CN103012698A - 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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- CN103012698A CN103012698A CN2012104959865A CN201210495986A CN103012698A CN 103012698 A CN103012698 A CN 103012698A CN 2012104959865 A CN2012104959865 A CN 2012104959865A CN 201210495986 A CN201210495986 A CN 201210495986A CN 103012698 A CN103012698 A CN 103012698A
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- nanoparticle
- parts
- surface energy
- resin
- low surface
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- 229920005989 resin Polymers 0.000 title claims abstract description 78
- 239000011347 resin Substances 0.000 title claims abstract description 78
- 230000003373 anti-fouling effect Effects 0.000 title claims abstract description 73
- 231100000252 nontoxic Toxicity 0.000 title claims abstract description 37
- 230000003000 nontoxic effect Effects 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 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 26
- 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
- 239000000178 monomer Substances 0.000 claims abstract description 16
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 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
- 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
- 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
- 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
- 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
- 239000005543 nano-size silicon particle Substances 0.000 claims description 8
- -1 azo compound Chemical class 0.000 claims description 7
- 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
- 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
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 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
- 150000001242 acetic acid derivatives Chemical class 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
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 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
- GAURFLBIDLSLQU-UHFFFAOYSA-N diethoxy(methyl)silicon Chemical compound CCO[Si](C)OCC GAURFLBIDLSLQU-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
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 claims description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- OYGYKEULCAINCL-UHFFFAOYSA-N triethoxy(hexadecyl)silane Chemical compound CCCCCCCCCCCCCCCC[Si](OCC)(OCC)OCC OYGYKEULCAINCL-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
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-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
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-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
- JMANVNJQNLATNU-UHFFFAOYSA-N glycolonitrile Natural products N#CC#N JMANVNJQNLATNU-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
- 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
- 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
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 1
- 230000007062 hydrolysis Effects 0.000 abstract description 5
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 5
- 238000004140 cleaning Methods 0.000 abstract description 2
- 239000004925 Acrylic resin Substances 0.000 abstract 2
- 229920000178 Acrylic resin Polymers 0.000 abstract 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 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
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000000203 mixture Substances 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
- 239000003643 water by type Substances 0.000 description 7
- 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
- 230000008901 benefit Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000000543 intermediate Substances 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
- 229920002050 silicone resin Polymers 0.000 description 2
- 239000007787 solid Substances 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
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 238000006243 chemical reaction Methods 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
- 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
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical class 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
- AYEFIAVHMUFQPZ-UHFFFAOYSA-N propane-1,2-diol;prop-2-enoic acid Chemical class CC(O)CO.OC(=O)C=C AYEFIAVHMUFQPZ-UHFFFAOYSA-N 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
- 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 the 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, be mainly used in the antifouling of boats and ships.This resin is to the marine organisms toxicological harmless, and the anti-performance such as stain of automatically cleaning, low surface energy and hydrolysis is dissolved in all over the body.
Background technology
Traditional antifouling paint because the poison material such as organotin, red precipitate, DDT that use more, its toxicity is larger, and is serious to marine organisms and ecological environmental pollution, directly affects the healthy of people by food chain, the market of antifouling paint has been withdrawed from the use that is under an embargo substantially.
At present, succeed that what use is tin-free self-polishing coating, it cooperates low toxicity Red copper oxide and other stain control agents to make to have hydrophilic acrylate copolymer from disappearing molten resin as base-material, has the effect from polishing and drag reduction, and the antifouling phase imitates and 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 the poison material oozes out, when repairing, the depressed place has a strong impact on the adhesion problem of lower road antifouling varnish construction, and the research surface is arranged, and copper+auxiliary toxic agent almost is equal to organotin to the harm of ocean, and such antifouling paint is finally also with 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 adhering to of various marine lifes, what is more important, and low surface energy anti-fouling paint is based on the low surface energy physical action of coating surface, plays long-term antifouling effect, does not have 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: the one, be difficult to obtain to have the more surfacing of low surface energy, make the contact angle of itself and water larger, make the more difficult adhesion of marine life; The 2nd, reconstruct easily occurs in it in seawater, its surface energy is increased in time, reduces with water contact angle, and marine life adheres to again easily.
