CN109983083A - 防污组合物 - Google Patents
防污组合物 Download PDFInfo
- Publication number
- CN109983083A CN109983083A CN201780069857.0A CN201780069857A CN109983083A CN 109983083 A CN109983083 A CN 109983083A CN 201780069857 A CN201780069857 A CN 201780069857A CN 109983083 A CN109983083 A CN 109983083A
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- CN
- China
- Prior art keywords
- coating composition
- antifouling coating
- composition according
- acrylate
- meth
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 230000003373 anti-fouling effect Effects 0.000 title claims abstract description 99
- 239000000203 mixture Substances 0.000 title claims abstract description 38
- 229920001577 copolymer Polymers 0.000 claims abstract description 89
- KNNOZYMZRGTZQM-UHFFFAOYSA-N tri(propan-2-yl)silyl 2-methylprop-2-enoate Chemical compound CC(C)[Si](C(C)C)(C(C)C)OC(=O)C(C)=C KNNOZYMZRGTZQM-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000003973 paint Substances 0.000 claims abstract description 27
- 229960002140 medetomidine Drugs 0.000 claims abstract description 21
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 13
- 239000001257 hydrogen Substances 0.000 claims abstract description 13
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 8
- 150000004292 cyclic ethers Chemical group 0.000 claims abstract description 7
- 125000001424 substituent group Chemical group 0.000 claims abstract description 6
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 5
- 239000001301 oxygen Substances 0.000 claims abstract description 5
- HRLIOXLXPOHXTA-UHFFFAOYSA-N medetomidine Chemical compound C=1C=CC(C)=C(C)C=1C(C)C1=CN=C[N]1 HRLIOXLXPOHXTA-UHFFFAOYSA-N 0.000 claims abstract 2
- 239000008199 coating composition Substances 0.000 claims description 65
- -1 tetraethoxysilane Chemical compound 0.000 claims description 57
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 30
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 30
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 30
- 238000000576 coating method Methods 0.000 claims description 27
- 239000011248 coating agent Substances 0.000 claims description 21
- 239000003139 biocide Substances 0.000 claims description 14
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 13
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 13
- 229940112669 cuprous oxide Drugs 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 10
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical class C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 8
- 230000003115 biocidal effect Effects 0.000 claims description 6
- QHNCWVQDOPICKC-UHFFFAOYSA-N copper;1-hydroxypyridine-2-thione Chemical compound [Cu].ON1C=CC=CC1=S.ON1C=CC=CC1=S QHNCWVQDOPICKC-UHFFFAOYSA-N 0.000 claims description 6
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 5
- YXYJVFYWCLAXHO-UHFFFAOYSA-N 2-methoxyethyl 2-methylprop-2-enoate Chemical compound COCCOC(=O)C(C)=C YXYJVFYWCLAXHO-UHFFFAOYSA-N 0.000 claims description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 4
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical class C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims description 3
- WFTWWOCWRSUGAW-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl 2-methylprop-2-enoate Chemical compound CCOCCOCCOC(=O)C(C)=C WFTWWOCWRSUGAW-UHFFFAOYSA-N 0.000 claims description 3
- FTALTLPZDVFJSS-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl prop-2-enoate Chemical compound CCOCCOCCOC(=O)C=C FTALTLPZDVFJSS-UHFFFAOYSA-N 0.000 claims description 3
- HFCUBKYHMMPGBY-UHFFFAOYSA-N 2-methoxyethyl prop-2-enoate Chemical compound COCCOC(=O)C=C HFCUBKYHMMPGBY-UHFFFAOYSA-N 0.000 claims description 3
- NUXLDNTZFXDNBA-UHFFFAOYSA-N 6-bromo-2-methyl-4h-1,4-benzoxazin-3-one Chemical compound C1=C(Br)C=C2NC(=O)C(C)OC2=C1 NUXLDNTZFXDNBA-UHFFFAOYSA-N 0.000 claims description 3
- 239000005749 Copper compound Substances 0.000 claims description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-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
- 150000001880 copper compounds Chemical class 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 3
- MUTNCGKQJGXKEM-UHFFFAOYSA-N tamibarotene Chemical compound C=1C=C2C(C)(C)CCC(C)(C)C2=CC=1NC(=O)C1=CC=C(C(O)=O)C=C1 MUTNCGKQJGXKEM-UHFFFAOYSA-N 0.000 claims description 3
