CN117447641A - Water-based self-polishing antifouling resin, preparation method and application thereof - Google Patents
Water-based self-polishing antifouling resin, preparation method and application thereof Download PDFInfo
- Publication number
- CN117447641A CN117447641A CN202311157272.8A CN202311157272A CN117447641A CN 117447641 A CN117447641 A CN 117447641A CN 202311157272 A CN202311157272 A CN 202311157272A CN 117447641 A CN117447641 A CN 117447641A
- Authority
- CN
- China
- Prior art keywords
- monomer
- aqueous
- self
- polishing
- oily
- 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.)
- Pending
Links
- 238000005498 polishing Methods 0.000 title claims abstract description 203
- 230000003373 anti-fouling effect Effects 0.000 title claims abstract description 169
- 239000011347 resin Substances 0.000 title claims abstract description 168
- 229920005989 resin Polymers 0.000 title claims abstract description 168
- 238000002360 preparation method Methods 0.000 title claims abstract description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 92
- 239000000178 monomer Substances 0.000 claims description 400
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 201
- 239000000243 solution Substances 0.000 claims description 155
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 109
- 239000003999 initiator Substances 0.000 claims description 97
- 150000007524 organic acids Chemical class 0.000 claims description 90
- 239000000203 mixture Substances 0.000 claims description 86
- 238000002156 mixing Methods 0.000 claims description 53
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 51
- 239000000839 emulsion Substances 0.000 claims description 51
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 45
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 39
- 239000007864 aqueous solution Substances 0.000 claims description 39
- 239000012046 mixed solvent Substances 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 27
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical group COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 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 description 19
- 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 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical group NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 17
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 14
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 7
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical group OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 5
- -1 hydroxy acrylic ester Chemical class 0.000 claims description 5
- ZEMHQYNMVKDBFJ-UHFFFAOYSA-N n-(3-hydroxypropyl)prop-2-enamide Chemical compound OCCCNC(=O)C=C ZEMHQYNMVKDBFJ-UHFFFAOYSA-N 0.000 claims description 5
- BONVROUPOZRCDU-UHFFFAOYSA-N 2-hydroxyprop-2-enamide Chemical compound NC(=O)C(O)=C BONVROUPOZRCDU-UHFFFAOYSA-N 0.000 claims description 4
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 4
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 claims description 3
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 3
- ZVYGIPWYVVJFRW-UHFFFAOYSA-N 3-methylbutyl prop-2-enoate Chemical compound CC(C)CCOC(=O)C=C ZVYGIPWYVVJFRW-UHFFFAOYSA-N 0.000 claims description 3
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 3
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 claims description 3
- JTHZUSWLNCPZLX-UHFFFAOYSA-N 6-fluoro-3-methyl-2h-indazole Chemical compound FC1=CC=C2C(C)=NNC2=C1 JTHZUSWLNCPZLX-UHFFFAOYSA-N 0.000 claims description 3
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-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
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical group OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 claims description 3
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 claims description 3
- UUORTJUPDJJXST-UHFFFAOYSA-N n-(2-hydroxyethyl)prop-2-enamide Chemical compound OCCNC(=O)C=C UUORTJUPDJJXST-UHFFFAOYSA-N 0.000 claims description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical group CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 claims description 3
- PQSIXYSSKXAOFE-UHFFFAOYSA-N tri(propan-2-yl)silyl prop-2-enoate Chemical group CC(C)[Si](C(C)C)(C(C)C)OC(=O)C=C PQSIXYSSKXAOFE-UHFFFAOYSA-N 0.000 claims description 3
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 claims description 2
- AZIQALWHRUQPHV-UHFFFAOYSA-N prop-2-eneperoxoic acid Chemical compound OOC(=O)C=C AZIQALWHRUQPHV-UHFFFAOYSA-N 0.000 claims description 2
- 239000003973 paint Substances 0.000 abstract description 15
- 239000000758 substrate Substances 0.000 abstract description 13
- 238000003860 storage Methods 0.000 abstract description 8
- 238000010276 construction Methods 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 4
- 238000000576 coating method Methods 0.000 description 41
- 239000011248 coating agent Substances 0.000 description 36
- 238000012360 testing method Methods 0.000 description 20
- 241000195493 Cryptophyta Species 0.000 description 12
- 239000002245 particle Substances 0.000 description 12
- 239000000523 sample Substances 0.000 description 12
- 238000002329 infrared spectrum Methods 0.000 description 11
- 238000005299 abrasion Methods 0.000 description 9
- 239000013535 sea water Substances 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 8
- 238000002791 soaking Methods 0.000 description 8
- 238000001035 drying Methods 0.000 description 6
- 239000003995 emulsifying agent Substances 0.000 description 6
- 238000011056 performance test Methods 0.000 description 6
- 230000002829 reductive effect Effects 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000005054 agglomeration Methods 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- 238000007720 emulsion polymerization reaction Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 239000004816 latex Substances 0.000 description 4
- 229920000126 latex Polymers 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 230000003068 static effect Effects 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 230000032798 delamination Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000012010 growth Effects 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- 230000005764 inhibitory process Effects 0.000 description 3
- 235000015097 nutrients Nutrition 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000000344 soap Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 101100112111 Caenorhabditis elegans cand-1 gene Proteins 0.000 description 2
- 241000195649 Chlorella <Chlorellales> Species 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 244000137852 Petrea volubilis Species 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 239000002519 antifouling agent Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000010556 emulsion polymerization method Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- HQVFKSDWNYVAQD-UHFFFAOYSA-N n-hydroxyprop-2-enamide Chemical compound ONC(=O)C=C HQVFKSDWNYVAQD-UHFFFAOYSA-N 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- FEWFXBUNENSNBQ-UHFFFAOYSA-N 2-hydroxyacrylic acid Chemical compound OC(=C)C(O)=O FEWFXBUNENSNBQ-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000005747 Chlorothalonil Substances 0.000 description 1
- 229910018540 Si C Inorganic materials 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000005791 algae growth Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000012496 blank sample Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000006664 bond formation reaction Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- CRQQGFGUEAVUIL-UHFFFAOYSA-N chlorothalonil Chemical compound ClC1=C(Cl)C(C#N)=C(Cl)C(C#N)=C1Cl CRQQGFGUEAVUIL-UHFFFAOYSA-N 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000015784 hyperosmotic salinity response Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000012844 infrared spectroscopy analysis Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229940113125 polyethylene glycol 3000 Drugs 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 235000011008 sodium phosphates Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 235000019794 sodium silicate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 150000003722 vitamin derivatives Chemical class 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
- C09D143/04—Homopolymers or copolymers of monomers containing silicon
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to a preparation method and application of an aqueous self-polishing anti-fouling resin. The aqueous self-polishing antifouling paint prepared by taking the aqueous self-polishing antifouling resin as a film forming material has good film forming performance, adhesion performance, storage stability and construction performance on a substrate, and has excellent antifouling effect.