Nanoparticle has distinctive small-size effect, surface effects, quantum effect, macro quanta tunnel effect etc., more and more is subject to investigator's favor.At present application method is nanoparticle and polymkeric substance directly to be carried out dispersing and mixing and the class matrix material that obtains widely, the advantage of the method is simple to operate, easily industrialization, if but with the nanoparticle of the ecosystem difficulty that is uniformly dispersed, 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 the prior art, the nanoparticle of the ecosystem difficulty that is uniformly dispersed, 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, the nano titanium oxide, 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, propyl group methyldiethoxysilane, dimethyldiethoxysilane, octyltri-ethoxysilane, octyl group Trimethoxy silane, hexadecyl triethoxyl silane, 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, the vinylformic acid pentyl ester, Ethyl acrylate, Isooctyl acrylate monomer, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, propyl methacrylate, butyl methacrylate, the methacrylic acid pentyl ester, N-Hexyl methacrylate, n octyl methacrylate, Isooctyl methacrylate, vinylformic acid, methacrylic acid, Hydroxyethyl acrylate, hydroxyethyl methylacrylate, Propylene glycol monoacrylate, Rocryl 410, in the glycidyl methacrylate one or more.
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 the sad tert-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), the tetrahydrofuran (THF).
The preparation method of described non-toxic long-acting low surface energy antifouling resin, first nanoparticle is carried out pre-treatment with organo-silicon coupling agent, then organo-silicon coupling agent is hydrolyzed, the silicone oligomer that again hydrolyzate is obtained and Acrylic Acid Monomer carry out polyreaction, comprise the steps:
1) pre-treatment of nanoparticle
Nanoparticle, ethanol are poured in the reactor, after stirring, begin to drip organo-silicon coupling agent, make and form take nanoparticle as nuclear, organo-silicon coupling agent is the mixing solutions of shell, then pour in the sand mill and to add the zirconium pearl or granulated glass sphere grinds, the final nanometer slurry that forms the nanoparticle that coats with organo-silicon coupling agent;
2) preparation of nanoparticle silicone oligomer
Mentioned solution is added in the reactor, open and stir; And in reactor, drip the mixing liquid that is formed by deionized water, hydrochloric acid (concentration 37wt%), after dropwising, continue to stir 20-30 minute, then be warming up to reflux temperature, it was reacted 2-4 hour under reflux state, then under vacuum condition, remove organic solvent, namely obtain take the silicone oligomer of nanoparticle as nuclear;
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 3/4 quality is poured in the dropping funnel in addition; Reactor is warming up to 100 ℃, begins to drip, be warming up to 130 ℃ after the dropping, keep being cooled to 50 ℃ with bottom discharge after 2-5 hour, 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 the step 1), the organo-silicon coupling agent time for adding is controlled at 20-30 minute; Step 2) in, the mixing liquid that deionized water, hydrochloric acid form, time for adding is controlled at 20-30 minute; In the step 3), the mixed solution time for adding is controlled at 1-1.5h.
The application of described non-toxic long-acting low surface energy antifouling resin, this antifouling resin add solidifying agent and catalyzer and fully react in use, form low surface energy anti-fouling paint.
Catalyzer is a kind of in dibutyl tin laurate or the stannous sulfate, catalyst levels is the 0.01-0.1wt% of described antifouling resin, solidifying agent is the polyisocyanates compounds, and the mol ratio of polyisocyanates compounds and described antifouling resin is pressed NCO/OH=1.0-2.0.
