CN111533854B - 硅改性丙烯酸树脂及应用 - Google Patents
硅改性丙烯酸树脂及应用 Download PDFInfo
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- CN111533854B CN111533854B CN202010488312.7A CN202010488312A CN111533854B CN 111533854 B CN111533854 B CN 111533854B CN 202010488312 A CN202010488312 A CN 202010488312A CN 111533854 B CN111533854 B CN 111533854B
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- Prior art keywords
- silicon
- monomer
- acrylic resin
- modified acrylic
- acrylate
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- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 25
- 239000010703 silicon Substances 0.000 title claims abstract description 25
- 239000004925 Acrylic resin Substances 0.000 title claims abstract description 20
- 229920000178 Acrylic resin Polymers 0.000 title claims abstract description 20
- 239000000178 monomer Substances 0.000 claims abstract description 62
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 15
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002519 antifouling agent Substances 0.000 claims abstract description 12
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 11
- 230000009477 glass transition Effects 0.000 claims abstract description 6
- 239000003973 paint Substances 0.000 claims description 32
- 230000003373 anti-fouling effect Effects 0.000 claims description 25
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 12
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 8
- 239000000945 filler Substances 0.000 claims description 8
- 239000000049 pigment Substances 0.000 claims description 7
- 150000002148 esters Chemical class 0.000 claims description 6
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical group NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 claims description 5
- QMBQNKZNTNORAY-UHFFFAOYSA-N ethyl(trimethoxy)silane;styrene Chemical compound C=CC1=CC=CC=C1.CC[Si](OC)(OC)OC QMBQNKZNTNORAY-UHFFFAOYSA-N 0.000 claims description 5
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical group CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 3
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
- 239000011347 resin Substances 0.000 abstract description 25
- 229920005989 resin Polymers 0.000 abstract description 25
- 238000005498 polishing Methods 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 230000007774 longterm Effects 0.000 abstract 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 24
- -1 butyl ethyl Chemical group 0.000 description 19
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 13
