finally to be formed with the nano slurry of the coated nanoparticle of organo-silicon coupling agent.
2. the preparation of nanoparticle silicone oligomer
Above-mentioned solution is added in reactor, opens and stir.And drip by deionized water 3 parts, hydrochloric acid (concentration 37wt%) 0.4 part of mixing liquid formed in reactor, time for adding controls at 20-30 minute, after dropwising, continue stirring 20 minutes, then reflux temperature is warming up to, make it react 3 hours at reflux, then remove organic solvent under vacuum, can obtain take nano silicon as the silicone oligomer of core.
3. the preparation of nanoparticle organosilicon modified crylic acid resin
According to the mass fraction, by above-mentioned nanoparticle silicone oligomer 15 parts, methyl methacrylate 30 parts, butyl acrylate 15 parts, Hydroxyethyl acrylate 9 parts, 1 part, vinylformic acid, azo-bis-isobutyl cyanide 0.4 part, dimethylbenzene 21 parts, butyl ester 9 parts mixes, and forms mixed solution; Pour the mixed solution of 1/4 quality into reactor, the mixed solution of another 3/4 quality is poured in dropping funnel.Reactor is warming up to 100 DEG C, start to drip, time for adding controls at 1.5h, is warming up to 130 DEG C after dropping, keeps after 2 hours, is cooled to 50 DEG C with bottom discharge, obtains non-toxic long-acting low surface energy antifouling resin.
Embodiment 3
1. the pre-treatment of nanoparticle
According to the mass fraction, nano silicon 10 parts, ethanol 60 parts are poured in reactor, after stirring, start to drip dimethyldiethoxysilane 30 parts, time for adding controls at 20-30 minute, and make formation take nanoparticle as core, organo-silicon coupling agent is the mixing solutions of shell, then pour in sand mill and add zirconium pearl or granulated glass sphere grinds, finally to be formed with the nano slurry of the coated nanoparticle of organo-silicon coupling agent.
2. the preparation of nanoparticle silicone oligomer
Above-mentioned solution is added in reactor, opens and stir.And drip by deionized water 6 parts, hydrochloric acid (concentration 37wt%) 0.8 part of mixing liquid formed in reactor, time for adding controls at 20-30 minute, after dropwising, continue stirring 20 minutes, then reflux temperature is warming up to, make it react 3 hours at reflux, then remove organic solvent under vacuum, can obtain take nano silicon as the silicone oligomer of core.
3. the preparation of nanoparticle organosilicon modified crylic acid resin
According to the mass fraction, by above-mentioned nanoparticle silicone oligomer 15 parts, methyl methacrylate 30 parts, butyl acrylate 15 parts, Hydroxyethyl acrylate 9 parts, 1 part, vinylformic acid, azo-bis-isobutyl cyanide 0.4 part, dimethylbenzene 21 parts, butyl ester 9 parts mixes, and forms mixed solution; Pour the mixed solution of 1/4 quality into reactor, the mixed solution of another 3/4 quality is poured in dropping funnel.Reactor is warming up to 100 DEG C, start to drip, time for adding controls at 1.2h, is warming up to 130 DEG C after dropping, keeps after 3 hours, is cooled to 50 DEG C with bottom discharge, obtains non-toxic long-acting low surface energy antifouling resin.
Embodiment 4
1. the pre-treatment of nanoparticle
According to the mass fraction, nano silicon 10 parts, ethanol 60 parts are poured in reactor, after stirring, start to drip dimethyldiethoxysilane 30 parts, time for adding controls at 20-30 minute, and make formation take nanoparticle as core, organo-silicon coupling agent is the mixing solutions of shell, then pour in sand mill and add zirconium pearl or granulated glass sphere grinds, finally to be formed with the nano slurry of the coated nanoparticle of organo-silicon coupling agent.
2. the preparation of nanoparticle silicone oligomer
Above-mentioned solution is added in reactor, opens and stir.And drip by deionized water 3 parts, hydrochloric acid (concentration 37wt%) 0.4 part of mixing liquid formed in reactor, time for adding controls at 20-30 minute, after dropwising, continue stirring 20 minutes, then reflux temperature is warming up to, make it react 3 hours at reflux, then remove organic solvent under vacuum, can obtain take nano silicon as the silicone oligomer of core.