Description
[ field of technology ]
The invention belongs to the technical field of marine fouling organism prevention and removal. More specifically, the invention relates to an aqueous self-polishing antifouling resin, a preparation method of the aqueous self-polishing antifouling resin and application of the aqueous self-polishing antifouling resin.
[ background Art ]
The self-polishing antifouling paint is the most important antifouling paint at present because of the advantages of high efficiency, lasting antifouling performance and easiness in construction. The self-polishing antifouling resin is a core component of the self-polishing antifouling paint, and the self-polishing antifouling resin still takes organic solvents such as dimethylbenzene, toluene, butanol, butyl acetate and the like as a dispersion system, releases a large amount of volatile organic matters in use, causes great harm to the ecological environment and also brings great waste of the organic solvents. In order to solve this problem, a great deal of research has been made on the aqueous nature of self-polishing antifouling resins at home and abroad in recent years. However, the progress achieved is extremely limited and it is still difficult to see a mature, commercial aqueous self-polishing antifouling coating that can be used on a large scale. This is because the aqueous self-polishing antifouling paint prepared by the prior art has the following problems: (1) the aqueous self-polishing antifouling resin has poor film forming property and water resistance, and the coating is easy to fall off; (2) the aqueous self-polishing antifouling resin emulsion is easy to break emulsion under the conditions of high-speed grinding and dispersing, long-time storage, low temperature and the like of the coating, and causes great difficulty in preparing and using the aqueous antifouling coating; (3) the drying time of the water-based self-polishing antifouling resin is slow in the construction process, and the resin is easily influenced by weather such as air temperature, rain and snow and the like.
The aqueous self-polishing antifouling resin prepared by the prior art has the problems above mainly because the preparation technology adopts soap emulsion polymerization, and a large amount of surfactant (about 6-10% of the mass of the monomer) is introduced into the resin. This makes the film-forming mechanism of the aqueous antifouling resin prepared by soap emulsion polymerization quite different from that of the oily antifouling resin prepared by solution polymerization. In the film forming process of the aqueous resin prepared by soap emulsion polymerization, emulsion particles need to overcome the blocking effect brought by an emulsifier first and then can be mutually approached and fused. Therefore, the aqueous self-polishing antifouling resin prepared by the prior art is difficult to form a better film layer, and the glass transition temperature of the resin needs to be lowered so as to promote the fusion film formation of the polymer in the latex particles. Under the condition of seawater soaking, a large amount of emulsifying agent seeps out from the coating, so that the water resistance of the coating is seriously reduced, and meanwhile, the drying speed of the coating is reduced, so that the construction progress is influenced. The above factors make the aqueous self-polishing antifouling paint less adhesive and greatly shortened in effective period. The emulsifier micelle or colloidal particle can enable the polymer particles to be stably dispersed in the water system, but is easy to be broken by the influences of shearing force, temperature, solid content, metal ions and the like, and has great hidden trouble of invalidating the aqueous resin emulsion and the aqueous coating.
In view of the above problems in the prior art, the present invention adds neutral hydrophilic monomer structural units and charged hydrophilic monomers in the preparation process, and adjusts the polymerization process to make the polymer have hydrophilic chain segments or structural units, so as to provide self-emulsifying function for the self-polishing polymer. This avoids the introduction of a large amount of emulsifier, which is beneficial to improving the film forming property of the resin. Meanwhile, the neutral hydrophilic monomer structural unit with active groups can act with the charged structural unit, and the water resistance and the adhesive force of the coating are improved through hydrogen bond or covalent bond formation. Through the cooperation of the functions, the aqueous self-polishing antifouling resin with greatly prolonged film forming property, water resistance and effective period and the coating thereof are obtained. The removal of the emulsifier also facilitates the drying of the paint film of the aqueous paint during construction. The self-emulsifying capability of the water-based self-polishing antifouling resin polymer also avoids the demulsification and caking problems of the water-based self-polishing antifouling resin under various conditions of preparation, storage and the like.
[ invention ]
[ problem to be solved ]
The invention aims to provide a preparation method of an aqueous self-polishing antifouling resin.
It is another object of the present invention to provide an aqueous self-polishing antifouling resin obtained by the production method.
It is another object of the present invention to provide the use of the aqueous self-polishing antifouling resin obtained by the production method.
Technical scheme
The invention is realized by the following technical scheme.
The invention relates to a preparation method of an aqueous self-polishing antifouling resin.