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- 235000019400 benzoyl peroxide Nutrition 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000008096 xylene Substances 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 8
- 230000007062 hydrolysis Effects 0.000 description 7
- 238000006460 hydrolysis reaction Methods 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 6
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 4
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- RWRIWBAIICGTTQ-UHFFFAOYSA-N difluoromethane Chemical compound FCF RWRIWBAIICGTTQ-UHFFFAOYSA-N 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 125000005702 oxyalkylene group Chemical group 0.000 description 4
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000000975 bioactive effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 229920001515 polyalkylene glycol Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 2
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 2
- UJPMYEOUBPIPHQ-UHFFFAOYSA-N 1,1,1-trifluoroethane Chemical compound CC(F)(F)F UJPMYEOUBPIPHQ-UHFFFAOYSA-N 0.000 description 2
- NPNPZTNLOVBDOC-UHFFFAOYSA-N 1,1-difluoroethane Chemical compound CC(F)F NPNPZTNLOVBDOC-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 2
- ATEBGNALLCMSGS-UHFFFAOYSA-N 2-chloro-1,1-difluoroethane Chemical compound FC(F)CCl ATEBGNALLCMSGS-UHFFFAOYSA-N 0.000 description 2
- VLZDYNDUVLBNLD-UHFFFAOYSA-N 3-(dimethoxymethylsilyl)propyl 2-methylprop-2-enoate Chemical compound COC(OC)[SiH2]CCCOC(=O)C(C)=C VLZDYNDUVLBNLD-UHFFFAOYSA-N 0.000 description 2
- JSOZORWBKQSQCJ-UHFFFAOYSA-N 3-[ethoxy(dimethyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CCO[Si](C)(C)CCCOC(=O)C(C)=C JSOZORWBKQSQCJ-UHFFFAOYSA-N 0.000 description 2
- JBDMKOVTOUIKFI-UHFFFAOYSA-N 3-[methoxy(dimethyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CO[Si](C)(C)CCCOC(=O)C(C)=C JBDMKOVTOUIKFI-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- XWCDCDSDNJVCLO-UHFFFAOYSA-N Chlorofluoromethane Chemical compound FCCl XWCDCDSDNJVCLO-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 235000019445 benzyl alcohol Nutrition 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 2
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 2
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 2
- 229940112669 cuprous oxide Drugs 0.000 description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 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