- 150000007984 tetrahydrofuranes Chemical class 0.000 claims description 3
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 2
- 125000000041 C6-C10 aryl group Chemical group 0.000 claims description 2
- LCXXNKZQVOXMEH-UHFFFAOYSA-N Tetrahydrofurfuryl methacrylate Chemical compound CC(=C)C(=O)OCC1CCCO1 LCXXNKZQVOXMEH-UHFFFAOYSA-N 0.000 claims description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims 2
- 229910000077 silane Inorganic materials 0.000 claims 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical class C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 abstract description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 abstract description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract description 5
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 abstract 1
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical class C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 abstract 1
- 125000001118 alkylidene group Chemical group 0.000 abstract 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract 1
- 150000002012 dioxanes Chemical class 0.000 abstract 1
- 150000004862 dioxolanes Chemical class 0.000 abstract 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 81
- 229920000642 polymer Polymers 0.000 description 24
- 241000238586 Cirripedia Species 0.000 description 20
- CUHVIMMYOGQXCV-UHFFFAOYSA-N medetomidine Chemical compound C=1C=CC(C)=C(C)C=1C(C)C1=CNC=N1 CUHVIMMYOGQXCV-UHFFFAOYSA-N 0.000 description 20
- 239000000835 fiber Substances 0.000 description 18
- 239000000178 monomer Substances 0.000 description 18
- 239000000243 solution Substances 0.000 description 17
- 239000011230 binding agent Substances 0.000 description 16
- 239000002904 solvent Substances 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 13
- 239000002519 antifouling agent Substances 0.000 description 11
- 238000005498 polishing Methods 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000005259 measurement Methods 0.000 description 9
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 239000010949 copper Substances 0.000 description 7
- 239000004800 polyvinyl chloride Substances 0.000 description 7
- 229920000915 polyvinyl chloride Polymers 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 239000013535 sea water Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- PQSIXYSSKXAOFE-UHFFFAOYSA-N tri(propan-2-yl)silyl prop-2-enoate Chemical compound CC(C)[Si](C(C)C)(C(C)C)OC(=O)C=C PQSIXYSSKXAOFE-UHFFFAOYSA-N 0.000 description 7
- 239000012855 volatile organic compound Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- FPIPGXGPPPQFEQ-OVSJKPMPSA-N all-trans-retinol Chemical compound OC\C=C(/C)\C=C\C=C(/C)\C=C\C1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-OVSJKPMPSA-N 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- 239000008096 xylene Substances 0.000 description 6
- 239000011324 bead Substances 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 238000005336 cracking Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 230000009477 glass transition Effects 0.000 description 5
- 230000007774 longterm Effects 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 4
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 4
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 4
- MYKDCLOMKLHFSQ-UHFFFAOYSA-N 3-bromo-1H-pyrrole-2-carbonitrile Chemical compound BrC1=C(NC=C1)C#N MYKDCLOMKLHFSQ-UHFFFAOYSA-N 0.000 description 4
- PORQOHRXAJJKGK-UHFFFAOYSA-N 4,5-dichloro-2-n-octyl-3(2H)-isothiazolone Chemical compound CCCCCCCCN1SC(Cl)=C(Cl)C1=O PORQOHRXAJJKGK-UHFFFAOYSA-N 0.000 description 4
- FFWSICBKRCICMR-UHFFFAOYSA-N 5-methyl-2-hexanone Chemical compound CC(C)CCC(C)=O FFWSICBKRCICMR-UHFFFAOYSA-N 0.000 description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 230000000844 anti-bacterial effect Effects 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 239000003899 bactericide agent Substances 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 4
- 238000000113 differential scanning calorimetry Methods 0.000 description 4
- HALQELOKLVRWRI-VDBOFHIQSA-N doxycycline hyclate Chemical compound O.[Cl-].[Cl-].CCO.O=C1C2=C(O)C=CC=C2[C@H](C)[C@@H]2C1=C(O)[C@]1(O)C(=O)C(C(N)=O)=C(O)[C@@H]([NH+](C)C)[C@@H]1[C@H]2O.O=C1C2=C(O)C=CC=C2[C@H](C)[C@@H]2C1=C(O)[C@]1(O)C(=O)C(C(N)=O)=C(O)[C@@H]([NH+](C)C)[C@@H]1[C@H]2O HALQELOKLVRWRI-VDBOFHIQSA-N 0.000 description 4