The preparation method comprises the following preparation steps:
A. preparation of oily acrylic monomer mixture
The hard oil acrylic monomer and the soft oil acrylic monomer and the self-polishing monomer are mixed according to the mole ratio of 0 to 30: 20-70: mixing 0-30 to obtain the oily acrylic acid monomer mixture;
B. preparing unsaturated organic acid aqueous solution
Uniformly mixing 3-20% of unsaturated organic acid based on the mol of oily acrylic acid monomer and 30-200% of water based on the mol of unsaturated organic acid, adding 10-100% of sodium hydroxide based on the mol of unsaturated organic acid, dissolving, and uniformly mixing to obtain an unsaturated organic acid aqueous solution;
C. preparing aqueous monomer solution
According to the mole ratio of the oily acrylic monomer to the aqueous monomer of 80-95: 5-25, adding one or more aqueous monomers into the unsaturated organic acid aqueous solution obtained in the step B, and then adding an initiator accounting for 0.1-1.5% of the total mass of the oily acrylic acid monomer and the aqueous monomers to obtain the aqueous monomer solution;
D. Preparation of aqueous self-polishing antifouling resin
Adding a mixed solvent consisting of deionized water and alcohol accounting for 100-300% of the total mass of oily acrylic acid monomers and water-based monomers into a four-neck flask provided with a stirrer, a condenser pipe and a thermometer, adding the oily acrylic acid monomer solution obtained in the step A and the water-based monomer solution obtained in the step C, wherein the addition amounts of the oily acrylic acid monomer solution and the water-based monomer solution are respectively 5-10% of the volumes of the oily acrylic acid monomer solution and the water-based monomer solution, and uniformly mixing to obtain a monomer mixture solution;
then, heating the monomer mixture solution to 70-85 ℃ under the conditions of nitrogen atmosphere and stirring speed of 50-500 rpm; when the reaction system generates blue light, dripping or adding the rest oily acrylic acid monomer solution and the water-based monomer solution in batches at the temperature within 0.5-1.5 h, then reducing the temperature to 60-70 ℃ and keeping the temperature for 0.8-1.2 h;
then, the initiator accounting for 0.01 to 0.02 percent of the total mass of all monomers is added, and the mixture is kept at the temperature of 60 to 70 ℃ for 0.4 to 0.6 hour and cooled to room temperature, thus obtaining the milky aqueous emulsion self-polishing antifouling resin.
According to a preferred embodiment of the present invention, in step a, the hard oil acrylic monomer is methyl acrylate, methyl methacrylate, ethyl acrylate or a mixture thereof; the soft oil acrylic monomer is propyl acrylate, butyl acrylate, isoamyl acrylate, dodecyl acrylate, stearyl acrylate or a mixture thereof; the self-polishing monomer is acryloxytriisopropyl silane, methacryloxytriisopropyl silane, gamma-methacryloxypropyl trimethoxysilane or a mixture thereof.
According to another preferred embodiment of the present invention, in step B, the unsaturated organic acid is acrylic acid, methacrylic acid, methylen succinic acid or a mixture thereof.
According to another preferred embodiment of the invention, in step C, the aqueous monomer is acrylamide, hydroxyacrylamide, vinylpyrrolidone, hydroxyacrylate or a mixture thereof.
According to another preferred embodiment of the present invention, the hydroxyacrylamide is N-methylolacrylamide, N-hydroxyethyl acrylamide or N-hydroxypropyl acrylamide; the hydroxy acrylic ester is hydroxyethyl acrylate, hydroxypropyl acrylate or 4-hydroxy butyl acrylate or a mixture thereof.
According to another preferred embodiment of the present invention, in the step C, the initiator is a mixture of water-soluble initiator and oil-soluble initiator in a mass ratio of 70 to 95:0 to 10;
according to another preferred embodiment of the present invention, the aqueous initiator is one or more initiators selected from the group consisting of azobisiso Ding Mi hydrochloride, azobisisopropylimidazoline, azobisisobutylamidine hydrochloride, potassium persulfate or ammonium persulfate; the oily initiator is one or more initiators selected from azodiisobutyronitrile, azodiisoheptonitrile, benzoyl peroxide tert-butyl ester or methyl ethyl ketone peroxide.
According to another preferred embodiment of the present invention, in step D, in the mixed solvent, the alcohol is one or more alcohols selected from methanol, ethanol, ethylene glycol or glycerol, and the amount of the alcohol is 3 to 20% by volume of the mixed solvent.
The invention also relates to the aqueous self-polishing antifouling resin prepared by the preparation method.
The invention also relates to application of the aqueous self-polishing antifouling resin prepared by the preparation method in the field of marine fouling organism control.
The present invention will be described in more detail below.
The invention relates to a preparation method of an aqueous self-polishing antifouling resin.
The aqueous self-polishing antifouling resin prepared by the soap-free emulsion polymerization method has self-emulsifying capability, avoids using an emulsifying agent, is beneficial to improving the film forming property, the water resistance and the effective period of the resin, and is not easy to break emulsion, agglomerate and the like under various conditions of preparation, storage and the like.
The preparation method comprises the following preparation steps:
A. preparation of oily acrylic monomer mixture
The hard oil acrylic monomer and the soft oil acrylic monomer and the self-polishing monomer are mixed according to the mole ratio of 0 to 30: 20-70: mixing 0-30 to obtain the oily acrylic acid monomer mixture;
In the context of the present invention, a hard oil acrylic monomer is understood to be an acrylic monomer having a glass transition temperature of above 0 ℃.
According to the invention, the main function of the hard oil acrylic monomer in preparing the aqueous self-polishing antifouling resin is to regulate the rigidity of a high molecular chain and improve the adhesion capability of the aqueous self-polishing antifouling resin.
The hard oil acrylic monomer used in the present invention is methyl acrylate, methyl methacrylate, ethyl acrylate or a mixture thereof, which are currently commercially available products such as methyl acrylate sold under the trade name methyl acrylate by Shanghai Ala Biochemical technology Co., ltd.
In the present invention, a soft oil acrylic monomer is understood to be an acrylic monomer having a glass transition temperature of less than 0 degrees celsius.
According to the invention, the main function of the soft oil acrylic monomer in preparing the water-based self-polishing antifouling resin is to improve the adhesion of the water-based self-polishing antifouling resin on a substrate.
The soft oily acrylic monomer used in the present invention is propyl acrylate, butyl acrylate, isoamyl acrylate, dodecyl acrylate, stearyl acrylate or mixtures thereof, all of which are currently commercially available products such as butyl acrylate sold under the trade name butyl acrylate by Tian Jiao chemical Co., ltd.
In the present invention, a self-polishing monomer is understood to be a functional monomer having chemical properties that are chemically hydrolyzable or biodegradable in seawater.
According to the invention, the main function of the self-polishing monomer in preparing the water-based self-polishing antifouling resin is to continuously dissolve and fall off the self-polishing monomer, so that the antifouling capacity of the water-based self-polishing antifouling resin is enhanced.
The self-polishing monomer used in the present invention is acryloxytriisopropylsilane, methacryloxytriisopropylsilane, γ -methacryloxypropyltrimethoxysilane or a mixture thereof, all of which are currently commercially available products such as methacryloxytriisopropylsilane sold under the trade name methacryloxytriisopropylsilane by the further development of technology, inc. of Wuhan, further city.