- 238000011156 evaluation Methods 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 150000002697 manganese compounds Chemical class 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- IZUPBVBPLAPZRR-UHFFFAOYSA-N pentachlorophenol Chemical compound OC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl IZUPBVBPLAPZRR-UHFFFAOYSA-N 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 229930195734 saturated hydrocarbon Chemical group 0.000 description 2
- 239000013535 sea water Substances 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- WMOVHXAZOJBABW-UHFFFAOYSA-N tert-butyl acetate Chemical compound CC(=O)OC(C)(C)C WMOVHXAZOJBABW-UHFFFAOYSA-N 0.000 description 2
- 229930195735 unsaturated hydrocarbon Chemical group 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- HHQAGBQXOWLTLL-UHFFFAOYSA-N (2-hydroxy-3-phenoxypropyl) prop-2-enoate Chemical compound C=CC(=O)OCC(O)COC1=CC=CC=C1 HHQAGBQXOWLTLL-UHFFFAOYSA-N 0.000 description 1
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- LTQBNYCMVZQRSD-UHFFFAOYSA-N (4-ethenylphenyl)-trimethoxysilane Chemical compound CO[Si](OC)(OC)C1=CC=C(C=C)C=C1 LTQBNYCMVZQRSD-UHFFFAOYSA-N 0.000 description 1
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 1
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 description 1
- LGJCFVYMIJLQJO-UHFFFAOYSA-N 1-dodecylperoxydodecane Chemical compound CCCCCCCCCCCCOOCCCCCCCCCCCC LGJCFVYMIJLQJO-UHFFFAOYSA-N 0.000 description 1
- ITUNZCVRYICLQM-UHFFFAOYSA-N 1-ethenyl-1,2,4-triazole Chemical compound C=CN1C=NC=N1 ITUNZCVRYICLQM-UHFFFAOYSA-N 0.000 description 1
- JWYVGKFDLWWQJX-UHFFFAOYSA-N 1-ethenylazepan-2-one Chemical compound C=CN1CCCCCC1=O JWYVGKFDLWWQJX-UHFFFAOYSA-N 0.000 description 1
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 1
- LEWNYOKWUAYXPI-UHFFFAOYSA-N 1-ethenylpiperidine Chemical compound C=CN1CCCCC1 LEWNYOKWUAYXPI-UHFFFAOYSA-N 0.000 description 1
- KMTMJNIEJGRRFY-UHFFFAOYSA-N 1h-pyridine-2-thione;zinc Chemical compound [Zn].SC1=CC=CC=N1 KMTMJNIEJGRRFY-UHFFFAOYSA-N 0.000 description 1
- AVTLBBWTUPQRAY-UHFFFAOYSA-N 2-(2-cyanobutan-2-yldiazenyl)-2-methylbutanenitrile Chemical compound CCC(C)(C#N)N=NC(C)(CC)C#N AVTLBBWTUPQRAY-UHFFFAOYSA-N 0.000 description 1
- 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 1
- PTDJGJIYBSUQLM-UHFFFAOYSA-N 2-(2-methylpropoxy)ethyl 2-methylprop-2-enoate Chemical compound CC(C)COCCOC(=O)C(C)=C PTDJGJIYBSUQLM-UHFFFAOYSA-N 0.000 description 1
- BHNHCQUVVRPWPB-UHFFFAOYSA-N 2-(2-methylpropoxy)ethyl prop-2-enoate Chemical compound CC(C)COCCOC(=O)C=C BHNHCQUVVRPWPB-UHFFFAOYSA-N 0.000 description 1
- ILHMVNZWPBUYKQ-UHFFFAOYSA-N 2-(diethoxymethylsilyl)ethyl prop-2-enoate Chemical compound C(C=C)(=O)OCC[SiH2]C(OCC)OCC ILHMVNZWPBUYKQ-UHFFFAOYSA-N 0.000 description 1