Among the present invention, the 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 France inferior (Rhodia) company in sieve ground
TMHDB-75MX, Tolonate HDT-90; The CORONATE2604 of Japanese polyurethane Co., Ltd., CORONATEHX-T, CORONATE2384, CORONATEHK.
The present invention has following advantage:
1, in the resin of the present invention by the adding of nanoparticle, solved other silicone resins and roughstuff and adhered to hypodynamic defective.The present invention is melted into a whole resin low surface energy and nanotechnology, be used for the antifouling resin that marine ship is used, this resin is a kind of take nanoparticle as nuclear, nontoxic, the low surface energy take organosilicon modified crylic acid resin as 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 intermediates through the hydrolysis rear surface, existence just because of this intermediate, nano-inorganic substance and vinylformic acid organism are very firmly coupled together, played " bridge " the same effect, made final nanoparticle organosilicon modified crylic acid resin have good stability.
3, the coating made with this resin of the present invention has very low surface energy, and marine organisms are difficult to adhere in film coated surface, even adhere to also insecurely, is easy to come off under current or other External Force Actings.
4, organo-silicon coupling agent of the present invention and Acrylic Acid Monomer reaction, generated-the si-o-c-key, this siloxane bond is easy to hydrolytic cleavage, thereby constantly there is newborn siloxanes to occur, form the coating of new low surface energy, solved the increase in time of common low surface energy coat, surface energy constantly increases, the defective that marine life is adhered to gradually easily.
Embodiment
The preparation method of non-toxic long-acting low surface energy antifouling resin of the present invention carries out pre-treatment with nanoparticle with organo-silicon coupling agent first, then organo-silicon coupling agent is hydrolyzed, and the silicone oligomer that again hydrolyzate is obtained and Acrylic Acid Monomer carry out polyreaction.
The present invention is described in more detail below by embodiment.
Embodiment 1
1. the pre-treatment of nanoparticle
According to the mass fraction, 60 parts of 10 parts of nano silicons, ethanol are poured in the reactor, after stirring, begin to drip 30 parts of dimethyldiethoxysilanes, time for adding is controlled at 20-30 minute, makes to form take nanoparticle as nuclear, and organo-silicon coupling agent is the mixing solutions of shell, then pour in the sand mill and to add the zirconium pearl or granulated glass sphere grinds, the final nanometer slurry that forms the nanoparticle that coats with organo-silicon coupling agent.
2. the preparation of nanoparticle silicone oligomer
Mentioned solution is added in the reactor, open and stir.And in reactor, drip by 3 parts of deionized waters, 0.4 part of mixing liquid that forms of hydrochloric acid (concentration 37wt%), time for adding is controlled at 20-30 minute, after dropwising, continue to stir 20 minutes, then be warming up to reflux temperature, it was reacted 3 hours under reflux state, then under vacuum condition, remove organic solvent, can obtain take the silicone oligomer of nano silicon as nuclear.
3. the preparation of nanoparticle organosilicon modified crylic acid resin
According to the mass fraction, with 15 parts of above-mentioned nanoparticle silicone oligomers, 30 parts of methyl methacrylates, 15 parts of butyl acrylates, 9 parts of Hydroxyethyl acrylates, 1 part in vinylformic acid, 0.4 part of azo-bis-isobutyl cyanide, 21 parts of dimethylbenzene, 9 parts of butyl esters mix, and form mixed solution; Pour the mixed solution of 1/4 quality into reactor, the mixed solution of 3/4 quality is poured in the dropping funnel in addition.Reactor is warming up to 100 ℃, begins to drip, time for adding is controlled at 1h, is warming up to 130 ℃ after the dropping, keeps being cooled to 50 ℃ with bottom discharge after 5 hours, obtains non-toxic long-acting low surface energy antifouling resin.