- 150000002148 esters Chemical group 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 4
- 239000004014 plasticizer Substances 0.000 description 4
- 239000001993 wax Substances 0.000 description 4
- 229940043810 zinc pyrithione Drugs 0.000 description 4
- PICXIOQBANWBIZ-UHFFFAOYSA-N zinc;1-oxidopyridine-2-thione Chemical compound [Zn+2].[O-]N1C=CC=CC1=S.[O-]N1C=CC=CC1=S PICXIOQBANWBIZ-UHFFFAOYSA-N 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000011717 all-trans-retinol Substances 0.000 description 3
- 235000019169 all-trans-retinol Nutrition 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229940047586 chemet Drugs 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 125000004185 ester group Chemical group 0.000 description 3
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- ACTRVOBWPAIOHC-XIXRPRMCSA-N succimer Chemical compound OC(=O)[C@@H](S)[C@@H](S)C(O)=O ACTRVOBWPAIOHC-XIXRPRMCSA-N 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 2
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- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 2
- WHBMMWSBFZVSSR-UHFFFAOYSA-N 3-hydroxybutyric acid Chemical compound CC(O)CC(O)=O WHBMMWSBFZVSSR-UHFFFAOYSA-N 0.000 description 2
- FMHKPLXYWVCLME-UHFFFAOYSA-N 4-hydroxy-valeric acid Chemical compound CC(O)CCC(O)=O FMHKPLXYWVCLME-UHFFFAOYSA-N 0.000 description 2
- 241000206761 Bacillariophyta Species 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
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- 241000195493 Cryptophyta Species 0.000 description 2
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- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
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- 229910019142 PO4 Inorganic materials 0.000 description 2
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
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- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical class OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
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- PGMYKACGEOXYJE-UHFFFAOYSA-N anhydrous amyl acetate Natural products CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 235000019445 benzyl alcohol Nutrition 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- BQVVSSAWECGTRN-UHFFFAOYSA-L copper;dithiocyanate Chemical compound [Cu+2].[S-]C#N.[S-]C#N BQVVSSAWECGTRN-UHFFFAOYSA-L 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 239000002274 desiccant Substances 0.000 description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
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- 230000000694 effects Effects 0.000 description 2
- 150000002084 enol ethers Chemical class 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 229920001002 functional polymer Polymers 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 2
- MNWFXJYAOYHMED-UHFFFAOYSA-M heptanoate Chemical compound CCCCCCC([O-])=O MNWFXJYAOYHMED-UHFFFAOYSA-M 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 150000002484 inorganic compounds Chemical class 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000001023 inorganic pigment Substances 0.000 description 2
- MLFHJEHSLIIPHL-UHFFFAOYSA-N isoamyl acetate Chemical compound CC(C)CCOC(C)=O MLFHJEHSLIIPHL-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 2
- 239000001095 magnesium carbonate Substances 0.000 description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 2
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- WYKYCHHWIJXDAO-UHFFFAOYSA-N tert-butyl 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)C WYKYCHHWIJXDAO-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- ILMRJRBKQSSXGY-UHFFFAOYSA-N tert-butyl(dimethyl)silicon Chemical group C[Si](C)C(C)(C)C ILMRJRBKQSSXGY-UHFFFAOYSA-N 0.000 description 1
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- DLSMLZRPNPCXGY-UHFFFAOYSA-N tert-butylperoxy 2-ethylhexyl carbonate Chemical compound CCCCC(CC)COC(=O)OOOC(C)(C)C DLSMLZRPNPCXGY-UHFFFAOYSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
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- XNFIRYXKTXAHAC-UHFFFAOYSA-N tralopyril Chemical compound BrC1=C(C(F)(F)F)NC(C=2C=CC(Cl)=CC=2)=C1C#N XNFIRYXKTXAHAC-UHFFFAOYSA-N 0.000 description 1