- IGRYVRNQZARURF-UHFFFAOYSA-N 2-(dimethoxymethylsilyl)ethyl 2-methylprop-2-enoate Chemical compound COC(OC)[SiH2]CCOC(=O)C(C)=C IGRYVRNQZARURF-UHFFFAOYSA-N 0.000 description 1
- BWBNNRRMRAJDBA-UHFFFAOYSA-N 2-(dimethoxymethylsilyl)ethyl prop-2-enoate Chemical compound C(C=C)(=O)OCC[SiH2]C(OC)OC BWBNNRRMRAJDBA-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
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- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000005028 tinplate Substances 0.000 description 1
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- 230000007704 transition Effects 0.000 description 1
- KEROTHRUZYBWCY-UHFFFAOYSA-N tridecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCOC(=O)C(C)=C KEROTHRUZYBWCY-UHFFFAOYSA-N 0.000 description 1
- UZIAQVMNAXPCJQ-UHFFFAOYSA-N triethoxysilylmethyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)COC(=O)C(C)=C UZIAQVMNAXPCJQ-UHFFFAOYSA-N 0.000 description 1
- WDUXKFKVDQRWJN-UHFFFAOYSA-N triethoxysilylmethyl prop-2-enoate Chemical compound CCO[Si](OCC)(OCC)COC(=O)C=C WDUXKFKVDQRWJN-UHFFFAOYSA-N 0.000 description 1
- RKLXSINPXIQKIB-UHFFFAOYSA-N trimethoxy(oct-7-enyl)silane Chemical compound CO[Si](OC)(OC)CCCCCCC=C RKLXSINPXIQKIB-UHFFFAOYSA-N 0.000 description 1
- SYYDEXILBJXXIA-UHFFFAOYSA-N trimethoxy(pent-4-enyl)silane Chemical compound CO[Si](OC)(OC)CCCC=C SYYDEXILBJXXIA-UHFFFAOYSA-N 0.000 description 1
- LFRDHGNFBLIJIY-UHFFFAOYSA-N trimethoxy(prop-2-enyl)silane Chemical compound CO[Si](OC)(OC)CC=C LFRDHGNFBLIJIY-UHFFFAOYSA-N 0.000 description 1
- YQIZKGWCIRJWKB-UHFFFAOYSA-N trimethoxy-(4-prop-1-en-2-ylphenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=C(C(C)=C)C=C1 YQIZKGWCIRJWKB-UHFFFAOYSA-N 0.000 description 1
- UOKUUKOEIMCYAI-UHFFFAOYSA-N trimethoxysilylmethyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)COC(=O)C(C)=C UOKUUKOEIMCYAI-UHFFFAOYSA-N 0.000 description 1
- JPPHEZSCZWYTOP-UHFFFAOYSA-N trimethoxysilylmethyl prop-2-enoate Chemical compound CO[Si](OC)(OC)COC(=O)C=C JPPHEZSCZWYTOP-UHFFFAOYSA-N 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
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- NDKWCCLKSWNDBG-UHFFFAOYSA-N zinc;dioxido(dioxo)chromium Chemical compound [Zn+2].[O-][Cr]([O-])(=O)=O NDKWCCLKSWNDBG-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及树脂制造技术领域，具体的更涉及硅改性丙烯酸树脂及应用。一种用于硅改性丙烯酸树脂，包括以乙烯基聚合单体为主体，在亲水单体存在下接枝共聚含硅单体得到；其中，所述硅改性丙烯酸树脂的数均分子量为10000～30000，玻璃化转变温度为30～45℃。通过以乙烯基聚合单体为主体，在亲水单体存在下接枝共聚含硅单体，制备得到的树脂能稳定的水解，提供长效的自抛光性，从而获得有良好的、长期的防污剂释放性。