Embodiment 2
1. the pre-treatment of nanoparticle
According to the mass fraction, 50 parts of 30 parts of nano silicons, ethanol are poured in the reactor, after stirring, begin to drip 30 parts of dimethyldiethoxysilanes, time for adding is controlled at 20-30 minute, makes to form take nanoparticle as nuclear, and organo-silicon coupling agent is the mixing solutions of shell, then pour in the sand mill and to add the zirconium pearl or granulated glass sphere grinds, the final nanometer slurry that forms the nanoparticle that coats with organo-silicon coupling agent.
2. the preparation of nanoparticle silicone oligomer
Mentioned solution is added in the reactor, open and stir.And in reactor, drip by 3 parts of deionized waters, 0.4 part of mixing liquid that forms of hydrochloric acid (concentration 37wt%), time for adding is controlled at 20-30 minute, after dropwising, continue to stir 20 minutes, then be warming up to reflux temperature, it was reacted 3 hours under reflux state, then under vacuum condition, remove organic solvent, can obtain take the silicone oligomer of nano silicon as nuclear.
3. the preparation of nanoparticle organosilicon modified crylic acid resin
According to the mass fraction, with 15 parts of above-mentioned nanoparticle silicone oligomers, 30 parts of methyl methacrylates, 15 parts of butyl acrylates, 9 parts of Hydroxyethyl acrylates, 1 part in vinylformic acid, 0.4 part of azo-bis-isobutyl cyanide, 21 parts of dimethylbenzene, 9 parts of butyl esters mix, and form mixed solution; Pour the mixed solution of 1/4 quality into reactor, the mixed solution of 3/4 quality is poured in the dropping funnel in addition.Reactor is warming up to 100 ℃, begins to drip, time for adding is controlled at 1.5h, is warming up to 130 ℃ after the dropping, keeps being cooled to 50 ℃ with bottom discharge after 2 hours, obtains non-toxic long-acting low surface energy antifouling resin.
Embodiment 3
1. the pre-treatment of nanoparticle
According to the mass fraction, 60 parts of 10 parts of nano silicons, ethanol are poured in the reactor, after stirring, begin to drip 30 parts of dimethyldiethoxysilanes, time for adding is controlled at 20-30 minute, makes to form take nanoparticle as nuclear, and organo-silicon coupling agent is the mixing solutions of shell, then pour in the sand mill and to add the zirconium pearl or granulated glass sphere grinds, the final nanometer slurry that forms the nanoparticle that coats with organo-silicon coupling agent.
2. the preparation of nanoparticle silicone oligomer
Mentioned solution is added in the reactor, open and stir.And in reactor, drip by 6 parts of deionized waters, 0.8 part of mixing liquid that forms of hydrochloric acid (concentration 37wt%), time for adding is controlled at 20-30 minute, after dropwising, continue to stir 20 minutes, then be warming up to reflux temperature, it was reacted 3 hours under reflux state, then under vacuum condition, remove organic solvent, can obtain take the silicone oligomer of nano silicon as nuclear.
3. the preparation of nanoparticle organosilicon modified crylic acid resin
According to the mass fraction, with 15 parts of above-mentioned nanoparticle silicone oligomers, 30 parts of methyl methacrylates, 15 parts of butyl acrylates, 9 parts of Hydroxyethyl acrylates, 1 part in vinylformic acid, 0.4 part of azo-bis-isobutyl cyanide, 21 parts of dimethylbenzene, 9 parts of butyl esters mix, and form mixed solution; Pour the mixed solution of 1/4 quality into reactor, the mixed solution of 3/4 quality is poured in the dropping funnel in addition.Reactor is warming up to 100 ℃, begins to drip, time for adding is controlled at 1.2h, is warming up to 130 ℃ after the dropping, keeps being cooled to 50 ℃ with bottom discharge after 3 hours, obtains non-toxic long-acting low surface energy antifouling resin.