- LGQXXHMEBUOXRP-UHFFFAOYSA-N tributyl borate Chemical compound CCCCOB(OCCCC)OCCCC LGQXXHMEBUOXRP-UHFFFAOYSA-N 0.000 description 1
- NKLYMYLJOXIVFB-UHFFFAOYSA-N triethoxymethylsilane Chemical compound CCOC([SiH3])(OCC)OCC NKLYMYLJOXIVFB-UHFFFAOYSA-N 0.000 description 1
- AJSTXXYNEIHPMD-UHFFFAOYSA-N triethyl borate Chemical compound CCOB(OCC)OCC AJSTXXYNEIHPMD-UHFFFAOYSA-N 0.000 description 1
- GKASDNZWUGIAMG-UHFFFAOYSA-N triethyl orthoformate Chemical compound CCOC(OCC)OCC GKASDNZWUGIAMG-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- TUQLLQQWSNWKCF-UHFFFAOYSA-N trimethoxymethylsilane Chemical compound COC([SiH3])(OC)OC TUQLLQQWSNWKCF-UHFFFAOYSA-N 0.000 description 1
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 description 1
- NHDIQVFFNDKAQU-UHFFFAOYSA-N tripropan-2-yl borate Chemical compound CC(C)OB(OC(C)C)OC(C)C NHDIQVFFNDKAQU-UHFFFAOYSA-N 0.000 description 1
- LTEHWCSSIHAVOQ-UHFFFAOYSA-N tripropyl borate Chemical compound CCCOB(OCCC)OCCC LTEHWCSSIHAVOQ-UHFFFAOYSA-N 0.000 description 1
- ZMCWFMOZBTXGKI-UHFFFAOYSA-N tritert-butyl borate Chemical compound CC(C)(C)OB(OC(C)(C)C)OC(C)(C)C ZMCWFMOZBTXGKI-UHFFFAOYSA-N 0.000 description 1
- FCTBKIHDJGHPPO-UHFFFAOYSA-N uranium dioxide Inorganic materials O=[U]=O FCTBKIHDJGHPPO-UHFFFAOYSA-N 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- AMHNZOICSMBGDH-UHFFFAOYSA-L zineb Chemical compound [Zn+2].[S-]C(=S)NCCNC([S-])=S AMHNZOICSMBGDH-UHFFFAOYSA-L 0.000 description 1
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Abstract
一种防污涂料组合物,包含(i)甲硅烷基酯共聚物,该甲硅烷基酯共聚物包含下述作为共聚单体:(a)甲基丙烯酸三异丙基甲硅烷基酯;(b)式(I)的化合物,其中,R1是氢或甲基,R2是环醚(诸如可选被烷基取代的氧杂环戊烷、噁烷、二氧戊环、二噁烷),并且X是C1‑C4亚烷基,和/或式(II)的化合物,其中,R3是氢或甲基,并且R4是具有至少一个氧或氮原子,优选至少一个氧原子的C3‑C18取代基;以及可选地(c)一种或多种式(III)的共聚单体,其中,R5是氢或甲基,并且R6是C1‑C8烃基;以及(ii)美托咪定。
Description
技术领域
本发明涉及海洋防污涂料组合物(marine antifouling coating composition),更具体地涉及包含甲硅烷基酯共聚物(silyl ester copolymer)的海洋防污涂料组合物,该甲硅烷基酯共聚物包含甲基丙烯酸三异丙基甲硅烷基酯(triisopropylsilylmethacrylate)和至少一种亲水性(甲基)丙烯酸酯作为共聚单体。该组合物另外含有美托咪定(美托咪啶,米托咪啶,medetomidine)作为杀菌剂。本发明还涉及保护物体免受污损的方法、以及涂覆有本发明的防污组合物的物体。
背景技术
浸没在海洋环境中的表面会附着污损生物,诸如细菌、硅藻、海藻、管蠕虫、藤壶和贻贝。在表面上生长的所有海洋生物中,藤壶是最坚韧的。在适当的条件下,藤壶可以非常快速地生长。藤壶分布在世界各地并且是沿海水域中最常遇到的污损生物。
在新建筑物的装配期间以及停泊时间较长或在贸易过程中长的静止期间的船舶上,藤壶在船舶上粘附和污损的风险通常最高。污损会严重影响船舶的运行效率。它导致流体动力学阻力增加,导致燃料消耗增加,速度降低以及操作范围减小。非常粗糙的污损船体可使燃料使用量增加多达40%。还有额外的干坞(干船坞,dry-docking)费用。去除附着的钙质生物诸如藤壶必须通过机械刮擦来完成。船舶上的污损还会导致非本地物种的扩散。这些都是要求防止生物污损的重要经济因素。
使用防污涂料以防止海洋生物的附着和生长。这些涂料通常包含成膜粘合剂和生物活性物质,以及不同的组分,诸如颜料、填料和溶剂。
目前市场上最成功的自抛光防污系统基于甲硅烷基酯共聚物。粘合剂基质由甲硅烷基酯共聚物经常和其它粘合剂诸如丙烯酸酯和松香或松香衍生物一起组成,以调节防污涂覆膜的自抛光性能和机械性能。这些涂料组合物例如在EP 0646630、EP 0802243、EP1342756、EP 1641862、EP 1695956、EP 2781567、WO 00/77102、WO 03/070832和WO 2009/007276中进行描述。
美托咪啶有效防止藤壶附着在淹没在海水中的表面上。它是氮杂环化合物。已知这些化合物对防污涂料组合物的储存稳定性、以及含有可水解粘合剂并且特别是甲硅烷基酯共聚物的防污涂料膜的长期机械性能具有负面影响。
本发明人现已令人惊讶地确定,合并了例如甲基丙烯酸三异丙基甲硅烷基酯和亲水性(甲基)丙烯酸酯共聚单体两者的甲硅烷基酯共聚物与美托咪定的组合,提供了具有改进的防污性能(特别是在防止在海洋表面的藤壶污损方面)的自抛光防污系统(self-polishing antifouling system)。此外,本发明的防污组合物具有优异的抗开裂性和优异的自抛光性能。
已经对含有美托咪定的防污涂料组合物进行了描述。WO 2011/118526要求保护含有美托咪定的防污涂料配方中的可水解共聚物,诸如甲硅烷基酯共聚物。仅例证了一种无亲水性共聚单体的丙烯酸三异丙基甲硅烷基酯共聚物。
WO 2007/015676、WO 2006/096129、WO 00/42851描述了美托咪定(与其它生物活性化合物组合)用于防止藤壶附着的用途。这些文献并非针对粘合剂技术。
含有甲基丙烯酸三异丙基甲硅烷基酯和亲水性共聚单体的防污涂料组合物是已知的。WO 2010/071180要求保护包含甲硅烷基共聚物的防污涂料组合物,其含有甲基丙烯酸三异丙基甲硅烷基酯和甲基丙烯酸甲氧基烷基酯以及松香的铜盐或松香衍生物的铜盐。优选的防污剂是氧化亚铜与除藻剂的组合。该涂料组合物在防止藤壶污损方面表现不佳。
JP 2016089167A要求保护含有甲硅烷基共聚物的无铜防污涂料组合物,其含有甲基丙烯酸三异丙基甲硅烷基酯和(甲基)丙烯酸甲氧基乙酯以及溴代吡咯腈(曲洛比利,tralopyril),具有优异的储存稳定性,并且形成具有优异的长期耐水性(例如抗开裂性)的防污涂覆膜。
WO 2013/073580要求保护甲硅烷基共聚物,其包含来自以特定比例的丙烯酸三异丙基甲硅烷基酯和甲基丙烯酸三异丙基甲硅烷基酯的结构单元,得到具有长期储存稳定性的防污涂料组合物和具有长期机械性能的防污涂料膜。比较例分别示出了丙烯酸三异丙基甲硅烷基酯共聚物和甲基丙烯酸三异丙基甲硅烷基酯共聚物的差的机械性能。所例证的甲硅烷基共聚物均不含任何亲水性共聚单体。
因此,需要甲硅烷基酯共聚物(以及因此防污组合物),其可以与美托咪定组合以提供防污涂料的受控降解,抗开裂性和优异的防污性能,尤其是优异的抗藤壶性(藤壶抗性,anti-barnacle properties)。还期望长期的储存稳定性。
发明内容
在一个方面,本发明涉及一种防污涂料组合物,该防污涂料组合物包含(i)甲硅烷基酯共聚物,该甲硅烷基酯共聚物包含下述作为共聚单体:
(a)甲基丙烯酸三异丙基甲硅烷基酯;
(b)式(I)的化合物
其中,R1是氢或甲基,R2是环醚(诸如可选被烷基取代的氧杂环戊烷(氧戊环,oxolane)、噁烷(氧丙环,oxane)、二氧戊环(dioxolane)、二噁烷(二氧六环,dioxane)),并且X是C1-C4亚烷基;
和/或式(II)的化合物
其中,R3是氢或甲基,并且R4是具有至少一个氧或氮原子,优选至少一个氧原子的C3-C18取代基;以及可选地
(c)一种或多种式(III)的共聚单体
其中,R5是氢或甲基,并且R6是C1-C8烃基;
以及(ii)美托咪定。
优选根据本文所述的实施例部分的方法,通过DSC测量,甲硅烷基酯共聚物具有至少20℃的玻璃化转变温度(Tg)。