Description
技术领域
本发明涉及树脂制造技术领域，具体的更涉及硅改性丙烯酸树脂及应用。
背景技术
海洋防污涂料有很多种类，但是目前，海洋防污涂料使用最广泛，效果最优的防污涂料是自抛光型防污涂料。在自抛光防污涂料组成成分中，成膜树脂是最为关键的技术，自抛光涂料的抛光效果是成膜树脂的水解作用产生的。因此，如何对树脂进行合成也成了研究的热点。一般由锌、铜、硅类改性的丙烯酸树脂为主要方向，其中以硅改性的效果最优、时效性最好，但控制难度也最大、成本也最高。
目前有机硅改性羟基丙烯酸树脂的制备主要是通过乳液聚合制备的，这种制备方法制得的有机硅改性羟基丙烯酸乳液的粒子粒径范围为30-500nm，涂膜的外观一般较差、光泽度较差。人们也有尝试采用含乙烯基的硅氧烷单体和乙烯基聚合单体进行溶液聚合，如US5795374公开了由船舶防污涂料用的含有三有机甲硅烷基的聚合物，但是所制备的聚合物薄膜水解速率非常低，根本无法应用于“高污染环境”，如内海或者允许船舶停在这种环境的国家的海域，或者船舶频繁停泊或者低速行驶的国家的这种海域。EP1127902A1中介绍了三有机甲硅烷基的聚合物在PH＝13的碱溶液中的水解速度大约是在0到很小的范围之间，而且几乎不依赖可水解硅基团的含量，根本无法满足高抛光速率用的防污涂料需求。中国专利CN103131289B中以有机甲硅烷基丙烯酸酯和含氟(甲基)丙烯酸酯共聚来获得自抛光性能及低表面性能的基体树脂，憎水憎油，但是以此树脂基体制备的防污涂料又严重依赖船速。此外，基于硅氧烷的水解问题，有机硅改性的分散体稳定性不是很好，容易发生分层及凝聚现象，限制了产品的应用。
发明内容
除非另有说明、从上下文暗示或属于现有技术的惯例，否则本申请中所有的份数和百分比都基于重量，且所用的测试和表征方法都是与本申请的提交日期同步的。如果现有技术中披露的具体术语的定义与本申请中提供的任何定义不一致，则以本申请中提供的术语定义为准。
本发明中的词语“优选的”、“优选地”、“更优选的”等是指，在某些情况下可提供某些有益效果的本发明实施方案。然而，在相同的情况下或其他情况下，其他实施方案也可能是优选的。此外，对一个或多个优选实施方案的表述并不暗示其他实施方案不可用，也并非旨在将其他实施方案排除在本发明的范围之外。本发明中未提及的组分的来源均为市售。
本发明人为了解决上述问题经过认真研究后发现，通过以乙烯基聚合单体为主体，在亲水单体存在下接枝共聚含硅单体，制备得到的树脂能稳定的水解，提供长效的自抛光性，从而获得有良好的、长期的防污剂释放性。
本发明第一个方面提供了一种用于硅改性丙烯酸树脂，包括以乙烯基聚合单体为主体，在亲水单体存在下接枝共聚含硅单体得到；其中，所述硅改性丙烯酸树脂的数均分子量为10000～30000，玻璃化转变温度为30～45℃。
通过使用凝胶渗透色谱(GPC)来测定聚合物的分子量分布。四氢呋喃(THF)用作溶剂，聚苯乙烯作为参考。通过使用T.G.Fox(Bull.Am.Phys.Soc.,1,123,1956)所述的方程式(I)来计算玻璃化转变温度。
在本发明的一些实施方式中，所述乙烯基聚合单体选自丙烯酸、丙烯酸的酯、乙烯基酰胺以及杂环取代的上述单体中的至少一种。
例如丙烯酸和丙烯酸的酯的实例，如丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丙酯、丙烯酸异丙酯、丙烯酸正丁酯、丙烯酸异丁酯、丙烯酸叔丁酯、丙烯酸丁基乙酯、丙烯酸戊酯、丙烯酸己酯、丙烯酸环己酯、丙烯酸苯酯、丙烯酸正辛酯、丙烯酸异辛酯、丙烯酸2-乙基己酯、丙烯酸3,5,5-三甲基己酯、丙烯酸十二烷基酯、丙烯酸十六烷基酯、丙烯酸十八烷基酯、丙烯酸2-羟乙酯、丙烯酸2-羟丙酯、丙烯酸4-羟丁酯、丙烯酸2-羟基-3-苯氧基丙酯、丙烯酸2-甲氧基乙酯、丙烯酸甲氧基丙酯、丙烯酸2-乙氧基乙酯、丙烯酸乙氧基丙酯、丙烯酸丙氧基乙酯、丙烯酸丁氧基乙酯、丙烯酸异丁氧基乙酯、丙烯酸苯氧基乙酯；
其中，作为甲基丙烯酸和甲基丙烯酸的酯的实例，如甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丙酯、甲基丙烯酸异丙酯、甲基丙烯酸正丁酯、甲基丙烯酸异丁酯、甲基丙烯酸叔丁酯、甲基丙烯酸戊酯、甲基丙烯酸己酯、甲基丙烯酸环己酯、甲基丙烯酸苯酯、甲基丙烯酸苄酯、甲基丙烯酸十三烷基酯、甲基丙烯酸十二烷基酯、甲基丙烯酸十八烷基酯、甲基丙烯酸2-乙基己酯、甲基丙烯酸2-羟乙酯、甲基丙烯酸2-羟丙酯、甲基丙烯酸甲氧基乙酯、甲基丙烯酸2-乙氧基乙酯、甲基丙烯酸乙氧基丙酯、甲基丙烯酸丙氧基乙酯、甲基丙烯酸2-丁氧基乙酯、甲基丙烯酸异丁氧基乙酯、甲基丙烯酸异丁氧基丁基二甘醇酯、甲基丙烯酸苯氧基乙酯、(甲基)丙烯酸2-氨基乙基酯、(甲基)丙烯酸二甲氨基乙基酯、(甲基)丙烯酸2-二乙氨基乙基酯、(甲基)丙烯酸3-氨基丙基酯、(甲基)丙烯酸2-丁基氨基乙基酯、(甲基)丙烯酸叔丁基氨基乙基酯。
作为乙烯基酰胺的实例，如丙烯酰胺、甲基丙烯酰胺、N-甲基丙烯酰胺、N-乙基丙烯酰胺、N-丙基丙烯酰胺、顺丁烯二酰亚胺、N-乙烯基酰胺，如N-乙烯基甲酰胺、N-乙烯基乙酰胺、N-乙烯基丙酰胺及如WO0162811中所述的其它N-乙烯基酰胺、N-乙烯基内酰胺，如N-乙烯基吡咯烷酮、N-乙烯基哌啶、N-乙烯基己内酰胺；
杂环取代的丙烯酸酯和甲基丙烯酸酯，如(甲基)丙烯酸糠酯、(甲基)丙烯酸四氢糠酯；杂环取代的乙烯基单体，如乙烯基咪唑、2-乙烯基嘧啶、4-乙烯基嘧啶、1-乙烯基-1,2,4-三唑、2-乙烯基-1,3-二氧戊环。
在本发明的一种优选的实施方式中，所述乙烯基聚合单体选自丙烯酸、甲基丙烯酸、丙烯酸丁酯、甲基丙烯酸丁酯、丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸乙酯、丙烯酸异冰片酯和丙烯酸异辛酯中的任意两种或多种的混合物。上述单体中，优选上述甲基丙烯酸酯单体的量为乙烯基聚合单体的90～100wt％、共聚用除甲基丙烯酸酯单体之外的另一种或多种的乙烯基聚合单体的量为0～10wt％。