3. the preparation of nanoparticle organosilicon modified crylic acid resin
According to the mass fraction, by above-mentioned nanoparticle silicone oligomer 25 parts, methyl methacrylate 25 parts, butyl acrylate 10 parts, Hydroxyethyl acrylate 9 parts, 1 part, vinylformic acid, azo-bis-isobutyl cyanide 0.4 part, dimethylbenzene 21 parts, butyl ester 9 parts mixes, and forms mixed solution; Pour the mixed solution of 1/4 quality into reactor, the mixed solution of another 3/4 quality is poured in dropping funnel.Reactor is warming up to 100 DEG C, start to drip, time for adding controls at 1h, is warming up to 130 DEG C after dropping, keeps after 4 hours, is cooled to 50 DEG C with bottom discharge, obtains non-toxic long-acting low surface energy antifouling resin.
Embodiment 5
1. the pre-treatment of nanoparticle
According to the mass fraction, nano silicon 20 parts, ethanol 80 parts are poured in reactor, after stirring, start to drip hexadecyl 20 parts, time for adding controls at 20-30 minute, and make formation take nanoparticle as core, organo-silicon coupling agent is the mixing solutions of shell, then pour in sand mill and add zirconium pearl or granulated glass sphere grinds, finally to be formed with the nano slurry of the coated nanoparticle of organo-silicon coupling agent.
2. the preparation of nanoparticle silicone oligomer
Above-mentioned solution is added in reactor, opens and stir.And drip by deionized water 5 parts, hydrochloric acid (concentration 37wt%) 0.6 part of mixing liquid formed in reactor, time for adding controls at 20-30 minute, after dropwising, continue stirring 20 minutes, then reflux temperature is warming up to, make it react 3 hours at reflux, then remove organic solvent under vacuum, can obtain take nano silicon as the silicone oligomer of core.
3. the preparation of nanoparticle organosilicon modified crylic acid resin
According to the mass fraction, by above-mentioned nanoparticle silicone oligomer 10 parts, glycidyl methacrylate 20 parts, Propylene glycol monoacrylate 15 parts, Isooctyl acrylate monomer 10 parts, methacrylic acid 5 parts, cross octanoic acid ter-butyl ester 0.6 part, dimethylbenzene 21 parts, butyl ester 9 parts mixes, and forms mixed solution; Pour the mixed solution of 1/4 quality into reactor, the mixed solution of another 3/4 quality is poured in dropping funnel.Reactor is warming up to 100 DEG C, start to drip, time for adding controls at 1h, is warming up to 130 DEG C after dropping, keeps after 4 hours, is cooled to 50 DEG C with bottom discharge, obtains non-toxic long-acting low surface energy antifouling resin.
Embodiment 6
1. the pre-treatment of nanoparticle
According to the mass fraction, nano silicon 30 parts, ethanol 90 parts are poured in reactor, after stirring, start to drip hydroxypropyl methyl diethoxy silane 40 parts, time for adding controls at 20-30 minute, and make formation take nanoparticle as core, organo-silicon coupling agent is the mixing solutions of shell, then pour in sand mill and add zirconium pearl or granulated glass sphere grinds, finally to be formed with the nano slurry of the coated nanoparticle of organo-silicon coupling agent.
2. the preparation of nanoparticle silicone oligomer
Above-mentioned solution is added in reactor, opens and stir.And drip by deionized water 8 parts, hydrochloric acid (concentration 37wt%) 0.8 part of mixing liquid formed in reactor, time for adding controls at 20-30 minute, after dropwising, continue stirring 20 minutes, then reflux temperature is warming up to, make it react 3 hours at reflux, then remove organic solvent under vacuum, can obtain take nano silicon as the silicone oligomer of core.
3. the preparation of nanoparticle organosilicon modified crylic acid resin
According to the mass fraction, by above-mentioned nanoparticle silicone oligomer 30 parts, propyl acrylate 12 parts, Isooctyl acrylate monomer 10 parts, n octyl methacrylate 8 parts, Hydroxyethyl acrylate 5 parts, t-butylperoxyl benzoate 0.1 part, dimethylbenzene 21 parts, butyl ester 9 parts mixes, and forms mixed solution; Pour the mixed solution of 1/4 quality into reactor, the mixed solution of another 3/4 quality is poured in dropping funnel.Reactor is warming up to 100 DEG C, start to drip, time for adding controls at 1h, is warming up to 130 DEG C after dropping, keeps after 4 hours, is cooled to 50 DEG C with bottom discharge, obtains non-toxic long-acting low surface energy antifouling resin.
Comparative example 1(is plus nano particle not)
1. the preparation of silicone oligomer
According to the mass fraction, ethanol 60 parts, dimethyldiethoxysilane 30 parts are poured in reactor, open and stir, and drip in reactor by deionized water 3 parts, hydrochloric acid (concentration 37wt%) 0.4 part of mixing liquid formed, time for adding controls at 20-30 minute, after dropwising, continue stirring 20 minutes, be then warming up to reflux temperature, make it react 3 hours at reflux, then remove organic solvent under vacuum, can obtain with silicone oligomer.