When the dosage of the soft oily acrylic monomer and the self-polishing monomer is in the range, the dosage of the hard oily acrylic monomer can be zero under the condition that the rigidity of the aqueous self-polishing antifouling resin coating meets the mechanical property requirement of no cracking; if the amount of the hard oily acrylic acid monomer is more than 30, the high molecular rigidity is excessively high, and the mechanical property of the prepared aqueous self-polishing antifouling resin is reduced, so that the adhesion of the aqueous self-polishing antifouling resin on a substrate is not facilitated. Therefore, the amount of the hard oil type acrylic monomer is reasonable to be 0 to 30, preferably 5 to 25.
When the dosage of the hard oil acrylic acid monomer and the self-polishing monomer is in the range, if the dosage of the soft oil acrylic acid monomer is lower than 20, the hardness of the obtained water self-polishing antifouling resin is smaller, which is not beneficial to the fusion and film formation of resin emulsion particles and the adhesion of the resin emulsion particles on a substrate; if the amount of the soft oily acrylic monomer is higher than 70, the glass transition temperature of the obtained water-based self-polishing antifouling resin is lower in film formation, and the obtained antifouling resin is smaller in hardness and lower in mechanical property. Therefore, it is reasonable to use the soft oil acrylic monomer in an amount of 20 to 70, preferably 30 to 65.
When the amounts of the hard oil-based acrylic acid monomer and the soft oil-based acrylic acid monomer are within the ranges, the amount of the self-polishing monomer may be zero under the condition that the self-polishing abrasion rate of the aqueous self-polishing antifouling resin coating is relatively stable; if the amount of the self-polishing monomer is more than 30, the self-polishing rate of the aqueous self-polishing antifouling resin coating is too fast, which is disadvantageous for long-term antifouling. Thus, the amount of self-polishing monomer is suitably from 0 to 30, preferably from 6 to 25.
Preferably, the molar ratio of the hard oil acrylic monomer to the soft oil acrylic monomer to the self-polishing monomer is 5 to 25: 30-65: 6 to 25.
B. Preparing unsaturated organic acid aqueous solution
Uniformly mixing 3-20% of unsaturated organic acid based on the mol of oily acrylic acid monomer and 30-200% of water based on the mol of unsaturated organic acid, adding 10-100% of sodium hydroxide based on the mol of unsaturated organic acid, dissolving, and uniformly mixing to obtain an unsaturated organic acid aqueous solution;
according to the invention, the unsaturated organic acid has a main effect in preparing the aqueous self-polishing antifouling resin in that the unsaturated organic acid can form hydrogen bonds with other monomers with hydroxyl groups, amino groups or carboxyl groups, thereby affecting the mechanical properties of the aqueous self-polishing antifouling resin.
The unsaturated organic acid used in the present invention is acrylic acid, methacrylic acid, methylene succinic acid or a mixture thereof, which are all products currently commercially available, such as acrylic acid sold under the trade name acrylic acid by the company Tianjin's metallocene chemical agent.
In this step, the main purpose of adding sodium hydroxide after uniformly mixing the unsaturated organic acid with water is to avoid excessive reaction temperature caused by neutralization of acid and base to release a large amount of heat.
In the present invention, when the amount of water is within the range described, if the amount of unsaturated organic acid is less than 3%, the mechanical properties of the aqueous self-polishing antifouling resin coating layer are reduced; if the amount of the unsaturated organic acid is more than 20%, the aqueous self-polishing antifouling resin coating layer is liable to become brittle, crack and fall off; thus, it is desirable that the amount of unsaturated organic acid is 3 to 20%, preferably 3 to 18%; when the dosage of the unsaturated organic acid is in the range, if the dosage of water in the acid-base neutralization reaction is lower than 30%, the temperature is lowered slowly, and a large amount of heat released by the neutralization reaction damages the balance of the reaction system; if the water usage amount is higher than 200%, the unsaturated organic acid is excessively diluted, and the acid-base neutralization reaction is not thorough; thus, a water content of 30 to 200% is appropriate, preferably 55 to 175%;
In this step, when the amount of the unsaturated organic acid and water is within the range, if the amount of sodium hydroxide is less than 10%, the reaction produces less acrylic monomer containing a carboxylate ion structure, the polymerization reaction is unstable, and the reaction rate is lowered; if the dosage of sodium hydroxide is higher than 100%, the acrylic monomer containing carboxylate ion structure generated by the reaction is more, which affects the performance of the aqueous self-polishing antifouling resin coating; thus, it is reasonable to use 10 to 100% sodium hydroxide, preferably 25 to 90%.
C. Preparing aqueous monomer solution
According to the mole ratio of the oily acrylic monomer to the aqueous monomer of 80-95: 5-25, adding one or more aqueous monomers into the unsaturated organic acid aqueous solution obtained in the step B, and then adding an initiator accounting for 0.1-1.5% of the total mass of the oily acrylic acid monomer and the aqueous monomers to obtain the aqueous monomer solution;
in the context of the present invention, an aqueous monomer is understood to be a monomer which has good solubility in water.
According to the invention, the main function of the aqueous monomer in preparing the aqueous self-polishing antifouling resin is to promote the reaction to be carried out normally and improve the antifouling performance of the aqueous self-polishing antifouling resin.
The aqueous monomer used in the invention is acrylamide, hydroxy acrylamide, vinyl pyrrolidone, hydroxy acrylic acid ester or a mixture thereof, wherein the hydroxy acrylamide is N-methylolacrylamide, N-hydroxyethyl acrylamide or N-hydroxypropyl acrylamide; the hydroxy acrylic ester is hydroxyethyl acrylate, hydroxypropyl acrylate or 4-hydroxybutyl acrylate or a mixture thereof, which are all products currently sold on the market, such as acrylamide sold under the trade name acrylamide by Jiulong chemical Co Ltd in Jiangxi, N-hydroxypropyl acrylamide sold under the trade name N-hydroxypropyl acrylamide by Qingdao Datang chemical Co Ltd, and hydroxyethyl acrylate sold under the trade name hydroxyethyl acrylate by Guogui chemical reagent Co Ltd.