Embodiment 4
1. the pre-treatment of nanoparticle
According to the mass fraction, 60 parts of 10 parts of nano silicons, ethanol are poured in the reactor, after stirring, begin to drip 30 parts of dimethyldiethoxysilanes, time for adding is controlled at 20-30 minute, makes to form take nanoparticle as nuclear, and organo-silicon coupling agent is the mixing solutions of shell, then pour in the sand mill and to add the zirconium pearl or granulated glass sphere grinds, the final nanometer slurry that forms the nanoparticle that coats with organo-silicon coupling agent.
2. the preparation of nanoparticle silicone oligomer
Mentioned solution is added in the reactor, open and stir.And in reactor, drip by 3 parts of deionized waters, 0.4 part of mixing liquid that forms of hydrochloric acid (concentration 37wt%), time for adding is controlled at 20-30 minute, after dropwising, continue to stir 20 minutes, then be warming up to reflux temperature, it was reacted 3 hours under reflux state, then under vacuum condition, remove organic solvent, can obtain take the silicone oligomer of nano silicon as nuclear.
3. the preparation of nanoparticle organosilicon modified crylic acid resin
According to the mass fraction, with 25 parts of above-mentioned nanoparticle silicone oligomers, 25 parts of methyl methacrylates, 10 parts of butyl acrylates, 9 parts of Hydroxyethyl acrylates, 1 part in vinylformic acid, 0.4 part of azo-bis-isobutyl cyanide, 21 parts of dimethylbenzene, 9 parts of butyl esters mix, and form mixed solution; Pour the mixed solution of 1/4 quality into reactor, the mixed solution of 3/4 quality is poured in the dropping funnel in addition.Reactor is warming up to 100 ℃, begins to drip, time for adding is controlled at 1h, is warming up to 130 ℃ after the dropping, keeps being cooled to 50 ℃ with bottom discharge after 4 hours, obtains non-toxic long-acting low surface energy antifouling resin.
Embodiment 5
1. the pre-treatment of nanoparticle
According to the mass fraction, 80 parts of 20 parts of nano silicons, ethanol are poured in the reactor, after stirring, begin to drip 20 parts of hexadecyl triethoxyl silanes, time for adding is controlled at 20-30 minute, makes to form take nanoparticle as nuclear, and organo-silicon coupling agent is the mixing solutions of shell, then pour in the sand mill and to add the zirconium pearl or granulated glass sphere grinds, the final nanometer slurry that forms the nanoparticle that coats with organo-silicon coupling agent.
2. the preparation of nanoparticle silicone oligomer
Mentioned solution is added in the reactor, open and stir.And in reactor, drip by 5 parts of deionized waters, 0.6 part of mixing liquid that forms of hydrochloric acid (concentration 37wt%), time for adding is controlled at 20-30 minute, after dropwising, continue to stir 20 minutes, then be warming up to reflux temperature, it was reacted 3 hours under reflux state, then under vacuum condition, remove organic solvent, can obtain take the silicone oligomer of nano silicon as nuclear.
3. the preparation of nanoparticle organosilicon modified crylic acid resin
According to the mass fraction, with 10 parts of above-mentioned nanoparticle silicone oligomers, 20 parts of glycidyl methacrylate, 15 parts of Propylene glycol monoacrylates, 10 parts of Isooctyl acrylate monomers, 5 parts of methacrylic acids, 0.6 part of the sad tert-butyl ester of mistake, 21 parts of dimethylbenzene, 9 parts of butyl esters mix, and form mixed solution; Pour the mixed solution of 1/4 quality into reactor, the mixed solution of 3/4 quality is poured in the dropping funnel in addition.Reactor is warming up to 100 ℃, begins to drip, time for adding is controlled at 1h, is warming up to 130 ℃ after the dropping, keeps being cooled to 50 ℃ with bottom discharge after 4 hours, obtains non-toxic long-acting low surface energy antifouling resin.