2. the preparation of organosilicon modified crylic acid resin
According to the mass fraction, by above-mentioned nanoparticle silicone oligomer 15 parts, methyl methacrylate 30 parts, butyl acrylate 15 parts, Hydroxyethyl acrylate 9 parts, 1 part, vinylformic acid, azo-bis-isobutyl cyanide 0.4 part, dimethylbenzene 21 parts, butyl ester 9 parts mixes, and forms mixed solution; Pour the mixed solution of 1/4 quality into reactor, the mixed solution of another 3/4 quality is poured in dropping funnel.Reactor is warming up to 100 DEG C, start to drip, time for adding controls at 1-1.5h, is warming up to 130 DEG C after dropping, keeps after 2-5 hour, is cooled to 50 DEG C with bottom discharge.
Comparative example 2(organo-silicon coupling agent is not hydrolyzed)
1. the pre-treatment of nanoparticle
According to the mass fraction, nano silicon 10 parts, ethanol 60 parts are poured in reactor, after stirring, start to drip dimethyldiethoxysilane 30 parts, time for adding controls at 20-30 minute, then pour in sand mill and add zirconium pearl or granulated glass sphere grinds, then being poured into by nano slurry has in the reactor of reflux, is warming up to reflux temperature, makes it react 3 hours at reflux, then organic solvent is removed under vacuum
2. the preparation of nanoparticle organosilicon modified crylic acid resin
According to the mass fraction, by above-mentioned nanoparticle pre-treatment thing 15 parts, methyl methacrylate 25 parts, butyl acrylate 10 parts, Hydroxyethyl acrylate 9 parts, 1 part, vinylformic acid, azo-bis-isobutyl cyanide 0.4 part, dimethylbenzene 21 parts, butyl ester 9 parts mixes, and forms mixed solution; Pour the mixed solution of 1/4 quality into reactor, the mixed solution of another 3/4 quality is poured in dropping funnel.Reactor is warming up to 100 DEG C, start to drip, time for adding controls at 1-1.5h, is warming up to 130 DEG C after dropping, keeps after 2-5 hour, is cooled to 50 DEG C with bottom discharge.
Performance comparision:
Antifouling resin in Example 1 and polyisocyanates compounds press the mass ratio of NCO/OH=1.1, and polyisocyanates compounds can use the D of Bayer Bitterfeld GmbH (Bayer) company
n75(solid content is 75wt%, NCO content is 16.4wt%).Add the dibutyl tin laurate accounting for described antifouling resin 0.05% quality again, after stirring, be made into varnish, be evenly applied on tinplate, test after freeze-day with constant temperature solidification.Can be 21.2mN/m by Static Contact angle measuring instrument test film coated surface, contact angle be 106 degree, illustrate this resin show can be very low.Film is placed in synthetic sea water 30 days, surveying its surface energy is 21.6mN/m, is not increased significantly, and illustrates that the hydrolysising group existed in resin can make film coated surface be in low surface energy state always, reaches lasting antifouling effect.
Resin in antifouling resin in Example 1, comparative example 1 presses the mass ratio of NCO/OH=1.1 with polyisocyanates compounds respectively, and polyisocyanates compounds can use Bayer Bitterfeld GmbH (Bayer) company
n75(solid content is 75wt%, NCO content is 16.4wt%).Add the dibutyl tin laurate accounting for described antifouling resin 0.05% quality again, be made into varnish after stirring, be evenly coated on epoxy rust-proofing primer respectively, the thickness of priming paint is 125um, the thickness of varnish is 50um, carries out pulling open the test of method sticking power after freeze-day with constant temperature solidification.The sticking power of embodiment 1 is 6MPa(5.3-6.7) 100%B, the sticking power of comparative example 1 is 3MPa(3.1-3.4) 100%B.As can be seen here, the sticking power between antifouling coating and roughstuff is significantly improved after adding Nano particles of silicon dioxide.
Resin in antifouling resin in embodiment 1, comparative example 2 is all placed in climatic chamber, compares the stability in storage of the two.After 3 months, the antifouling resin in embodiment 1 is without considerable change, and the resin in comparative example 2 has demixing phenomenon.After 6 months, there is demixing phenomenon in the antifouling resin in embodiment 1, the resin severe delamination in comparative example 2, and return thick phenomenon.By both contrasts, illustrate that the coupling agent passing through hydrolysis can increase the connection effect between inorganics nanoparticle and organism, system can be made more stable.