防污涂料组合物包含美托咪定和可选的其它防污剂。其它防污剂可以是氧化亚铜、吡啶硫酮铜(吡硫鎓铜,copper pyrithione)、溴代吡咯腈(曲洛比利,tralopyril)或吡啶硫酮锌(zinc pyrithione)。在一个实施方式中,除了美托咪定之外,防污涂料组合物还包含氧化亚铜和吡啶硫酮铜。在另一个实施方式中,除了美托咪定之外,防污涂料组合物还包含溴代吡咯腈和吡啶硫酮锌。因此,在这方面,防污涂料组合物可以不含无机铜类防污剂(无机铜基防污剂)。
在另一个方面,本发明提供了一种用于保护物体免于污损(污垢,fouling)的方法,所述方法包括用本文所定义的防污涂料组合物涂覆经受污损的所述物体的至少一部分。
本发明还涉及涂覆有本文定义的防污涂料组合物的物体。
从另一个方面来看,本发明涉及本文定义的甲硅烷基酯共聚物在包含美托咪定的防污涂料组合物中的用途,即作为这种组合物的粘合剂。
定义
术语“海洋防污涂料组合物”、“防污涂料组合物”或简称“涂料组合物”是指适用于海洋环境的组合物。
术语“烃基”是指仅含有C原子和H原子的任何基团,因此包括烷基、烯基、芳基、环烷基和芳烷基等。
术语“(甲基)丙烯酸酯”是指甲基丙烯酸酯或丙烯酸酯。
在下文中使用的术语“松香”用于涵盖“松香或其衍生物”。
术语“粘合剂”定义了组合物中包括甲硅烷基酯共聚物和任何其它组分的一部分,它们一起形成基质,向组合物赋予物质和强度。通常,本文使用的术语“粘合剂”是指甲硅烷基酯共聚物以及可以包括的任何松香。
具体实施方式
在一个实施方式中,本发明的防污涂料组合物包含甲硅烷基酯共聚物,该甲硅烷基酯共聚物至少包含共聚单体甲基丙烯酸三异丙基甲硅烷基酯和亲水性(甲基)丙烯酸酯。如本文所述,可以另外存在另外的甲硅烷基酯(甲基)丙烯酸酯共聚单体、亲水性(甲基)丙烯酸酯共聚单体和/或非亲水性(甲基)丙烯酸酯共聚单体。
甲硅烷基酯共聚物
共聚单体
在一个实施方式中,甲硅烷基酯共聚物至少包括共聚单体甲基丙烯酸三异丙基甲硅烷基酯(a)和至少一种亲水性单体(b)。
当给出甲硅烷基酯共聚物中给定共聚单体的wt%时,wt%是相对于共聚物中存在的每种共聚单体的总和(重量)的。因此,如果甲基丙烯酸三异丙基甲硅烷基酯(a)和亲水性(甲基)丙烯酸酯单体(b)是甲硅烷基酯共聚物中仅有的共聚单体,则甲基丙烯酸三异丙基甲硅烷基酯的wt%计算为[甲基丙烯酸三异丙基甲硅烷基酯(a)(重量)/(甲基丙烯酸三异丙基甲硅烷基酯)(重量)+亲水性(甲基)丙烯酸酯单体(b)(重量))]×100%。如果仅存在甲基丙烯酸三异丙基甲硅烷基酯(a)、亲水性(甲基)丙烯酸酯单体(b)和甲基丙烯酸甲酯,则甲基丙烯酸三异丙基甲硅烷基酯的wt%计算为[甲基丙烯酸三异丙基甲硅烷基酯(a)(重量)/(甲基丙烯酸三异丙基甲硅烷基酯(重量)+亲水性(甲基)丙烯酸酯单体(b)(重量)+甲基丙烯酸甲酯(重量))]×100%。
共聚物优选包含>80wt%,优选>90wt%,更优选>95wt%,特别是>98wt%的甲基丙烯酸三异丙基甲硅烷基酯(a)、亲水性(甲基)丙烯酸酯共聚单体(b)和非亲水性(甲基)丙烯酸酯共聚单体(c)的组合。
组分(a)是甲基丙烯酸三异丙基甲硅烷基酯,其优选占共聚物的5wt%-80wt%,优选25wt%-75wt%,特别是30wt%-70wt%。
组分(b)(总)优选占共聚物的2wt%-50wt%,优选共聚物的2wt%-40wt%,特别是共聚物的5wt%-40wt%,更特别是5wt%-35wt%。这些wt%值是指存在的组分(b)共聚单体的总量。
(a):(b)(重量/重量)的比优选在40:60至95:5的范围内,优选在50:50至95:5的范围内,特别是在50:50至90:10的范围内,最优选在50:50至85:15的范围内。优选共聚物中(a)的重量分数大于组分(b)的重量分数。
共聚物中(a)+(b)的量优选为至多95wt%,诸如至多90wt%,特别是至多85wt%。共聚物中(a)+(b)的量可以在30wt%-95wt%或40wt%-85wt%的范围内。
亲水性(甲基)丙烯酸酯共聚单体组分(b)
在某些实施方式中,甲硅烷基酯共聚物含有至少一种式(I)的共聚单体,
其中,R1是氢或甲基,R2是环醚(诸如可选被烷基取代的氧杂环戊烷、噁烷、二氧戊环、二噁烷),并且X是C1-C4亚烷基,优选C1-C2亚烷基。
环醚可以在环中含有单个氧原子或在环中含有2或3个氧原子。环醚可以含有包含2-8个碳原子的环,诸如3-5个碳原子的环。整个环可以包含4至8个原子,诸如5或6个原子。
环醚环可以被取代,诸如被一个或多个,诸如一个C1-C6烷基取代。该取代基可以在环上的任何位置,包括与X基团结合的位置。
合适的式(I)的化合物包括丙烯酸四氢糠基酯(tetrahydrofurfuryl acrylate)、甲基丙烯酸四氢糠基酯(tetrahydrofurfuryl methacrylate)、甲基丙烯酸异丙叉基甘油酯(isopropylideneglycerol methacrylate)、甘油缩甲醛甲基丙烯酸酯(甲基丙烯酸甘油甲酯,glycerolformal methacrylate)和环状三羟甲基丙烷缩甲醛丙烯酸酯(cyclictrimethylolpropane formal acrylate)。
式(I)最优选代表具有以下结构的丙烯酸四氢糠基酯:
在进一步的实施方式中,共聚物可以包括一种或多种式(II)的共聚单体:
其中,R3是氢或甲基,并且R4是含有至少一个氧或氮原子,优选至少一个氧原子的C3-C18取代基。
如上式所示,术语“亲水性(甲基)丙烯酸酯”要求式(II)中的R4基团包括至少一个氧或氮原子,优选至少一个氧原子。如下面详细解释的,还可以存在另外的式(III)的非亲水性(甲基)丙烯酸酯共聚单体,其中,R6单元仅由C和H原子组成。
在一个实施方式中,甲硅烷基酯共聚物含有至少一种上述式(II)的共聚单体,其中,R4基团具有式-(CH2CH2O)m-R7,其中,R7是C1-C10烃基取代基,优选C1-C10烷基,或者C6-C10芳基取代基,并且m是在1至6,优选1至3范围内的整数。优选R4具有式-(CH2CH2O)m-R7,其中,R7是烷基取代基,优选甲基或乙基,并且m是在1至3范围内的整数,优选1或2。
在一个实施方式中,甲硅烷基酯共聚物包括甲基丙烯酸2-甲氧基乙酯、丙烯酸2-甲氧基乙酯、甲基丙烯酸2-乙氧基乙酯、甲基丙烯酸2-(2-乙氧基乙氧基)乙酯和丙烯酸2-(2-乙氧基乙氧基)乙酯中的一种或多种。
特别优选的共聚单体(b)包括丙烯酸2-甲氧基乙酯、甲基丙烯酸2-甲氧基乙酯、甲基丙烯酸2-乙氧基乙酯、丙烯酸2-(2-乙氧基乙氧基)乙酯、甲基丙烯酸2-(2-乙氧基乙氧基)乙酯、丙烯酸四氢糠基酯和甲基丙烯酸四氢糠基酯。
如本文所用,式(I)和式(II)定义了“极性”(甲基)丙烯酸酯共聚单体或“亲水性”(甲基)丙烯酸酯共聚单体。这些共聚单体与甲基丙烯酸三异丙基甲硅烷基酯的使用确保形成具有受控降解(controlled degradation)的粘合剂。
如果甲硅烷基酯共聚物包含式(I)的共聚单体或式(II)的共聚单体,则是优选的。通常不优选具有存在来自这些式的单体。
另外的非亲水性(甲基)丙烯酸酯共聚单体(c)
甲硅烷基酯共聚物可以包括一种或多种式(III)的另外的非亲水性(甲基)丙烯酸酯共聚单体,
其中,R5是氢或甲基,并且R6是C1-C8烃基取代基,优选C1-C8烷基取代基,最优选甲基、乙基、正丁基或2-乙基己基。根据式(III)的共聚单体在本文中称为“非亲水性”共聚单体。
在本发明的所有实施方式中,甲硅烷基酯共聚物优选包括至少一种另外的非亲水性甲基丙烯酸酯和/或非亲水性丙烯酸酯共聚单体。当存在一种或多种非亲水性(甲基)丙烯酸酯共聚单体时,甲硅烷基酯共聚物中这些非亲水性(甲基)丙烯酸酯共聚单体的总和优选为至多60wt%,优选不大于55wt%,诸如在10wt%-55wt%的范围内,特别是在10wt%-50wt%的范围内。
在优选的实施方式中,在甲硅烷基酯共聚物中,共聚单体甲基丙烯酸三异丙基甲硅烷基酯(a)、组分(b)和根据式(III)的任何非亲水性(甲基)丙烯酸酯共聚单体一起占共聚单体的>80wt%,优选>90wt%,特别是>95wt%。
在优选的实施方式中,甲硅烷基酯共聚物包含一种或多种非亲水性共聚单体甲基丙烯酸甲酯和/或丙烯酸正丁酯。
在本发明的所有实施方式中,优选包含甲基丙烯酸甲酯。当存在时,甲基丙烯酸甲酯优选以共聚物的2wt%-60wt%,优选5wt%-50wt%的量存在。在优选的实施方式中,在甲硅烷基酯共聚物中,甲基丙烯酸三异丙基甲硅烷基酯(a)、组分(b)和甲基丙烯酸甲酯一起占共聚单体的>50wt%,优选>55wt%,特别是>60wt%。
当存在时,丙烯酸正丁酯优选以1wt%-30wt%,特别是2wt%-25wt%的量存在。
另外的(甲基)丙烯酸甲硅烷基酯共聚单体
甲硅烷基酯共聚物可以包括另外的(甲基)丙烯酸甲硅烷基酯共聚单体。当存在时,除了甲基丙烯酸三异丙基甲硅烷基酯之外的任何另外的(甲基)丙烯酸甲硅烷基酯共聚单体优选占共聚物的不超过20wt%,优选占共聚物的不超过10wt%。当存在时,合适的(甲基)丙烯酸甲硅烷基酯共聚单体优选具有式(IV),
其中,
R8各自独立地选自直链或支链C1-C4烷基;
R9各自独立地选自由以下组成的组:直链或支链C1-C20烷基、C3-C12环烷基、可选取代的C6-C20芳基和-OSi(R10)3基团;
每个R10独立地为直链或支链C1-C4烷基,
n是0至5的整数;
Y是烯键式不饱和基团,诸如丙烯酰氧基、甲基丙烯酰氧基、(甲基丙烯酰氧基)亚烷基羰氧基和(丙烯酰氧基)亚烷基羰氧基。应当理解,甲基丙烯酸三异丙基甲硅烷基酯应视为从式(IV)中排除,因为它总是存在于本发明的甲硅烷基酯共聚物中。
术语“烷基”旨在涵盖直链或支链烷基两者,诸如甲基、乙基、异丙基、丙基和丁基。特别优选的环烷基包括环己基和取代的环己基。
取代的芳基的实例包括被至少一个选自卤素、具有1至约8个碳原子的烷基、酰基或硝基的取代基取代的芳基。特别优选的芳基包括取代和未取代的苯基、苄基、苯基烷基(phenalkyl)或萘基。
理想地,优选的甲硅烷基酯单体基于其中n为0的式(IV)的化合物,即式Y-Si(R9)3的那些化合物。