Embodiment 6
1. the pre-treatment of nanoparticle
According to the mass fraction, 90 parts of 30 parts of nano silicons, ethanol are poured in the reactor, after stirring, begin to drip 40 parts of propyl group methyldiethoxysilane, time for adding is controlled at 20-30 minute, makes to form take nanoparticle as nuclear, and organo-silicon coupling agent is the mixing solutions of shell, then pour in the sand mill and to add the zirconium pearl or granulated glass sphere grinds, the final nanometer slurry that forms the nanoparticle that coats with organo-silicon coupling agent.
2. the preparation of nanoparticle silicone oligomer
Mentioned solution is added in the reactor, open and stir.And in reactor, drip by 8 parts of deionized waters, 0.8 part of mixing liquid that forms of hydrochloric acid (concentration 37wt%), time for adding is controlled at 20-30 minute, after dropwising, continue to stir 20 minutes, then be warming up to reflux temperature, it was reacted 3 hours under reflux state, then under vacuum condition, remove organic solvent, can obtain take the silicone oligomer of nano silicon as nuclear.
3. the preparation of nanoparticle organosilicon modified crylic acid resin
According to the mass fraction, with 30 parts of above-mentioned nanoparticle silicone oligomers, 12 parts of propyl acrylates, 10 parts of Isooctyl acrylate monomers, 8 parts of n octyl methacrylates, 5 parts of Hydroxyethyl acrylates, 0.1 part of t-butylperoxyl benzoate, 21 parts of dimethylbenzene, 9 parts of butyl esters mix, and form mixed solution; Pour the mixed solution of 1/4 quality into reactor, the mixed solution of 3/4 quality is poured in the dropping funnel in addition.Reactor is warming up to 100 ℃, begins to drip, time for adding is controlled at 1h, is warming up to 130 ℃ after the dropping, keeps being cooled to 50 ℃ with bottom discharge after 4 hours, obtains non-toxic long-acting low surface energy antifouling resin.
Comparative example 1(is the plus nano particle not)
1. the preparation of silicone oligomer
According to the mass fraction, 30 parts of 60 parts of ethanol, dimethyldiethoxysilane are poured in the reactor, open and stir, and drip by 3 parts of deionized waters, 0.4 part of mixing liquid that forms of hydrochloric acid (concentration 37wt%) in reactor, time for adding is controlled at 20-30 minute, after dropwising, continue to stir 20 minutes, then be warming up to reflux temperature, it was reacted 3 hours under reflux state, then under vacuum condition, remove organic solvent, can obtain with silicone oligomer.
2. the preparation of organosilicon modified crylic acid resin
According to the mass fraction, with 15 parts of above-mentioned nanoparticle silicone oligomers, 30 parts of methyl methacrylates, 15 parts of butyl acrylates, 9 parts of Hydroxyethyl acrylates, 1 part in vinylformic acid, 0.4 part of azo-bis-isobutyl cyanide, 21 parts of dimethylbenzene, 9 parts of butyl esters mix, and form mixed solution; Pour the mixed solution of 1/4 quality into reactor, the mixed solution of 3/4 quality is poured in the dropping funnel in addition.Reactor is warming up to 100 ℃, begins to drip, time for adding is controlled at 1-1.5h, is warming up to 130 ℃ after the dropping, keeps being cooled to 50 ℃ with bottom discharge after 2-5 hour.
Comparative example 2(organo-silicon coupling agent is not hydrolyzed)
1. the pre-treatment of nanoparticle
According to the mass fraction, 60 parts of 10 parts of nano silicons, ethanol are poured in the reactor, after stirring, begin to drip 30 parts of dimethyldiethoxysilanes, time for adding is controlled at 20-30 minute, then pour in the sand mill and to add the zirconium pearl or granulated glass sphere grinds, then the nanometer slurry is poured in the reactor with reflux, be warming up to reflux temperature, it was reacted 3 hours under reflux state, then under vacuum condition, remove organic solvent
2. the preparation of nanoparticle organosilicon modified crylic acid resin
According to the mass fraction, with 15 parts of above-mentioned nanoparticle pre-treatment things, 25 parts of methyl methacrylates, 10 parts of butyl acrylates, 9 parts of Hydroxyethyl acrylates, 1 part in vinylformic acid, 0.4 part of azo-bis-isobutyl cyanide, 21 parts of dimethylbenzene, 9 parts of butyl esters mix, and form mixed solution; Pour the mixed solution of 1/4 quality into reactor, the mixed solution of 3/4 quality is poured in the dropping funnel in addition.Reactor is warming up to 100 ℃, begins to drip, time for adding is controlled at 1-1.5h, is warming up to 130 ℃ after the dropping, keeps being cooled to 50 ℃ with bottom discharge after 2-5 hour.