In the present invention, when the amount of the aqueous monomer is within the range, if the amount of the oily acrylic monomer is less than 80, the adhesion property of the aqueous self-polishing antifouling resin to the substrate is poor; if the amount of the oily acrylic monomer is more than 95, the emulsion may be unstable; therefore, it is appropriate that the amount of the oily acrylic monomer is 80 to 95; when the amount of the oily acrylic acid monomer is in the range, if the amount of the aqueous monomer is less than 5, emulsion breaking and stability reduction are caused; if the amount of the aqueous monomer is more than 25, the water resistance of the coating is lowered and the coating falls off; therefore, it is reasonable to use 5 to 25 aqueous monomers.
According to the invention, the main role of the initiator in preparing the aqueous self-polishing antifouling resin is that the initiator is decomposed into active free radicals, so that the monomer is initiated to carry out polymerization reaction to generate the aqueous self-polishing antifouling resin.
According to the invention, the initiator is a water-soluble initiator and an oil-soluble initiator according to the mass ratio of 70-95: 0 to 10; in which water-soluble initiator is understood to be an initiator having a solubility of at least 1g/100g of deionized water at a temperature of 20℃and 1 atmosphere, the main function of which is to promote the participation of the aqueous monomer in the copolymerization. An oil-soluble initiator is understood to be an initiator having a solubility of less than 1g/100g deionized water at 20℃and 1 atmosphere, and its main function is to promote the participation of oily monomers in the copolymerization.
In the present invention, when the amount of the oil-soluble initiator is within the range, if the amount of the water-soluble initiator is less than 70, incomplete reaction of the aqueous monomer may be caused; if the amount of the water-soluble initiator is more than 95%, the prepared emulsion is easy to phase-separate, and the polymerization of the oily monomer in the emulsion is incomplete; therefore, the amount of the water-soluble initiator to be used is suitably 70 to 95. When the amount of the water-soluble initiator is within the range, the amount of the oil-soluble initiator may be 0 in the case where the oily monomer is completely involved in the polymerization; if the amount of the oil-soluble initiator is higher than 10, the viscosity of the emulsion is higher, and large-particle emulsion particles are formed in the emulsion; thus, it is preferable that the amount of the oil-soluble initiator is 0 to 10.
The aqueous initiator used in the present invention is one or more initiators selected from the group consisting of azobisiso Ding Mi hydrochloride, azobisiso imidazoline, azobisisobutylamidine hydrochloride, potassium persulfate or ammonium persulfate, all of which are currently commercially available products such as azobisisobutylamidine hydrochloride sold under the trade name azobisisobutylamidine hydrochloride by the company of the metallocene chemical reagent of Tianjin;
the oily initiator used in the present invention is one or more initiators selected from azobisisobutyronitrile, azobisisoheptonitrile, benzoyl peroxide, t-butyl benzoyl peroxide or methyl ethyl ketone peroxide, all of which are currently commercially available products such as azobisisobutyronitrile sold under the trade name azobisisobutyronitrile by the company Tianjin's metallocene chemical reagent.
In this step, the initiator is used in an amount of 0.1 to 1.5% based on the total mass of the oily acrylic monomer and the aqueous monomer. If the amount of the initiator is less than 0.1%, unstable or no initiation of the polymerization reaction may be caused; if the amount of the initiator is higher than 1.5%, the molecular weight of the aqueous self-polishing antifouling resin is reduced, which is unfavorable for improving the mechanical properties of the aqueous self-polishing antifouling resin; thus, the amount of initiator is reasonable to be 0.1 to 1.5%, preferably 0.3 to 1.2%.
D. Preparation of aqueous self-polishing antifouling resin
Adding a mixed solvent consisting of deionized water and alcohol accounting for 100-300% of the total mass of oily acrylic acid monomers and water-based monomers into a four-neck flask provided with a stirrer, a condenser pipe and a thermometer, adding the oily acrylic acid monomer solution obtained in the step A and the water-based monomer solution obtained in the step C, wherein the addition amounts of the oily acrylic acid monomer solution and the water-based monomer solution are respectively 5-10% of the volumes of the oily acrylic acid monomer solution and the water-based monomer solution, and uniformly mixing to obtain a monomer mixture solution;
the use of a mixed solvent of deionized water and alcohol in the formulation of the monomer mixture solution is primarily aimed at enhancing the solubility of the oily monomer in the solvent medium, helping to form smaller particle size latex particles and accelerating the soap-free emulsion polymerization rate.
According to the invention, in the mixed solvent, the alcohol is one or more alcohols selected from methanol, ethanol, ethylene glycol or glycerol, and the amount of the alcohol is 3-20% by volume of the mixed solvent. An amount of alcohol exceeding the above range is not preferable because an excessive amount of alcohol increases the emission of volatile organic compounds, which adversely affects the economical aspects and environmental aspects.
In this step, the main purpose of adding 5 to 10% of the oily acrylic monomer solution obtained in step A and 5 to 10% of the aqueous monomer solution obtained in step C is to allow the initiator to slowly decompose and initiate the polymerization reaction during the system temperature rising process, so that the polymerization reaction can be initiated and carried out more stably.
Then, heating the monomer mixture solution to 70-85 ℃ under the conditions of nitrogen atmosphere and stirring speed of 50-500 rpm; when the reaction system generates blue light, the rest oily acrylic acid monomer solution and the water-based monomer solution are added dropwise or in batches within 0.5 to 1.5 hours, then the temperature is reduced to 60 to 70 ℃, and the temperature is kept for 0.8 to 1.2 hours;
in this step, nitrogen was introduced to remove oxygen from the reaction system, thereby ensuring that the initiator was fully functional.
Then, the initiator accounting for 0.01 to 0.02 percent of the total mass of all monomers is added, and the mixture is kept at the temperature of 60 to 70 ℃ for 0.4 to 0.6 hour and cooled to room temperature, thus obtaining the milky aqueous emulsion self-polishing antifouling resin.
The reaction vessel, the electric stirring device, the oil bath pot, the drying device and the like used in the invention are all chemical equipment or devices commonly used in the technical field of chemical industry.