Claims (3)
1. a non-toxic long-acting low surface energy antifouling resin, is characterized in that: according to the mass fraction, and the component of this resin is as follows:
Nanoparticle 10-30 part; Ethanol 50-100 part; Organo-silicon coupling agent 10-50 part; Water 2-9 part; Hydrochloric acid 0.1-1.0 part; Acrylic monomer 30-60 part; Initiator 0.01-1.0 part; Organic solvent 20-100 part;
Nanoparticle is one or more in nano silicon, nano aluminium oxide, nano titanium oxide, and the granularity of nanoparticle is 50-200nm;
Organo-silicon coupling agent be propyl-triethoxysilicane, propyl trimethoxy silicane, hydroxypropyl methyl diethoxy silane, dimethyldiethoxysilane, octyltri-ethoxysilane, octyl group Trimethoxy silane, hexadecyl, hexadecyl trimethoxy silane one or more;
Acrylic monomer is methyl acrylate, ethyl propenoate, propyl acrylate, butyl acrylate, amyl acrylate, Ethyl acrylate, Isooctyl acrylate monomer, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, propyl methacrylate, butyl methacrylate, pentylmethacrylate, N-Hexyl methacrylate, n octyl methacrylate, Isooctyl methacrylate, vinylformic acid, methacrylic acid, Hydroxyethyl acrylate, hydroxyethyl methylacrylate, Propylene glycol monoacrylate, Rocryl 410, one or more in glycidyl methacrylate,
Initiator is Diisopropyl azodicarboxylate, t-butylperoxyl benzoate or mistake octanoic acid ter-butyl ester;
Organic solvent is benzene, toluene, dimethylbenzene, N-BUTYL ACETATE, vinyl acetic monomer, ethanol, propyl carbinol, isopropylcarbinol, sec-butyl alcohol, acetone, ethylene glycol ether acetate, 1-Methoxy-2-propyl acetate, ethylene glycol ethyl ether, ethylene glycol monobutyl ether, glycol propyl ether, propylene-glycol ethyl ether, propylene glycol propyl ether, propandiol butyl ether, pimelinketone, methyl ethyl ketone, methylethylketone, methyl iso-butyl ketone (MIBK), methyl isopropyl ketone, methyl n-butyl ketone, methyl iso-butyl ketone (MIBK), one or more in tetrahydrofuran (THF),
First nanoparticle organo-silicon coupling agent is carried out pre-treatment, then organo-silicon coupling agent is hydrolyzed, then the silicone oligomer obtained by hydrolyzate and acrylic monomer carry out polyreaction, comprise the steps:
1) pre-treatment of nanoparticle
Nanoparticle, ethanol are poured in reactor, after stirring, start to drip organo-silicon coupling agent, formation is made to take nanoparticle as core, organo-silicon coupling agent is the mixing solutions of shell, then pour in sand mill and add zirconium pearl or granulated glass sphere grinds, finally formed with the nano slurry of the coated nanoparticle of organo-silicon coupling agent;
2) preparation of nanoparticle silicone oligomer
Above-mentioned solution is added in reactor, opens and stir; And in reactor, drip the mixing liquid be made up of deionized water, hydrochloric acid, after dropwising, continue to stir 20-30 minute, then reflux temperature is warming up to, it is made to react 2-4 hour at reflux, then remove organic solvent under vacuum, namely obtaining take nanoparticle as the silicone oligomer of core;
3) preparation of nanoparticle organosilicon modified crylic acid resin
Get silicone oligomer 5-30 part by mass fraction, nanoparticle silicone oligomer, acrylic monomer, initiator, organic solvent are mixed, form mixed solution; Pour the mixed solution of 1/4 quality into reactor, the mixed solution of another 3/4 quality is poured in dropping funnel; Reactor is warming up to 100 DEG C, starts to drip, be warming up to 130 DEG C after dropping, keep after 2-5 hour, be cooled to 50 DEG C with bottom discharge, obtain non-toxic long-acting low surface energy antifouling resin.
2. according to non-toxic long-acting low surface energy antifouling resin according to claim 1, it is characterized in that, in step 1), organo-silicon coupling agent time for adding controls at 20-30 minute; Step 2) in, the mixing liquid of deionized water, hydrochloric acid composition, time for adding controls at 20-30 minute; In step 3), mixed solution time for adding controls at 1-1.5h.
3. according to the application of non-toxic long-acting low surface energy antifouling resin according to claim 1, it is characterized in that, this antifouling resin in use, adds solidifying agent and catalyzer fully reacts, and forms low surface energy anti-fouling paint; Catalyzer is the one in dibutyl tin laurate or stannous sulfate, catalyst levels is the 0.01-0.1wt% of described antifouling resin, solidifying agent is polyisocyanates compounds, and the mol ratio of polyisocyanates compounds and described antifouling resin presses NCO/OH=1.0-2.0.
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