Performance Ratio is:
Get antifouling resin among the embodiment 1 and polyisocyanates compounds by the mass ratio of NCO/OH=1.1, the polyisocyanates compounds can use the D of Bayer Bitterfeld GmbH (Bayer) company
The N75(solid content is 75wt%, and NCO content is 16.4wt%).Add the dibutyl tin laurate that accounts for described antifouling resin 0.05% quality again, be made into varnish after stirring, evenly be applied on the tinplate, freeze-day with constant temperature is tested after solidifying.Can be 21.2mN/m with Static Contact angle measuring instrument test film coated surface, contact angle is 106 degree, illustrates that showing of this resin can be very low.To film placed synthetic sea water 30 days, and surveying its surface energy is 21.6mN/m, is not increased significantly, and illustrated that the hydrolysising group that exists in the resin can make film coated surface be in the low surface energy state always, reached to continue antifouling effect.
Get antifouling resin among the embodiment 1, the resin in the comparative example 1 respectively with the mass ratio of polyisocyanates compounds by NCO/OH=1.1, the polyisocyanates compounds can use Bayer Bitterfeld GmbH (Bayer) company
The N75(solid content is 75wt%, and NCO content is 16.4wt%).Add again the dibutyl tin laurate that accounts for described antifouling resin 0.05% quality, be made into varnish after stirring, be evenly coated in respectively on the epoxy rust-proofing primer, the thickness of priming paint is 125um, the thickness of varnish is 50um, pulls open the test of method sticking power after freeze-day with constant temperature solidifies.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.This shows, obviously improved the sticking power between antifouling coating and roughstuff behind the adding Nano particles of silicon dioxide.
Resin in antifouling resin among the embodiment 1, the comparative example 2 is all placed climatic chamber, relatively the stability in storage of the two.After 3 months, the antifouling resin among the embodiment 1 is without considerable change, and the resin in the comparative example 2 has demixing phenomenon.After 6 months, demixing phenomenon appears in the antifouling resin among the embodiment 1, the serious layering of the resin in the comparative example 2, and return thick phenomenon.By both contrasts, illustrate through the coupling agent that is hydrolyzed to increase the effect that is connected between inorganics nanoparticle and the organism, and can make system more stable.
Claims (10)
1. non-toxic long-acting low surface energy antifouling resin, it is characterized in that: 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 0.1-1.0 part; Acrylic Acid Monomer 30-60 part; Initiator 0.01-1.0 part; Organic solvent 20-100 part.
2. according to non-toxic long-acting low surface energy antifouling resin claimed in claim 1, it is characterized in that: nanoparticle is one or more in nano silicon, nano aluminium oxide, the nano titanium oxide, and the granularity of nanoparticle is 50-200nm.
3. according to non-toxic long-acting low surface energy antifouling resin claimed in claim 1, it is characterized in that: organo-silicon coupling agent be propyl-triethoxysilicane, propyl trimethoxy silicane, propyl group methyldiethoxysilane, dimethyldiethoxysilane, octyltri-ethoxysilane, octyl group Trimethoxy silane, hexadecyl triethoxyl silane, hexadecyl Trimethoxy silane one or more.