在本发明的一种优选的实施方式中，所述含硅单体为含双键有机硅单体；其具有如下通式：Rn(CH2＝CH)mSiO(4-n-m)/2，其中，R选自取代或未取代的C1-10的烷基、羟基、苯基、氨基，n、m满足0≦n＜4，0＜m≦4，0＜n+m≦4。
在本发明的一种更优选的实施方式中，所述R选自羟基、甲基、苯基，n、m满足0≦n＜4，0＜m≦4，0＜n+m≦4。
作为含双键有机硅单体的实例，可以列举：具有乙烯基作为端基或侧链基团的聚二甲基硅氧烷、聚二苯基硅氧烷、聚甲基苯基硅氧烷或其中2种或3种的无规或嵌段共聚物、1,3-二乙烯基四甲基二硅氧烷、1,3,5,7-四乙烯基环四硅氧烷等。其次，作为含双键有机硅单体还可以是(甲基)丙烯酰氧基亚烷基烷氧基硅烷、直链和/或支链的烯基烷氧基硅烷、芳族不饱和烷氧基硅烷。合适的(甲基)丙烯酰氧基亚烷基烷氧基硅烷包括丙烯酰氧基甲基三甲氧基硅烷、丙烯酰氧基甲基二甲氧基甲基硅烷、丙烯酰氧基甲基甲氧基二甲基硅烷、甲基丙烯酰氧基甲基三甲氧基硅烷、甲基丙烯酰氧基甲基二甲氧基甲基硅烷、甲基丙烯酰氧基甲基甲氧基二甲基硅烷、2-丙烯酰氧基乙基三甲氧基硅烷、2-丙烯酰氧基乙基二甲氧基甲基硅烷、2-丙烯酰氧基乙基甲氧基二甲基硅烷、2-甲基丙烯酰氧基乙基三甲氧基硅烷、2-甲基丙烯酰氧基乙基二甲氧基甲基硅烷、2-甲基丙烯酰氧基乙基甲氧基二甲基硅烷、3-丙烯酰氧基丙基三甲氧基硅烷、3-丙烯酰氧基丙基二甲氧基甲基硅烷、3-丙烯酰氧基丙基甲氧基二甲基硅烷、3-甲基丙烯酰氧基丙基三甲氧基硅烷、3-甲基丙烯酰氧基丙基二甲氧基甲基硅烷、3-甲基丙烯酰氧基丙基甲氧基二甲基硅烷、8-丙烯酰氧基辛基三甲氧基硅烷、8-甲基丙烯酰氧基辛基三甲氧基硅烷、丙烯酰氧基甲基三乙氧基硅烷、丙烯酰氧基甲基二乙氧基甲基硅烷、丙烯酰氧基甲基乙氧基二甲基硅烷、甲基丙烯酰氧基甲基三乙氧基硅烷、甲基丙烯酰氧基甲基二乙氧基甲基硅烷、甲基丙烯酰氧基甲基乙氧基二甲基硅烷、2-丙烯酰氧基乙基三乙氧基硅烷、2-丙烯酰氧基乙基二乙氧基甲基硅烷、2-丙烯酰氧基乙基乙氧基二甲基硅烷、2-甲基丙烯酰氧基乙基三乙氧基硅烷、2-甲基丙烯酰氧基乙基二乙氧基甲基硅烷、2-甲基丙烯酰氧基乙基乙氧基二甲基硅烷、3-丙烯酰氧基丙基三乙氧基硅烷、3-丙烯酰氧基丙基二乙氧基甲基硅烷、3-丙烯酰氧基丙基乙氧基二甲基硅烷、3-甲基丙烯酰氧基丙基三乙氧基硅烷、3-甲基丙烯酰氧基丙基二乙氧基甲基硅烷、3-甲基丙烯酰氧基丙基乙氧基二甲基硅烷、8-丙烯酰氧基辛基三乙氧基硅烷、8-甲基丙烯酰氧基辛基三乙氧基硅烷。
合适的直链和/或支链的烯基烷氧基硅烷的实例，如乙烯基三甲氧基硅烷、乙烯基二甲氧基甲基硅烷、乙烯基甲氧基二甲基硅烷、烯丙基三甲氧基硅烷、烯丙基二甲氧基甲基硅烷、烯丙基甲氧基二甲基硅烷、甲基丙烯酰基三甲氧基硅烷、甲基丙烯酰基二甲氧基甲基硅烷、甲基丙烯酰基甲氧基二甲基硅烷、4-三甲氧基甲硅烷基-1-丁烯、5-三甲氧基甲硅烷基-1-戊烯、6-三甲氧基甲硅烷基-1-己烯、7-三甲氧基甲硅烷基-1-庚烯、8-三甲氧基甲硅烷基-1-辛烯。
合适的芳族不饱和烷氧基硅烷的实例，如对三甲氧基甲硅烷基苯乙烯、1,4-二乙烯基-2-三甲氧基甲硅烷基苯、对三甲氧基甲硅烷基-α-甲基苯乙烯。以上它含双键有机硅单体可以单独使用或以混合物的形式使用。具体的是，由于获得较佳的反应性，优选3-甲基丙烯酰氧基丙基三甲氧基硅烷(KH570)和苯乙烯乙基三甲氧基硅烷。如果KH570含量过高，则产品往往会丧失贮存稳定性，而针对这一问题，优选使用KH570和苯乙烯乙基三甲氧基硅烷混合物，苯环的存在提高涂层硬度的同时，增加了聚合后树脂的分子量，促进与颜填料这种生物活性物质的相互作用，使其能被更好的固定在涂层之中，最后随着树脂水解被释放。
在本发明的一种优选的实施方式中，所述亲水单体中含有至少一个亲水基团、至少一个碳碳双键；更优选亲水基团为氧化亚烷基的含双键的亲水单体。其中氧化亚烷基优选具有2-6个碳原子的氧化亚烷基；氧化亚烷基的数目可以为从2至200，优选3-50，尤其是4-30。
作为适合本发明的亲水单体，例如聚亚烷基二醇单(甲基)丙烯酸酯、聚亚烷基二醇二(甲基)丙烯酸酯、聚乙二醇单甲基丙烯酸酯、聚丙二醇单甲基丙烯酸酯、甲氧基聚乙二醇甲基丙烯酸酯。
在本发明的一种优选的实施方式中，作为上述合适的亲水单体具有如下通式：CH2＝CX1COO-(RO)n-X2(Ⅰ)；其中X1是氢原子或甲基；X2是氢原子或不饱和的或饱和的具有1-22个碳原子的烃基；R是具有2-6个碳原子的亚烷基；并且n为4-30的整数。
在本发明的一种优选的实施方式中，所述X1是氢原子或甲基；X2是氢原子或不饱和的或饱和的具有1-12个碳原子的烃基；R为亚乙基或亚异丙基；并且n为4-20的整数。
在本发明的一种更优选的实施方式中，所述亲水单体包括如下结构式的化合物：
CH2＝CX1COO-(CH2CH2O)n-H；
CH2＝CX1-(CH2CH2O)n-CH3；
CH2＝CX1COO-(CH2CH(CH3)O)n-H；
CH2＝CX1COO-(CH2CH(CH3)O)n-CH3；
CH2＝CX1COO-(CH2CH2O)5-(CH2CH(CH3)O)2-H；
CH2＝CX1COO-(CH2CH2O)5-(CH2CH(CH3)O)3-CH3；
CH2＝CX1COO-(CH2CH2O)6-(CH2CH(CH3)O)3-H；
CH2＝CX1COO-(CH2CH2O)8-(CH2CH(CH3)O)6-CH2CH(C2H5)C4H9；
CH2＝CX1COO-(CH2CH2O)23-OOC(CH3)C＝CH2；
CH2＝CX1COO-(CH2CH2O)20-(CH2CH(CH3)O)5-CH2-CH＝CH2。