含有甲硅烷基酯官能团的单体的实例是众所周知的。由通式(IV)定义的单体包括:
丙烯酸和甲基丙烯酸的甲硅烷基酯单体,诸如丙烯酸三异丙基甲硅烷基酯、(甲基)丙烯酸三乙基甲硅烷基酯、(甲基)丙烯酸三正丙基甲硅烷基酯、(甲基)丙烯酸三正丁基甲硅烷基酯、(甲基)丙烯酸三异丁基甲硅烷基酯、(甲基)丙烯酸三叔丁基甲硅烷基酯、(甲基)丙烯酸三仲丁基甲硅烷基酯、(甲基)丙烯酸三正戊基甲硅烷基酯、(甲基)丙烯酸三异戊基甲硅烷基酯、(甲基)丙烯酸三正己基甲硅烷基酯、(甲基)丙烯酸三正辛基甲硅烷基酯、(甲基)丙烯酸三正十二烷基甲硅烷基酯、(甲基)丙烯酸三苯基甲硅烷基酯、(甲基)丙烯酸三(对甲基苯基)甲硅烷基酯、(甲基)丙烯酸三苄基甲硅烷基酯、(甲基)丙烯酸乙基二甲基甲硅烷基酯、(甲基)丙烯酸正丙基二甲基甲硅烷基酯、(甲基)丙烯酸酯异丙基二甲基甲硅烷基酯、(甲基)丙烯酸正丁基二甲基甲硅烷基酯、(甲基)丙烯酸异丁基二甲基甲硅烷基酯、(甲基)丙烯酸叔丁基二甲基甲硅烷基酯、(甲基)丙烯酸正戊基二甲基甲硅烷基酯、(甲基)丙烯酸正己基二甲基甲硅烷基酯、(甲基)丙烯酸新己基二甲基甲硅烷基酯、(甲基)丙烯酸叔己基二甲基甲硅烷基酯(thexyldimethylsilyl(meth)acrylate)、(甲基)丙烯酸正辛基二甲基甲硅烷基酯、(甲基)丙烯酸正癸基二甲基甲硅烷基酯、(甲基)丙烯酸十二烷基二甲基甲硅烷基酯、(甲基)丙烯酸正十八烷基二甲基甲硅烷基酯、(甲基)丙烯酸环己基二甲基甲硅烷基酯、(甲基)丙烯酸苯基二甲基甲硅烷基酯、(甲基)丙烯酸苄基二甲基甲硅烷基酯、(甲基)丙烯酸苯乙基二甲基甲硅烷基酯、(甲基)丙烯酸(3-苯基丙基)二甲基甲硅烷基酯、(甲基)丙烯酸对甲苯基二甲基甲硅烷基酯、(甲基)丙烯酸异丙基二乙基甲硅烷基酯、(甲基)丙烯酸正丁基二异丙基甲硅烷基酯、(甲基)丙烯酸正辛基二异丙基甲硅烷基酯、(甲基)丙烯酸甲基二正丁基甲硅烷基酯、(甲基)丙烯酸甲基二环己基甲硅烷基酯、(甲基)丙烯酸甲基二苯基甲硅烷基酯、(甲基)丙烯酸叔丁基二苯基甲硅烷基酯、(甲基)丙烯酸九甲基四甲硅烷氧基酯(nonamethyltetrasiloxy(meth)acrylate)、(甲基)丙烯酸双(三甲基甲硅烷氧基)甲基甲硅烷基酯、(甲基)丙烯酸三(三甲基甲硅烷氧基)甲硅烷基酯,以及WO 2014/064048和WO 03/080747中记载的其它单体。
甲硅烷基酯共聚物可以包含丙烯酸三异丙基甲硅烷基酯和甲基丙烯酸三异丙基甲硅烷基酯两者。
甲硅烷基酯共聚物的性能
含有有机甲硅烷基酯基团的聚合物可以通过在聚合引发剂存在下通过任何各种方法对单体混合物进行聚合而获得,诸如以常规方式或通过受控聚合技术的溶液聚合、本体聚合、乳液聚合和悬浮聚合。在使用该含有机甲硅烷基酯基团的聚合物制备涂料组合物时,优选用有机溶剂稀释聚合物以得到具有适当粘度的聚合物溶液。从这个观点出发,希望采用溶液聚合。
聚合引发剂的实例包括偶氮化合物,诸如二甲基2,2'-偶氮双(2-甲基丙酸酯)、2,2'-偶氮双(2-甲基丁腈)、2,2'-偶氮双(异丁腈)和1,1'-偶氮双(氰基环己烷);以及过氧化物,诸如过氧新戊酸叔戊酯、过氧新戊酸叔丁酯、过氧-2-乙基己酸叔戊酯、过氧-2-乙基己酸叔丁酯、过氧-2-乙基己酸1,1,3,3-四甲基丁基酯、过氧二乙基乙酸叔丁酯、过氧异丁酸叔丁酯、过氧苯甲酸叔丁酯、1,1-二(叔戊基过氧)环己烷、叔戊基过氧2-乙基己基碳酸酯、叔丁基过氧异丙基碳酸酯、叔丁基过氧2-乙基己基碳酸酯、聚醚聚叔丁基过氧碳酸酯、二-叔丁基过氧化物和二苯甲酰过氧化物。这些化合物可单独使用或以其两种或更多种的混合物使用。
有机溶剂的实例包括芳族烃,诸如二甲苯、甲苯、均三甲苯;酮类,诸如甲基乙基酮、甲基异丁基酮、甲基戊基酮、甲基异戊基酮、环戊酮、环己酮;酯类,诸如乙酸丁酯、乙酸叔丁酯、乙酸戊酯、乙二醇甲醚乙酸酯;醚类,诸如乙二醇二甲醚、二乙二醇二甲醚、二丁醚、二噁烷、四氢呋喃;醇类,诸如正丁醇、异丁醇、苯甲醇;醚醇,诸如丁氧基乙醇、1-甲氧基-2-丙醇;脂肪族烃,诸如白色溶剂油(石油溶剂油,白酒,松香水,white spirit);和可选的两种或更多种溶剂的混合物。这些化合物可单独使用或以其两种或更多种的混合物使用。共聚物优选是无规共聚物。
由此获得的含有机甲硅烷基酯基团的聚合物的重均分子量优选为5,000至100,000,优选10,000至80,000,更优选20,000至60,000。如实施例部分所述对Mw进行测量。
共聚物的玻璃化转变温度(Tg)优选为至少15℃,优选至少20℃,诸如至少22℃,所有值均根据实施例部分中描述的Tg测试来测量。优选低于80℃的值,诸如低于75℃,例如低于60℃。
甲硅烷基酯共聚物可以作为聚合物溶液提供。希望将聚合物溶液调节至固体含量为30wt%-90wt%,优选40wt%-85wt%,更优选40wt%-75wt%。
本发明的最终防污涂料组合物基于总涂料组合物,优选包含0.5wt%-45wt%,诸如1wt%-30wt%,特别是5wt%-25wt%的甲硅烷基酯共聚物。
本发明的防污涂料组合物可可选地包含本发明的甲硅烷基酯共聚物和例如在US4,593,055、EP 0 646 630、WO 2009/007276和EP 2 781 567中所述的其它甲硅烷基酯共聚物的混合物。
松香成分
松香可用于调节防污涂覆膜的自抛光性能和机械性能。本发明的防污涂料组合物优选包含至少0.5wt%,诸如至少1wt%的松香。松香组分的上限可以为25wt%,诸如15wt%。
用于本发明的松香可以是松香或其衍生物,诸如例如如下所述的它们的盐。松香材料的实例包括木松香、妥尔油松香和脂松香(gum rosin);松香衍生物,诸如氢化和部分氢化的松香,歧化松香,二聚松香,聚合松香,松香和氢化松香的马来酸酯、富马酸酯、甘油酯、甲酯、季戊四醇酯和其它酯,松香和聚合松香的树脂酸铜、树脂酸锌、树脂酸钙、树脂酸镁和其它树脂酸金属盐以及如WO 97/44401中所述的其它物质。优选的是脂松香和脂松香的衍生物。
在本发明中,防污组合物优选包含0.5wt%-25wt%,优选1wt%-20wt%的松香材料,优选2wt%-15wt%。
可以通过改变甲硅烷基酯共聚物和松香组分的相对量对防污涂料的性能进行调节。
其它粘合剂组分
除了甲硅烷基酯共聚物和可选的松香外,还可以使用另外的粘合剂对防污涂覆膜的性能进行调节。除了本发明的甲硅烷基酯共聚物和松香之外,可以使用的粘合剂的实例包括:
(甲基)丙烯酸聚合物和共聚物,特别是丙烯酸酯粘合剂,诸如聚(丙烯酸正丁酯)、聚(丙烯酸正丁酯-共-异丁基乙烯基醚),以及在WO 03/070832和EP 2128208中所述的其它物质;
乙烯基醚聚合物和共聚物,诸如聚(甲基乙烯基醚)、聚(乙基乙烯基醚)、聚(异丁基乙烯基醚)、聚(氯乙烯-共-异丁基乙烯基醚);
酸性官能聚合物(酸官能聚合物),例如EP 0204456和EP 0342276中所述其酸基被与一价有机残基键合的二价金属封端;或者例如GB 2311070和EP 0982324中所述其酸基被与羟基残基键合的二价金属封端;或例如EP 0529693中所述其酸基被胺封端;
亲水性共聚物,例如GB 2152947中所述的(甲基)丙烯酸酯共聚物和聚(N-乙烯基吡咯烷酮)共聚物,以及EP 0526441中所述的其它共聚物;脂肪族聚酯,诸如聚(乳酸)、聚(乙醇酸)、聚(2-羟基丁酸)、聚(3-羟基丁酸)、聚(4-羟基戊酸)、聚己酸内酯,以及含有选自上述单元的两个或更多个单元的脂肪族聚酯共聚物;
含金属聚酯,例如在EP 1033392和EP 1072625中所述;
如WO 2009/100908中所述的聚草酸酯(聚草酸盐,polyoxalate)和WO 96/14362中描述的其它缩聚物;
醇酸树脂和改性的醇酸树脂;
烃树脂,例如如WO 2011/092143中所述,诸如仅由选自C5脂肪族单体、C9芳族单体、茚香豆酮单体(indene coumarone monomer)或萜烯的至少一种单体或其混合物的聚合形成的烃树脂。
如果除了松香和甲硅烷基酯共聚物之外还存在另外的粘合剂,则甲硅烷基共聚物:粘合剂的重量比可以为30:70至95:5,优选35:65至90:10,特别是40:60到80:20的范围。这些优选的比例仅涉及甲硅烷基共聚物和另外的粘合剂的量,即松香不包括在内。
特别合适的另外的粘合剂是(甲基)丙烯酸聚合物和共聚物。
杀菌剂
防污涂料另外包含能够防止或消除表面上或来自表面的海洋污损的化合物。在这方面,必须存在4-[1-(2,3-二甲基苯基)乙基]-1H-咪唑[美托咪定]。
除了这种杀菌剂外,还可以存在其它防污化合物。术语防污剂(antifoulingagent)、抗污剂(anti-foulant)、杀菌剂、毒剂(toxicant)用于在工业上描述在表面上用于防止海洋污损的已知化合物。本发明的防污剂是海洋防污剂。
涂料组合物可包括铜杀菌剂,优选氧化亚铜(Cu2O)和/或吡啶硫酮铜。氧化亚铜材料的典型粒径分布为0.1μm-70μm,并且平均粒径(d50)为1μm-25μm。氧化亚铜材料可含有稳定剂以防止表面氧化和附聚。可商购的氧化亚铜的实例包括:来自Nordox AS的Nordox氧化亚铜红漆级(Nordox Cuprous Oxide Red Paint Grade)、Nordox XLT,来自FurukawaChemicals Co.,Ltd.的氧化亚铜;来自American Chemet Corporation的Red Copp 97N、Purple Copp、Lolo Tint 97N、Chemet CDC、Chemet LD;来自Spiess-Urania的氧化亚铜红(Cuprous Oxide Red);来自Taixing Smelting Plant Co.,Ltd(泰兴冶炼厂有限公司)的焙烧氧化亚铜(Cuprous oxide Roast)、电解氧化亚铜(Cuprous oxide Electrolytic)。