4. according to non-toxic long-acting low surface energy antifouling resin claimed in claim 1, it is characterized in that: Acrylic Acid Monomer is methyl acrylate, ethyl propenoate, propyl acrylate, butyl acrylate, the vinylformic acid pentyl ester, Ethyl acrylate, Isooctyl acrylate monomer, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, propyl methacrylate, butyl methacrylate, the methacrylic acid pentyl ester, N-Hexyl methacrylate, n octyl methacrylate, Isooctyl methacrylate, vinylformic acid, methacrylic acid, Hydroxyethyl acrylate, hydroxyethyl methylacrylate, Propylene glycol monoacrylate, Rocryl 410, in the glycidyl methacrylate one or more.
5. according to non-toxic long-acting low surface energy antifouling resin claimed in claim 1, it is characterized in that: initiator is azo compound or acetate compounds.
6. according to non-toxic long-acting low surface energy antifouling resin claimed in claim 5, it is characterized in that: azo compound is azo-two isobutyl cyanogen, and acetate compounds is t-butylperoxyl benzoate or crosses the sad tert-butyl ester.
7. according to non-toxic long-acting low surface energy antifouling resin claimed in claim 1, it is characterized in that: 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), in the tetrahydrofuran (THF) one or more.
8. according to the preparation method of the described non-toxic long-acting low surface energy of one of claim 1-7 antifouling resin, it is characterized in that, first nanoparticle is carried out pre-treatment with organo-silicon coupling agent, then organo-silicon coupling agent is hydrolyzed, the silicone oligomer that again hydrolyzate is obtained and Acrylic Acid Monomer carry out polyreaction, comprise the steps:
1) pre-treatment of nanoparticle
Nanoparticle, ethanol are poured in the reactor, after stirring, begin to drip organo-silicon coupling agent, make and form take nanoparticle as nuclear, organo-silicon coupling agent is the mixing solutions of shell, then pour in the sand mill and to add the zirconium pearl or granulated glass sphere grinds, the final nanometer slurry that forms the nanoparticle that coats with organo-silicon coupling agent;
2) preparation of nanoparticle silicone oligomer
Mentioned solution is added in the reactor, open and stir; And in reactor, drip the mixing liquid that is formed by deionized water, hydrochloric acid, after dropwising, continue to stir 20-30 minute, then be warming up to reflux temperature, it was reacted 2-4 hour under reflux state, then under vacuum condition, remove organic solvent, namely obtain take the silicone oligomer of nanoparticle as nuclear;
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 3/4 quality is poured in the dropping funnel in addition; Reactor is warming up to 100 ℃, begins to drip, be warming up to 130 ℃ after the dropping, keep being cooled to 50 ℃ with bottom discharge after 2-5 hour, obtain non-toxic long-acting low surface energy antifouling resin.
9. according to the preparation method of non-toxic long-acting low surface energy antifouling resin claimed in claim 8, it is characterized in that in the step 1), the organo-silicon coupling agent time for adding is controlled at 20-30 minute; Step 2) in, the mixing liquid that deionized water, hydrochloric acid form, time for adding is controlled at 20-30 minute; In the step 3), the mixed solution time for adding is controlled at 1-1.5h.
10. according to the application of non-toxic long-acting low surface energy antifouling resin claimed in claim 1, it is characterized in that this antifouling resin adds solidifying agent and catalyzer and fully reacts in use, forms low surface energy anti-fouling paint; Catalyzer is a kind of in dibutyl tin laurate or the stannous sulfate, catalyst levels is the 0.01-0.1wt% of described antifouling resin, solidifying agent is the polyisocyanates compounds, and the mol ratio of polyisocyanates compounds and described antifouling resin is pressed NCO/OH=1.0-2.0.
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| CN113166579A (en) * | 2019-12-04 | 2021-07-23 | 厦门双瑞船舶涂料有限公司 | Organic-inorganic nano composite antifouling coating for environment-friendly antifouling paint and preparation method thereof |
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