The resulting milky aqueous emulsion self-polishing antifouling resin was subjected to conventional infrared spectroscopic analysis, and the analysis results thereof are shown in FIG. 1.
As can be seen from FIG. 1a, the aqueous self-polishing antifouling resins prepared in examples 1 to 5 (designated as resins MA0, MA10, MA20, MA30 and MA40, respectively) were 2957cm -1 To 2869cm -1 The C-H stretching vibration of saturated alkane on the main chain and the side chain of the macromolecule appears at 1726cm -1 There appears a stretching vibration peak of-c=o belonging to saturated ester (-c=o (-COO-)) at 1726cm -1 And 932cm -1 The extensional vibration peak of-C=O and the flexural vibration peak of-O-H, which belong to carboxylic acid (-COOH), respectively appear, and are at 3500cm -1 Up to 3000cm -1 The broad and diffuse absorption peak is the stretching vibration peak of-O-H of carboxylic acid (-COOH). At 1500cm -1 To 1450cm -1 A symmetrical stretching vibration peak belonging to carboxylate radical appears. At 3364cm -1 、1688cm -1 、1567cm -1 And 1246cm -1 The occurrence of the amide (-CONH) 2 ) -N-H stretching vibration peak, -C=O stretching vibration peak, -N-H bending vibration peak and-C-N stretching vibration peak. These infrared spectral results show that characteristic absorption peaks of the participating comonomers (butyl acrylate, methyl acrylate, acrylic acid and acrylamide) appear in the infrared absorption spectra of resins MA0, MA10, MA20, MA30 and MA40, thus determining the expected aqueous self-polishing antifouling resin.
As can be seen from FIG. 1b, the aqueous self-polishing antifouling resins prepared in examples 6 to 10 (splitAre identified as resins TSi5, TSi10, TSi15, TSi20 and TSi 25) at 2956cm -1 To 2864cm -1 The C-H stretching vibration of saturated alkane on the main chain and the side chain of the macromolecule appears at 1726cm -1 There appears a stretching vibration peak of c=o belonging to saturated ester (-c=o (-COO-)) at 1726cm -1 There appears a stretching vibration peak of-c=o belonging to carboxylic acid (-COOH), and at 3500cm -1 Up to 3000cm -1 The broad and diffuse absorption peak is the stretching vibration peak of the O-H of carboxylic acid (-COOH). At 1500cm -1 To 1450cm -1 A symmetrical stretching vibration peak belonging to carboxylate radical appears. At 3379cm -1 And 1726cm -1 The occurrence of the amide (-CONH) 2 ) -N-H and-c=o. At 1087cm -1 The stretching vibration peak belonging to the-Si-O bond appears at 837cm -1 The stretching vibration peak belonging to-Si-C appears on the left and right. These infrared spectral results show that the characteristic absorption peaks of the participating comonomers (butyl acrylate, methyl acrylate, acrylic acid, acrylamide and methacryloxytriisopropylsilane) appear in the infrared absorption spectra of resins TSi5, TSi10, TSi15, TSi20 and TSi25, thus determining the expected aqueous self-polishing antifouling resin.
The invention also relates to the aqueous self-polishing antifouling resin prepared by the preparation method.
The invention also relates to application of the aqueous self-polishing antifouling resin in the field of marine fouling organism control. The invention examines the emulsion performance by observing the emulsion state, examines the adhesion performance of the aqueous self-polishing antifouling resin coating by a static bubble plate method, examines the self-polishing performance by calculating the self-polishing abrasion rate, examines the antifouling performance by inhibiting microalgae adhesion, and the like, and particularly please refer to the embodiment part.
[ advantageous effects ]
The beneficial technical effects of the invention are as follows: the aqueous self-polishing antifouling resin prepared by the soap-free emulsion polymerization method has self-emulsifying capacity, is beneficial to improving the film forming property, water resistance and effective period of the resin, and overcomes the technical defects existing in the prior art. The aqueous self-polishing emulsion disclosed by the invention has good stability, the problems of phase separation, agglomeration and the like can not occur after the aqueous self-polishing emulsion is stored for a long time, and the problems of demulsification, agglomeration and the like are not easy to occur under various conditions such as preparation, storage and the like. The aqueous self-polishing antifouling paint prepared by taking the aqueous self-polishing antifouling resin prepared by the invention as a film forming material has good film forming performance, adhesion performance, storage stability and construction performance on a substrate, and has excellent antifouling effect.
[ description of the drawings ]
FIG. 1 is an infrared spectrum of an aqueous self-polishing antifouling resin of the present invention;
in the figure: a-examples 1-5, b-examples 6-10;
FIG. 2 is a graph showing the results of an adhesion test of the aqueous self-polishing antifouling resin of the present invention;
in the figure: a-examples 1-5, b-examples 6-10;
FIG. 3 is a graph showing the results of a self-polishing performance test of the aqueous self-polishing antifouling resin of the present invention;
In the figure: a-examples 1-5, b-examples 6-10;
FIG. 4 is a graph showing the results of an algae inhibiting performance test of the aqueous self-polishing antifouling resin of the present invention;
in the figure: a-examples 1-5, b-examples 6-10;
FIG. 5 is a graph of the results of an actual sea-plate test of an antifouling paint using the aqueous self-polishing antifouling resin of the present invention as a film former:
in the figure: a-example 3, b-example 6.
[ detailed description ] of the invention
The invention will be better understood by the following examples.