在较佳的一种实施方式中，亲水单体选为Bisomer系列产品，例如包括BisomerPEM63P HD、Bisomer PPM5 LI、Bisomer PEM6 LD、Bisomer MPEG550MA，因为分子中具有特殊的亲水基团，能够和体系中的丙烯酸树脂相容在一起，现有的一些技术中会采用(甲基)丙烯酸羟酯等，但在聚合时硅羟基发生反应，导致体系容易凝胶反应性不好，本发明人采用该特殊结构的亲水单体避免以上问题的同时，意外发现涂层具有优异的耐污性能，可能是因为其分子链中含有的亚烷基结构工整，分子链排列紧密，与丙烯酸内聚力强，亲水单体的氧原子的电子云密度比硅氧键的电子云密度低，平衡了溶剂极化作用力，利于形成具有均匀厚度和性能的膜，在海水中，树脂中由于亲水键的存在，酯化连接键会更容易打开，进一步促进树脂的水解亲和力。
本发明所述硅改性丙烯酸树脂是以乙烯基聚合单体为主体，在亲水单体存在下接枝共聚含硅单体得到；制备方法为将乙烯基聚合单体、亲水单体、含硅单体在适合的聚合方法中在适合溶剂中利用适当的引发剂将上述单体进行聚合得到。
适合的聚合方法包括如溶液聚合、本体聚合、半分批聚合、配位聚合、悬浮聚合或乳液聚合中的自由基或离子聚合。在本发明中更优选为溶液聚合。
适合的溶剂包括使用水；芳烃，如二甲苯、石油溶剂油、甲苯；脂肪烃，如己烷和庚烷；氯代烃，如二氯甲烷、三氯乙烷、四氯乙烷；氟代烃，如二氟甲烷、二氟乙烷、三氟乙烷、四氟乙烷；氟氯-脂肪烃和芳烃，如氯氟甲烷、氯二氟乙烷、对氯三氟甲苯；酮，如丙酮、甲基乙基酮、甲基异丁基酮、环己酮；酯，如乙酸甲酯、乙酸乙酯、乙酸丁酯、乙酸叔丁酯、乙酸乙二醇甲醚酯；醚，如乙二醇二甲醚、二乙二醇二甲醚、二丁基醚、二噁烷、四氢呋喃；醇，如甲醇、乙醇、丙醇、异丙醇、丁醇、苄醇；醚醇，如丁氧基乙醇、丙二醇单甲醚；酰胺，如N-甲基吡咯烷酮、二甲基甲酰胺；或二甲亚砜；以上溶剂可以单独使用也可以两种以上混合使用，优选二甲苯和丁醇的混合物，其中，二甲苯和丁醇的质量比为4～1.5：1。
适合的自由基引发剂包括过氧化物(如过氧化苯甲酰、二叔丁基过氧化物、二癸酰基过氧化物和双十二烷基过氧化物、叔丁基-过氧化-2-乙基己酸酯、叔丁基-过氧化新戊酸酯、叔丁基-过氧化二乙基乙酸酯、叔戊基-过氧化-2-乙基己酸酯和2,5-二甲基-2,5-二(2-乙基己酰基过氧化)己烷)和偶氮化合物(如2,2’-偶氮双(异丁腈)和2,2’-偶氮双(2-甲基丁腈))；优选过氧化二苯甲酰、过氧化苯甲酸叔丁酯、过氧化二叔丁基或过氧化环己酮中的至少一种。
本发明第二个方面提供了上述硅改性丙烯酸树脂在防污涂料中的应用。这种防污涂料由于含有防污剂，可利用适合水解的树脂成分精确控制生物活性物质比如防污剂的释放速率。这种适合水解的树脂成分从非水解、机械较强的不溶聚合物到水解、机械较弱的部分溶解聚合物的转变导致涂料具有独特的防污特性。
本发明第三个方面提供了一种海洋防污漆，包括所述的硅改性丙烯酸树脂；还包括溶剂、防污剂以及颜填料。
防污剂包括无机防污剂以及有机防污剂；通常无机防污剂最为常见，例如包括不同的铜化合物，如氧化物、盐、金属和合金，它们可以单独使用或者两种以上组合使用。具体的说，优选氧化铜、硫氰酸铜、金属铜及金属铜镍、甲基硼酸钡。通常这类防污剂在防污漆中含量小于干漆70wt％，优选小于60wt％，特别优选小于50wt％。有机防污剂包括有机金属化合物包括有机铜、锌和锰化合物。有机铜化合物的实例包括2-巯基吡啶铜、铜、8-羟基喹啉铜、壬基苯酚磺酸铜、环烷酸铜、乙酸铜、双(乙二胺)双十二烷基苯磺酸铜和双(五氯苯酚)铜。有机锌化合物的实例包括2-巯基吡啶锌、二甲基二硫代氨基甲酸锌、乙烯-双(二硫代氨基甲酸)锌及用锌盐配合的乙烯-双(二硫代氨基甲酸)锰的聚合物。有机锰化合物的实例是乙烯-双(二硫代氨基甲酸)锰的聚合物。通常有机和有机防污剂在组合使用时，用量需小于各自单独使用的量，具体的说，优选含量小于干漆30wt％，更优选小于20wt％。
溶剂的实例包括水；芳烃如二甲苯、石油溶剂油、含芳烃量高的溶剂、甲苯；脂肪烃，如己烷和庚烷；氯代烃，如二氯甲烷、三氯乙烷、四氯乙烷；氟代烃，如二氟甲烷、二氟乙烷、三氟乙烷、四氟乙烷；氟氯-脂肪烃和芳烃，如氯氟甲烷、氯二氟乙烷、对氯三氟甲苯；酮，如丙酮、甲基乙基酮、甲基异丁基酮、环己酮；酯，如乙酸甲酯、乙酸乙酯、乙酸丁酯、乙酸叔丁酯、乙酸乙二醇甲醚酯；醚，如乙二醇二甲醚、二乙二醇二甲醚、二丁基醚、二噁烷、四氢呋喃；醇，如甲醇、乙醇、丙醇、异丙醇、丁醇、苄醇；醚醇，如丁氧基乙醇、丙二醇单甲醚；酰胺，如N-甲基吡咯烷酮、二甲基甲酰胺；或溶剂，如二甲亚砜；任选上述溶剂的混合物。
在许多海洋防污漆中，颜填料的重要性质是水溶解程度，可分为对水敏感或在水中可溶及对水不敏感或在水中不可溶的。第一类包括具有生物活性的颜填料，这些实例包括氧化亚铜、硫氰酸亚铜、氧化锌、氯化银、氧化银、氟化钙、磷酸氢钙、磷酸钙、硅酸钙、碳酸铁、羰基铁、氢氧化镁、二氢氧化镁、碳酸镁、碳酸锰、铬酸锌、碳酸锌、硫化锌。一般在防污漆中这类颜填料可用来调节漆的抛光速率，可单独使用或组合使用，含量小于干漆60wt％，更优选小于干漆20wt％。
第二类水不溶的颜填料，其可降低漆的抛光速率。这些实例包括滑石、白云石、钙碳酸、云母、硫酸钡、高岭土、硅藻土、珍珠岩、氧化镁、方解石和石英粉、二氧化钛、氧化铁、石墨和炭黑。这类颜填料通常与上述的第一类水可溶的成分组合使用，含量小于干漆60wt％，更优选小于干漆20wt％。
具体实施方式
下面通过实施例对本发明进行具体的描述，以下实施例只能用于本发明做进一步说明，并不能理解为本发明保护的限制，该领域的专业技术人员根据上述发明的内容作出的非本质的改正和调整，仍属于本发明的保护的范围。
Bisomer PEM6 LD为聚乙二醇(6)单甲基丙烯酸酯，结构式如下：
Bisomer PPM5LI为聚丙二醇(5)单甲基丙烯酸酯，结构式如下：
BisomerPEM63P HD为聚亚烷基二醇单甲基丙烯酸酯，结构式如下：
Bisomer MPEG550MA为甲氧基聚乙二醇(550)单甲基丙烯酸酯，结构式如下：
Bisomer S20W为甲氧基聚乙二醇甲基丙烯酸酯的水溶液，结构式如下：
市购得到。
实施例1