本发明的涂料组合物可以含有其它杀菌剂,诸如WO 2014/064048中所述。优选的另外的生物活性剂是氧化亚铜、硫氰酸铜、吡啶硫酮锌、吡啶硫酮铜、亚乙基双(二硫代氨基甲酸)锌[代森锌]、2-(叔丁基氨基)-4-(环丙基氨基)-6-(甲硫基)-1,3,5-三嗪[cubutryne]、4,5-二氯-2-正辛基-4-异噻唑啉-3-酮[DCOIT]、N-二氯氟甲硫基-N',N'-二甲基-N-苯基磺酰胺[抑菌灵]、N-二氯氟甲硫基-N',N'-二甲基-N-对甲苯基磺酰胺[对甲抑菌灵]、三苯基硼烷吡啶[TPBP]和4-溴-2-(4-氯苯基)-5-(三氟甲基)-1H-吡咯-3-甲腈[溴代吡咯腈]。
如本领域已知的,可以使用杀菌剂的混合物,因为不同的杀菌剂可以对抗不同的海洋污损生物起作用。
更优选的是对海洋无脊椎动物、植物和细菌有活性的杀菌剂的混合物,海洋无脊椎动物诸如藤壶、管虫、苔藓虫和水螅虫;植物诸如海藻,藻类和硅藻。
在一个实施方式中,该组合物不含无机铜杀菌剂。在这方面,最优选的选择是美托咪定、溴代吡咯腈以及一种或多种选自吡啶硫酮锌、代森锌和4,5-二氯-2-辛基-4-异噻唑啉-3-酮的所选择杀菌剂的组合。
在可替换的实施方式中,除了美托咪定之外,防污涂料组合物还包含氧化亚铜和/或硫氰酸铜以及一种或多种选自吡啶硫酮铜、代森锌和4,5-二氯-2-辛基-4-异噻唑啉-3-酮的杀菌剂。
在可替换的实施方式中,防污涂层不含铜。
杀菌剂的组合的量可以占涂料组合物的至多70wt%,诸如0.1wt%-60wt%,例如0.2wt%-60wt%。当存在无机铜化合物时,涂料组合物中杀菌剂的合适量可以为20wt%-60wt%。在避免无机铜化合物的情况下,可以使用较低的量,诸如0.1wt%-20wt%,例如0.2wt%-15wt%。应理解,杀菌剂的量将根据最终用途和所用的杀菌剂而变化。
美托咪定的用量很低。组合物中的典型量为0.02wt%-1.0wt%,诸如0.05wt%-0.5wt%,特别是0.1wt%-0.4wt%。
一些杀菌剂可以被包封或吸附在惰性载体上或与其它材料结合以控制释放。这些百分比是指存在的活性杀菌剂的量,因此不是指所使用的任何载体。
其它组分
除了甲硅烷基酯共聚物和上述任何可选的组分外,根据本发明的防污涂料组合物还可可选地包含选自其它粘合剂、无机或有机颜料、增量剂和填料、添加剂、溶剂和稀释剂中的一种或多种组分。
颜料的实例是无机颜料,诸如二氧化钛、铁氧化物(氧化铁)、氧化锌、磷酸锌和石墨;有机颜料,诸如酞菁化合物(phthalocyanine compound)、偶氮颜料和炭黑。
增量剂和填料的实例是矿物,诸如白云石、塑石(plastorite)、方解石、石英、重晶石、菱镁矿、文石(霰石,aragonite)、硅石、硅灰石、滑石、绿泥石(亚氯酸盐,chlorite)、云母、高岭土和长石;合成无机化合物,诸如碳酸钙、碳酸镁、硫酸钡、硅酸钙和硅石;聚合和无机微球,诸如未涂覆或涂覆的中空玻璃珠和实心玻璃珠、未涂覆或涂覆的中空陶瓷珠和实心陶瓷珠,聚合物材料的多孔珠和致密珠,聚合物材料诸如聚(甲基丙烯酸甲酯)、聚(甲基丙烯酸甲酯-共-乙二醇二甲基丙烯酸酯)、聚(苯乙烯-共-乙二醇二甲基丙烯酸酯)、聚(苯乙烯-共-二乙烯基苯)、聚苯乙烯、聚(氯乙烯)。
可添加到防污涂料组合物中的添加剂的实例是增强剂、触变剂、增稠剂、防沉剂(抗沉降剂,anti-settling agent)、润湿剂和分散剂、增塑剂以及溶剂。
增强剂的实例是薄片(flake)和纤维。纤维包括天然和合成的无机纤维,诸如含硅纤维、碳纤维、氧化物纤维、碳化物纤维、氮化物纤维、硫化物纤维、磷酸盐纤维、矿物纤维;金属纤维;天然和合成的有机纤维,诸如纤维素纤维、橡胶纤维、丙烯酸纤维、聚酰胺纤维、聚酰亚胺、聚酯纤维、聚酰肼纤维、聚氯乙烯纤维、聚乙烯纤维和WO 00/77102中所述的其它纤维。优选地,纤维的平均长度为25μm-2,000μm,并且平均厚度为1μm-50μm,其中平均长度与平均厚度之比为至少5。
触变剂、增稠剂和防沉剂的实例是硅石,诸如热解硅石(fumed silica)、有机改性的粘土、酰胺蜡、聚酰胺蜡、酰胺衍生物、聚乙烯蜡、氧化的聚乙烯蜡、氢化的蓖麻油蜡、乙基纤维素、硬脂酸铝及其混合物。
增塑剂的实例是聚合增塑剂(聚合物增塑剂)、氯化石蜡(chlorinatedparaffin)、邻苯二甲酸酯(邻苯二甲酸盐,phthalate)、磷酸酯、磺酰胺、己二酸酯(己二酸盐)、环氧化的植物油和乙酸异丁酸蔗糖酯(sucrose acetate isobutyrate)。
脱水剂和干燥剂的实例包括无水硫酸钙、硫酸钙半水合物、无水硫酸镁、无水硫酸钠、无水硫酸锌、分子筛和沸石;原酸酯,诸如原甲酸三甲酯、原甲酸三乙酯、原甲酸三丙酯、原甲酸三异丙酯、原甲酸三丁酯、原乙酸三甲酯和原乙酸三乙酯;缩酮;缩醛(acetal);烯醇醚(enolether);原硼酸酯,诸如硼酸三甲酯、硼酸三乙酯、硼酸三丙酯、硼酸三异丙酯、硼酸三丁酯和硼酸三叔丁酯;硅烷,诸如四乙氧基硅烷、三甲氧基甲基硅烷、三乙氧基甲基硅烷、苯基三甲氧基硅烷、乙烯基三甲氧基硅烷、乙烯基三乙氧基硅烷和聚硅酸乙酯;和异氰酸酯,例如对甲苯磺酰异氰酸酯。
优选的脱水剂和干燥剂是硅烷诸如四乙氧基硅烷和无机化合物。特别优选使用硅烷和松香或其衍生物。
有助于防污涂料组合物的储存稳定性的稳定剂的实例是碳二亚胺化合物,诸如双(2,6-二异丙基苯基)碳二亚胺和1,3-二-对甲苯基碳二亚胺(1,3-di-p-tolylcarbodiimide),以及如EP 2725073中所述的其它化合物。
通常,这些可选组分中的任何一种可以以防污组合物的0.1wt%-20wt%,通常0.5wt%-20wt%,优选0.75wt%-15wt%范围的量存在。应理解,这些可选组分的量将根据最终用途而变化。
如果防污组合物含有溶剂,则是高度优选的。此类溶剂优选是挥发性的并且优选是有机的。有机溶剂和稀释剂的实例是芳族烃,诸如二甲苯、甲苯、均三甲苯;酮类,诸如甲基乙基酮、甲基异丁基酮、甲基异戊基酮、甲基戊基酮、二异丁基酮、甲基丙基酮、环戊酮、环己酮;酯类,诸如乙酸丁酯、乙酸叔丁酯、乙酸戊酯、乙酸异戊酯、乙二醇甲醚乙酸酯、丙酸丙酯、丙酸丁酯;醚类,诸如乙二醇二甲醚、二乙二醇二甲醚、二丁醚、二噁烷、四氢呋喃;醇类,诸如正丁醇、异丁醇、苯甲醇;醚醇,诸如丁氧基乙醇、1-甲氧基-2-丙醇;脂肪族烃,诸如白色溶剂油;以及可选的两种或更多种溶剂和稀释剂的混合物。
优选的溶剂是芳族溶剂,尤其是二甲苯和芳族烃的混合物。
溶剂的量优选尽可能低。溶剂含量可以高达组合物的50wt%,优选高达组合物的45wt%,诸如高达40wt%,但可以低至15wt%或更低,例如10wt%或更低。同样,技术人员将理解的是,溶剂的含量将根据存在的其它组分和涂料组合物的最终用途而变化。
可替换地,涂料可以分散于在涂料组合物中或水分散体中用于成膜组分的有机非溶剂中。
本发明的防污涂料组合物的固体含量应优选高于40vol%,例如高于45vol%,诸如高于50vol%,优选高于55vol%。
更优选地,防污涂料组合物的挥发性有机化合物(VOC)的含量应低于500g/L,优选低于400g/L,例如低于390g/L。可以计算(ASTM D5201-01)或测量,优选测量VOC含量。
本发明的防污涂料组合物可以施加(施用,涂覆)至任何经受污损的物体表面的整体或部分上。表面可以永久地或间歇地在水下(例如通过潮汐运动,不同的货物装载或膨胀)。物体表面通常是船舶的船体或固定的海洋物体,诸如石油平台或浮标的表面。可以通过任何方便的方式,例如通过将涂料涂抹(例如用刷子或辊)或喷涂到物体上来完成涂料组合物的施加。通常,表面需要与海水分离以允许进行涂覆。涂料的施加可以如本领域中常规已知的来实现。
当将防污涂料施加到物体(例如船体)上时,物体的表面不是仅由单层防污涂层保护。根据表面的特性,防污涂料可以直接施加到现有的涂料体系,该涂料体系包括几层不同类型的涂料层(例如环氧树脂、聚酯、乙烯基树脂或丙烯酸或其混合物)。以未涂覆的表面(例如钢、铝、塑料、复合材料、玻璃纤维或碳纤维)开始,全涂料体系通常包括一层或两层防腐涂层、一层粘结涂层(tie-coat)以及一层或两层防污涂层(antifouling paint)。在特殊情况下,可以施加另外的防污涂料层。如果表面是来自以前施加的清洁且完整的防污涂料,则可以直接施加新的防污涂料,通常作为一层或两层涂层,其中在特殊情况下可以更多。
现在将参考以下非限制性实施例对本发明进行定义。
实施例
材料和方法
测试
聚合物溶液粘度的测定
根据ASTM D2196,使用具有LV-2或LV-4锭子(轴,spindle)的Brookfield DV-I粘度计,在12rpm下,对聚合物的粘度进行测定。在测量之前,将聚合物调温至23.0℃±0.5℃。
聚合物溶液的固含量的测定
根据ISO 3251对聚合物溶液中的固体含量进行测定。取出0.5g±0.1g的试样并在通风烘箱中在150℃下干燥30分钟。残余材料的重量被认为是非挥发性物质(NVM)。非挥发性物质含量以重量百分比表示。给出的值是三个平行试验的平均值。
聚合物平均分子量分布的测定
通过凝胶渗透色谱(GPC)测量对聚合物进行表征。使用具有两个来自PolymerLaboratories(聚合物实验室)的串联PLgel 5μm Dixed-D柱的Polymer Laboratories PL-GPC 50仪器对分子量分布(MWD)进行测定,在环境温度下以四氢呋喃(THF)作为洗脱液,恒定流速为1mL/min,使用折射率(RI)检测器。使用来自Polymer Laboratories的聚苯乙烯标准品Easivials PS-H对柱进行校准。使用来自Polymer Labs的Cirrus软件对数据进行处理。通过将相当于25mg干燥聚合物的量的聚合物溶液溶解在5mL THF中来制备样品。在取样进行GPC测量之前,将样品在室温下保持最少3小时。表中记载了重均分子量(Mw)、数均分子量(Mn)和以Mw/Mn给出的多分散指数(PDI)。
玻璃化转变温度的测定