Example 1: preparation of the aqueous self-polishing antifouling resin
The implementation of this example is as follows:
A. preparation of oily acrylic monomer mixture
Methyl acrylate hard oil acrylic acid monomer, butyl acrylate soft oil acrylic acid monomer and methacryloxy triisopropyl silane self-polishing monomer are mixed according to the molar ratio of 10:70:0, mixing to obtain the oily acrylic monomer mixture;
B. preparing unsaturated organic acid aqueous solution
Uniformly mixing 3.6% of unsaturated organic acid of acrylic acid based on the mol of oily acrylic acid monomer with 140% of water based on the mol of unsaturated organic acid, adding 89% of sodium hydroxide based on the mol of unsaturated organic acid, dissolving, and uniformly mixing to obtain an unsaturated organic acid aqueous solution;
C. Preparing aqueous monomer solution
According to the mol ratio of the oily acrylic monomer to the aqueous monomer of 85:15, adding an acrylamide aqueous monomer into the unsaturated organic acid aqueous solution obtained in the step B, and adding an initiator accounting for 1.1 percent of the total mass of the oily acrylic acid monomer and the aqueous monomer, wherein the initiator is an azo diisobutylamidine hydrochloride water-soluble initiator and an azo diisobutyronitrile oil-soluble initiator according to the mass ratio of 80:8 to obtain the aqueous monomer solution;
D. preparation of aqueous self-polishing antifouling resin
Adding a mixed solvent which is 130% of the total mass of the oily acrylic acid monomer and the aqueous monomer and consists of deionized water and methanol into a four-neck flask provided with a stirrer, a condenser pipe and a thermometer, wherein the dosage of the methanol is 14% of the volume of the mixed solvent, and then adding the oily acrylic acid monomer solution obtained in the step A and the aqueous monomer solution obtained in the step C, wherein the addition amounts of the oily acrylic acid monomer solution and the aqueous monomer solution are 10% of the respective volumes of the oily acrylic acid monomer solution and the aqueous monomer solution, and uniformly mixing to obtain a monomer mixture solution;
then, the monomer mixture solution was heated to a temperature of 70℃under a nitrogen atmosphere at a stirring speed of 300 rpm; when the reaction system generates blue light, dripping the rest oily acrylic monomer solution and the water-based monomer solution at the temperature within 1h, then reducing the temperature to 70 ℃ and keeping the temperature for 1h;
Next, the initiator was added in an amount of 0.01% by mass based on the total mass of all the monomers, and the mixture was kept at 70℃for 0.5 hours and cooled to room temperature to obtain a milky aqueous emulsion self-polishing antifouling resin, which was designated MA0.
The infrared spectrum of the milky aqueous emulsion self-polishing antifouling resin was examined according to the method described in the present specification, and the results are shown in FIG. 1a.
Example 2: preparation of the aqueous self-polishing antifouling resin
The implementation of this example is as follows:
A. preparation of oily acrylic monomer mixture
Methyl acrylate hard oil acrylic acid monomer, butyl acrylate soft oil acrylic acid monomer and methacryloxy triisopropyl silane self-polishing monomer are mixed according to the molar ratio of 15:70:0, mixing to obtain the oily acrylic monomer mixture;
B. preparing unsaturated organic acid aqueous solution
Uniformly mixing 3.6% of unsaturated organic acid of acrylic acid based on the mol of oily acrylic acid monomer with 140% of water based on the mol of unsaturated organic acid, adding 89% of sodium hydroxide based on the mol of unsaturated organic acid, dissolving, and uniformly mixing to obtain an unsaturated organic acid aqueous solution;
C. preparing aqueous monomer solution
According to the mol ratio of the oily acrylic monomer to the aqueous monomer of 85:15, adding an acrylamide aqueous monomer into the unsaturated organic acid aqueous solution obtained in the step B, and adding an initiator accounting for 1.1 percent of the total mass of the oily acrylic acid monomer and the aqueous monomer, wherein the initiator is an azo diisobutylamidine hydrochloride water-soluble initiator and an azo diisobutyronitrile oil-soluble initiator according to the mass ratio of 80:8 to obtain the aqueous monomer solution;
D. preparation of aqueous self-polishing antifouling resin
Adding a mixed solvent which is 130% of the total mass of the oily acrylic acid monomer and the aqueous monomer and consists of deionized water and methanol into a four-neck flask provided with a stirrer, a condenser pipe and a thermometer, wherein the dosage of the methanol is 14% of the volume of the mixed solvent, and then adding the oily acrylic acid monomer solution obtained in the step A and the aqueous monomer solution obtained in the step C, wherein the addition amounts of the oily acrylic acid monomer solution and the aqueous monomer solution are 10% of the respective volumes of the oily acrylic acid monomer solution and the aqueous monomer solution, and uniformly mixing to obtain a monomer mixture solution;
then, the monomer mixture solution was heated to a temperature of 70℃under a nitrogen atmosphere at a stirring speed of 300 rpm; when the reaction system generates blue light, dripping the rest oily acrylic monomer solution and the water-based monomer solution at the temperature within 1h, then reducing the temperature to 70 ℃ and keeping the temperature for 1h;
Next, the initiator was added in an amount of 0.01% by weight based on the total mass of all the monomers, and the mixture was kept at 70℃for 0.5 hours and cooled to room temperature to give a milky aqueous emulsion self-polishing antifouling resin, designated MA10.
The infrared spectrum of the milky aqueous emulsion self-polishing antifouling resin was examined according to the method described in the present specification, and the results are shown in FIG. 1a.
Example 3: preparation of the aqueous self-polishing antifouling resin
The implementation of this example is as follows:
A. preparation of oily acrylic monomer mixture
Methyl acrylate hard oil acrylic acid monomer, butyl acrylate soft oil acrylic acid monomer and methacryloxy triisopropyl silane self-polishing monomer are mixed according to the molar ratio of 20:65:0, mixing to obtain the oily acrylic monomer mixture;
B. preparing unsaturated organic acid aqueous solution
Uniformly mixing 3.6% of unsaturated organic acid of acrylic acid based on the mol of oily acrylic acid monomer with 140% of water based on the mol of unsaturated organic acid, adding 89% of sodium hydroxide based on the mol of unsaturated organic acid, dissolving, and uniformly mixing to obtain an unsaturated organic acid aqueous solution;
C. preparing aqueous monomer solution
According to the mol ratio of the oily acrylic monomer to the aqueous monomer of 85:15, adding an acrylamide aqueous monomer into the unsaturated organic acid aqueous solution obtained in the step B, and adding an initiator accounting for 1.1 percent of the total mass of the oily acrylic acid monomer and the aqueous monomer, wherein the initiator is an azo diisobutylamidine hydrochloride water-soluble initiator and an azo diisobutyronitrile oil-soluble initiator according to the mass ratio of 80:8 to obtain the aqueous monomer solution;
D. preparation of aqueous self-polishing antifouling resin
Adding a mixed solvent which is 130% of the total mass of the oily acrylic acid monomer and the aqueous monomer and consists of deionized water and methanol into a four-neck flask provided with a stirrer, a condenser pipe and a thermometer, wherein the dosage of the methanol is 14% of the volume of the mixed solvent, and then adding the oily acrylic acid monomer solution obtained in the step A and the aqueous monomer solution obtained in the step C, wherein the addition amounts of the oily acrylic acid monomer solution and the aqueous monomer solution are 10% of the respective volumes of the oily acrylic acid monomer solution and the aqueous monomer solution, and uniformly mixing to obtain a monomer mixture solution;
then, the monomer mixture solution was heated to a temperature of 70℃under a nitrogen atmosphere at a stirring speed of 300 rpm; when the reaction system generates blue light, dripping the rest oily acrylic monomer solution and the water-based monomer solution at the temperature within 1h, then reducing the temperature to 70 ℃ and keeping the temperature for 1h;
Next, the initiator was added in an amount of 0.01% by mass based on the total mass of all the monomers, and the mixture was kept at 70℃for 0.5 hours and cooled to room temperature to give a milky aqueous emulsion self-polishing antifouling resin, which was designated as MA20.