将二甲苯和丁醇(80mL，3：1)投入反应釜中，升温至100℃，滴加溶有0.4g过氧化二苯甲酰的混合单体，混合单体为甲基丙烯酸乙酯(53g)、丙烯酸异辛酯(3g)、KH570(15g)、苯乙烯乙基三甲氧基硅烷(10g)、Bisomer PEM63P HD(19g)；滴加完成后同温维持2h，再加入过氧化二苯甲酰0.05g，至单体转化率99％以上得到该树脂计A1。
实施例2
将二甲苯和丁醇(80mL，3：1)投入反应釜中，升温至100℃，滴加溶有0.4g过氧化二苯甲酰的混合单体，混合单体为甲基丙烯酸丁酯(66g)、丙烯酸异冰片酯(3.4g)、KH570(15g)、苯乙烯乙基三甲氧基硅烷(10g)、Bisomer PEM63P HD(19g)；滴加完成后同温维持2h，再加入过氧化二苯甲酰0.05g，至单体转化率99％以上得到该树脂计A2。
实施例3
将二甲苯和丁醇(80mL，3：1)投入反应釜中，升温至100℃，滴加溶有0.4g过氧化二苯甲酰的混合单体，混合单体为甲基丙烯酸丁酯(66g)、丙烯酸异冰片酯(3.4g)、KH570(15g)、苯乙烯乙基三甲氧基硅烷(10g)、Bisomer PPM5 LI(14g)；滴加完成后同温维持2h，再加入过氧化二苯甲酰0.05g，至单体转化率99％以上得到该树脂计A3。
实施例4
将二甲苯和丁醇(80mL，3：1)投入反应釜中，升温至100℃，滴加溶有0.4g过氧化二苯甲酰的混合单体，混合单体为甲基丙烯酸乙酯(53g)、丙烯酸异辛酯(3g)、KH570(15g)、苯乙烯乙基三甲氧基硅烷(10g)、Bisomer PEM6LD(14g)；滴加完成后同温维持2h，再加入过氧化二苯甲酰0.05g，至单体转化率99％以上得到该树脂计A4。
实施例5
将二甲苯和丁醇(80mL，3：1)投入反应釜中，升温至100℃，滴加溶有0.4g过氧化二苯甲酰的混合单体，混合单体为甲基丙烯酸乙酯(53g)、丙烯酸异辛酯(3g)、KH570(15g)、苯乙烯乙基三甲氧基硅烷(10g)、Bisomer MPEG550MA(22g)；滴加完成后同温维持2h，再加入过氧化二苯甲酰0.05g，至单体转化率99％以上得到该树脂计A5。
比较例1
将二甲苯和丁醇(80mL，3：1)投入反应釜中，升温至100℃，滴加溶有0.4g过氧化二苯甲酰的混合单体，混合单体为甲基丙烯酸乙酯(53g)、丙烯酸异辛酯(3g)、KH570(15g)、苯乙烯乙基三甲氧基硅烷(10g)、Bisomer S20W(19g)；滴加完成后同温维持2h，再加入过氧化二苯甲酰0.05g，至单体转化率99％以上得到该树脂计A6。
比较例2
将二甲苯和丁醇(80mL，3：1)投入反应釜中，升温至100℃，滴加溶有0.4g过氧化二苯甲酰的混合单体，混合单体为甲基丙烯酸乙酯(53g)、丙烯酸异辛酯(3g)、KH570(15g)、苯乙烯乙基三甲氧基硅烷(10g)；滴加完成后同温维持2h，再加入过氧化二苯甲酰0.05g，至单体转化率99％以上得到该树脂计A7。
比较例3
将二甲苯和丁醇(80mL，3：1)投入反应釜中，升温至100℃，滴加溶有0.4g过氧化二苯甲酰的混合单体，混合单体为甲基丙烯酸乙酯(53g)、丙烯酸异辛酯(3g)、KH570(25g)、Bisomer PEM63P HD(19g)；滴加完成后同温维持2h，再加入过氧化二苯甲酰0.05g，至单体转化率99％以上得到该树脂计A8。
性能评价
实施例1-5以及比较例1-3得到的树脂A1-A8涂于马口铁片上，自然风干一周后，将涂膜刮下，与KBr压片进行红外测试(德国Bruker公司的Vector-22红外光谱仪，测试范围400～4000cm-1)，结果显示1640cm-1处的碳碳双键吸收峰消失，证明双键被反应完全，在1135cm-1处出现Si-O-C的吸收峰以及1064cm-1处出现Si-O-C的吸收峰证明单体被反应完全成功接枝。通过使用凝胶渗透色谱(GPC)来测定聚合物的分子量分布，四氢呋喃(THF)用作溶剂，聚苯乙烯作为参考，40℃下得树脂A1-A8的数均分子量10000～30000；玻璃化转变温度按照GB/T19466.2-2004标准通过差示扫描量热仪测试，样品皿类型：Al，吹扫气体流速(氮气：99.999％)：50ml/min得树脂A1-A8的玻璃化转变温度为30～45℃。
将实施例1-5以及比较例1-3得到的树脂A1-A8制成防污漆，防污漆组成如下：二甲苯80g、树脂A 50g、氧化亚铜(Cu2O)15g，吡啶硫酮铜5g、红氧化铁20g、有机膨润土2g。
1.防污效果测试
测试方法：在玻璃纤维增强塑料(FRP板25cm×35cm)板上涂覆300μm防污漆，待干燥后将其浸在海水中(天津港南10码头，深度为0.5m处)。分别在3个月和6个月目测生物污染物在板上的附着情况并从1-5给出评价结果，数值越大表示附着量越多，性能越差。
2、膜水解程度测试
将上述的涂覆防污漆板固定在救生艇的叶轮上，使叶轮在海水中以15海里/h进行旋转。1个月后，测量防污漆厚度。
表1
Claims (5)
1.一种用于防污涂料的硅改性丙烯酸树脂，其特征在于，包括以乙烯基聚合单体为主体，在亲水单体存在下接枝共聚含硅单体得到；其中，所述硅改性丙烯酸树脂的数均分子量为10000～30000；
所述含硅单体为3-甲基丙烯酰氧基丙基三甲氧基硅烷和苯乙烯乙基三甲氧基硅烷；
所述亲水单体为Bisomer系列产品，包括PEM63P HD、Bisomer PPM5 LI、Bisomer PEM6LD、Bisomer MPEG550MA中的任意一种或多种。
2.如权利要求1所述的用于防污涂料的硅改性丙烯酸树脂，其特征在于，所述硅改性丙烯酸树脂的玻璃化转变温度为30～45℃。
3.如权利要求1所述的用于防污涂料的硅改性丙烯酸树脂，其特征在于，所述乙烯基聚合单体选自丙烯酸、丙烯酸的酯、乙烯基酰胺以及杂环取代的上述单体中的至少一种。
4.一种海洋防污漆，其特征在于，包括权利要求1-3中任一项所述的硅改性丙烯酸树脂。
5.如权利要求4所述的海洋防污漆，其特征在于，还包括溶剂、防污剂以及颜填料。
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