通过差示扫描量热法(DSC)测量获得玻璃化转变温度(Tg)。DSC测量在TAInstruments DSC Q200上进行。通过将少量聚合物溶液转移到铝盘中并在50℃下将样品干燥最少10小时,随后在150℃下干燥3小时来制备样品。在开口铝盘中,对大约10mg干燥聚合物材料的样品进行测量,并且在-50℃至150℃的温度范围内,以10℃/min的加热速率和10℃/min的冷却速率记录扫描,其中空盘作为参照。使用来自TA Instruments的UniversalAnalysis软件对数据进行处理。如ASTM E1356-08中所定义,将第二次加热的玻璃化转变范围的拐点报告为聚合物的Tg。
制备防污涂料组合物的一般过程
将组分以表2中给出的比例混合。使用振动振荡器将混合物在玻璃珠(直径约2mm)存在下,在250ml的涂料罐中分散15分钟。在测试之前将玻璃珠过滤。
使用锥板粘度计测定涂料粘度
根据ISO 2884-1:1999,使用数字锥板粘度计对防污涂料组合物的粘度进行测定,设定温度为23℃,在10000s-1的剪切速率下工作,并提供0-10P范围内的粘度测量。结果以三次测量的平均值给出。
防污涂料组合物中的挥发性有机化合物(VOC)含量的计算
防污涂料组合物中的挥发性有机化合物(VOC)含量根据ASTM D5201进行计算。
涂覆膜的加速开裂试验
用适当的防腐底漆涂覆PVC板。使用间隙尺寸为800μm的膜涂布器将防污涂料施加在板上。将板在52℃下干燥72小时,然后浸入40℃的海水中。定期取出板并进行评估。在室温下干燥24小时后,在10×放大倍数下并且视觉上对板的开裂进行评价,并在52℃下干燥24小时后再次评价。然后将板重新浸入。表3中报告了在52℃下干燥后的评级。
板评级如下:
0-无裂纹
1-很少裂纹
2-中等数量的裂纹
3-大量裂纹
4-密集开裂
海水中旋转盘上防污涂覆膜抛光率的测定
通过测量涂覆膜随时间的膜厚度的减少来测定抛光率(polishing rate)。对于该测试,使用PVC盘。使用间隙尺寸为300μm的膜涂布器将涂料组合物作为径向条纹施加在盘上。通过表面轮廓仪测量干涂覆膜的厚度。典型的初始干膜取决于所施加的防污涂料组合物的固含量和施加速度。实施例部分中测试的涂层的典型初始膜厚度为100μm±10μm。将PVC盘安装在轴上并在容器中旋转,海水流过该容器。旋转轴的速度使盘上的平均模拟速度为16节(海里/小时,knot)。使用经过过滤并将温度调节至25℃±2℃的天然海水。定期取出PVC盘以测量膜厚度。对盘进行漂洗并使其在室温下干燥过夜,然后测量膜厚度。结果以膜减少量的形式给出,即初始膜厚度和在给定时间测量的厚度之间的差异。当通常厚度为10μm-20μm的薄的非抛光沥滤层保留在表面上时,或者当膜完全抛光离开表面时,认为涂覆膜被彻底抛光(抛光穿过,polished through)。这在结果表中表示为PT。
通过海水中静态浸泡试验测定抗藤壶性
通过施涂一层乙烯基环氧树脂粘结涂料(Safeguard Plus,由Jotun制造)涂层和一层防污涂料(SeaQuantum Ultra S,由Jotun制造)涂层制备PVC板。通过使用间隙尺寸为400μm的膜涂布器施加本发明的防污涂料组合物,得到约120cm2的总测试面积。将干燥的测试板浸入美国佛罗里达州外的亚热带水域的海中,并定期进行检查。
抗藤壶性评级如下:
0:无
1:藤壶污损覆盖率<5%
2:藤壶污损覆盖率为5-10%
3:藤壶污损覆盖率为10-15%
4:藤壶污损覆盖率>15%
评定量表仅适用于100-150cm2的测试面积。如ASTM D6990-05,第7.5节中所述,当对涂覆膜进行评级时,排除了板上的边缘效应。
共聚物溶液S1和S9的制备过程
将53重量份二甲苯装入配有搅拌器、冷凝器、氮气入口和进料入口的温度控制反应容器中。将反应容器加热并保持在85℃的反应温度。制备以表1中给出的比例的甲基丙烯酸三异丙基甲硅烷基酯、甲基丙烯酸2-甲氧基乙酯、丙烯酸正丁酯和甲基丙烯酸甲酯,与1.0份2,2'-偶氮双(2-甲基丁腈)的预混物。在氮气氛下,在2小时内以恒定速率将预混物加入反应容器中。然后加入0.5份过氧-2-乙基己酸叔丁酯。将反应容器在反应温度下保持另外的2小时。然后将反应器加热至110℃并在该温度下保持1小时。加入30份二甲苯用于稀释,并且将反应器冷却至室温。
制备共聚物溶液S2-S8和比较共聚物溶液CS3-CS4的一般过程
将一定量的溶剂加入到配有搅拌器、冷凝器、氮气入口和进料入口的温度控制的反应容器中。将反应容器加热并保持在表1中给出的反应温度。制备单体、引发剂、溶剂和可选的链转移剂的预混物。在氮气氛下,在2小时内以恒定速率将预混物加入反应容器中。再过30分钟后,加入后添加的增效引发剂溶液。将反应容器在反应温度下保持另外的2小时。然后将反应器加热至110℃并在该温度下保持1小时。加入另外的溶剂用于稀释,并将反应器冷却至室温。
比较共聚物溶液CS1的制备过程
重复EP 2551309中用于制备甲硅烷基酯共聚物(a3-1)的制备实施例4,以制备比较共聚物溶液CS1。
将100重量份二甲苯引入装有搅拌器、冷凝器、氮气入口和进料入口的温度控制的反应容器中,并在氮气流中在85℃的温度下加热并搅拌。保持该温度,在2小时内将60份丙烯酸三异丙基甲硅烷基酯、40份甲基丙烯酸甲酯和0.3份2,2'-偶氮双(异丁腈)的混合物加入反应容器中。然后,在该温度下进行搅拌4小时,然后加入0.4份2,2'-偶氮双(异丁腈),并且在该温度下进一步进行搅拌4小时,以得到含有甲硅烷基酯共聚物的无色透明的反应混合物。
比较共聚物溶液CS2的制备过程
使用制备共聚物溶液CS1所述的过程制备共聚物溶液CS2。以表1中给出的比例使用成分。
表2.成分以重量份的涂料配方。
表3涂覆膜的抗开裂性。
表5:防污涂料性能的结果
PT=彻底抛光
表5中的结果表明,与用包含丙烯酸三异丙基甲硅烷基酯的共聚物制备的比较防污涂料(CPA1-CPA3)相比,用包含甲基丙烯酸三异丙基甲硅烷基酯的共聚物制成的防污涂料(PA1-PA9)表现出更好的储存稳定性和更受控的抛光(膜消耗)。如在防污涂料组合物(CPA4)中,包含甲基丙烯酸三异丙基甲硅烷基酯的共聚物中亲水性共聚单体的缺失,得到极慢的抛光(膜消耗)。由于美托咪定的存在,涂料实施例和比较例两者都显示出良好的抗藤壶性。
表7.用于比较防污涂料组合物的以重量份的成分。
表8:防污涂料性能的结果
表9:防污涂料性能的结果
表8和表9中的结果表明,与用包含丙烯酸三异丙基甲硅烷基酯的共聚物制备的比较防污涂料(CPB1-CPB3)相比,用包含甲基丙烯酸三异丙基甲硅烷基酯的共聚物制备的防污涂料(PB1-PB13)表现出更好的抗开裂性。如在防污涂料组合物(CPB4)中,在包含甲基丙烯酸三异丙基甲硅烷基酯的共聚物中羧酸诸如松香的缺失也会降低抗开裂性。由于美托咪定的存在,涂料实施例和比较例两者都显示出良好的抗藤壶性。
Claims (17)
1.一种防污涂料组合物,包含(i)甲硅烷基酯共聚物,所述甲硅烷基酯共聚物包含下述作为共聚单体:
(a)甲基丙烯酸三异丙基甲硅烷基酯,
(b)式(I)的化合物
其中,R1是氢或甲基,R2是环醚(诸如可选被烷基取代的氧杂环戊烷、噁烷、二氧戊环、二噁烷),并且X是C1-C4亚烷基,
和/或式(II)的化合物
其中,R3是氢或甲基,并且R4是具有至少一个氧或氮原子,优选至少一个氧原子的C3-C18取代基,以及可选地
(c)一种或多种式(III)的共聚单体
其中,R5是氢或甲基,并且R6是C1-C8烃基;
以及(ii)美托咪定。
2.根据前述权利要求中任一项所述的防污涂料组合物,其中,在所述甲硅烷基酯共聚物中组分(b)的量在2wt%-50wt%的范围内,优选在2wt%-40wt%的范围内,更优选在5wt%-35wt%的范围内。
3.根据前述权利要求中任一项所述的防污涂料组合物,其中,在所述甲硅烷基酯共聚物中(a)的量在所述共聚物的5wt%-80wt%,优选25wt%-75wt%,特别是30wt%-70wt%的范围内。
4.根据前述权利要求中任一项所述的防污涂料组合物,其中,在式(II)中,R4是式-(CH2CH2O)m-R7的基团,其中,R7是C1-C10烷基或C6-C10芳基取代基,并且m是在1至6,优选1至3范围内的整数。
5.根据权利要求4所述的防污涂料组合物,其中,R4是式-(CH2CH2O)m-R7的基团,其中,R7是C1-C10烷基取代基,优选甲基或乙基,并且m是在1至3范围内的整数,优选1或2。
6.根据前述权利要求中任一项所述的防污涂料组合物,其中,组分(b)包含丙烯酸2-甲氧基乙酯、甲基丙烯酸2-甲氧基乙酯、甲基丙烯酸2-乙氧基乙酯、丙烯酸2-(2-乙氧基乙氧基)乙酯、甲基丙烯酸2-(2-乙氧基乙氧基)乙酯、丙烯酸四氢糠基酯和甲基丙烯酸四氢糠基酯中的一种或多种。
7.根据前述权利要求中任一项所述的防污涂料组合物,包含一种或多种式(III)的非亲水性共聚单体:
其中,R5是氢或甲基,并且R6是C1-C8烃基取代基。
8.根据前述权利要求中任一项所述的防污涂料组合物,包含甲基丙烯酸甲酯和丙烯酸正丁酯中的一种或多种。
9.根据前述权利要求中任一项所述的防污涂料组合物,包含以2wt%-60wt%,优选5wt%-50wt%的量的甲基丙烯酸甲酯作为共聚单体。
10.根据前述权利要求中任一项所述的防污涂料组合物,包含以1wt%-30wt%,优选2wt%-25wt%的量的丙烯酸正丁酯作为共聚单体。
11.根据前述权利要求中任一项所述的防污涂料组合物,包含松香或其衍生物。
12.根据前述权利要求中任一项所述的防污涂料组合物,所述防污涂料组合物不含无机铜化合物。
13.根据权利要求1-12所述的防污涂料组合物,其中,所述杀菌剂包括氧化亚铜和/或吡啶硫酮铜。
14.根据前述权利要求中任一项所述的防污涂料组合物,包含硅烷,诸如四乙氧基硅烷。
15.根据前述权利要求中任一项所述的防污涂料组合物,包含硅烷,诸如四乙氧基硅烷,以及松香或其衍生物。
16.一种用于保护物体免于污损的方法,所述方法包括用根据权利要求1-15中任一项所述的防污涂料组合物涂覆经受污损的所述物体的至少一部分。
17.一种涂覆有根据权利要求1-15中任一项所述的防污涂料组合物的物体。
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