The infrared spectrum of the milky aqueous emulsion self-polishing antifouling resin was examined according to the method described in the present specification, and the results are shown in FIG. 1a.
Example 4: preparation of the aqueous self-polishing antifouling resin
The implementation of this example is as follows:
A. preparation of oily acrylic monomer mixture
Methyl acrylate hard oil acrylic acid monomer, butyl acrylate soft oil acrylic acid monomer and methacryloxy triisopropyl silane self-polishing monomer are mixed according to a molar ratio of 25:60:0, mixing to obtain the oily acrylic monomer mixture;
B. preparing unsaturated organic acid aqueous solution
Uniformly mixing 3.6% of unsaturated organic acid of acrylic acid based on the mol of oily acrylic acid monomer with 140% of water based on the mol of unsaturated organic acid, adding 89% of sodium hydroxide based on the mol of unsaturated organic acid, dissolving, and uniformly mixing to obtain an unsaturated organic acid aqueous solution;
C. preparing aqueous monomer solution
According to the mol ratio of the oily acrylic monomer to the aqueous monomer of 85:15, adding an acrylamide aqueous monomer into the unsaturated organic acid aqueous solution obtained in the step B, and adding an initiator accounting for 1.1 percent of the total mass of the oily acrylic acid monomer and the aqueous monomer, wherein the initiator is an azo diisobutylamidine hydrochloride water-soluble initiator and an azo diisobutyronitrile oil-soluble initiator according to the mass ratio of 80:8 to obtain the aqueous monomer solution;
D. preparation of aqueous self-polishing antifouling resin
Adding a mixed solvent which is 130% of the total mass of the oily acrylic acid monomer and the aqueous monomer and consists of deionized water and methanol into a four-neck flask provided with a stirrer, a condenser pipe and a thermometer, wherein the dosage of the methanol is 14% of the volume of the mixed solvent, and then adding the oily acrylic acid monomer solution obtained in the step A and the aqueous monomer solution obtained in the step C, wherein the addition amounts of the oily acrylic acid monomer solution and the aqueous monomer solution are 10% of the respective volumes of the oily acrylic acid monomer solution and the aqueous monomer solution, and uniformly mixing to obtain a monomer mixture solution;
then, the monomer mixture solution was heated to a temperature of 70℃under a nitrogen atmosphere at a stirring speed of 300 rpm; when the reaction system generates blue light, dripping the rest oily acrylic monomer solution and the water-based monomer solution at the temperature within 1h, then reducing the temperature to 70 ℃ and keeping the temperature for 1h;
Next, the initiator was added in an amount of 0.01% by weight based on the total mass of all the monomers, and the mixture was kept at 70℃for 0.5 hours and cooled to room temperature to give a milky aqueous emulsion self-polishing antifouling resin, which was designated as MA30.
The infrared spectrum of the milky aqueous emulsion self-polishing antifouling resin was examined according to the method described in the present specification, and the results are shown in FIG. 1a.
Example 5: preparation of the aqueous self-polishing antifouling resin
The implementation of this example is as follows:
A. preparation of oily acrylic monomer mixture
Methyl acrylate hard oil acrylic acid monomer, butyl acrylate soft oil acrylic acid monomer and methacryloxy triisopropyl silane self-polishing monomer are mixed according to the molar ratio of 30:55:0, mixing to obtain the oily acrylic monomer mixture;
B. preparing unsaturated organic acid aqueous solution
Uniformly mixing 3.6% of unsaturated organic acid of acrylic acid based on the mol of oily acrylic acid monomer with 140% of water based on the mol of unsaturated organic acid, adding 89% of sodium hydroxide based on the mol of unsaturated organic acid, dissolving, and uniformly mixing to obtain an unsaturated organic acid aqueous solution;
C. preparing aqueous monomer solution
According to the mol ratio of the oily acrylic monomer to the aqueous monomer of 85:15, adding an acrylamide aqueous monomer into the unsaturated organic acid aqueous solution obtained in the step B, and adding an initiator accounting for 1.1 percent of the total mass of the oily acrylic acid monomer and the aqueous monomer, wherein the initiator is an azo diisobutylamidine hydrochloride water-soluble initiator and an azo diisobutyronitrile oil-soluble initiator according to the mass ratio of 80:8 to obtain the aqueous monomer solution;
D. preparation of aqueous self-polishing antifouling resin
Adding a mixed solvent which is 130% of the total mass of the oily acrylic acid monomer and the aqueous monomer and consists of deionized water and methanol into a four-neck flask provided with a stirrer, a condenser pipe and a thermometer, wherein the dosage of the methanol is 14% of the volume of the mixed solvent, and then adding the oily acrylic acid monomer solution obtained in the step A and the aqueous monomer solution obtained in the step C, wherein the addition amounts of the oily acrylic acid monomer solution and the aqueous monomer solution are 10% of the respective volumes of the oily acrylic acid monomer solution and the aqueous monomer solution, and uniformly mixing to obtain a monomer mixture solution;
then, the monomer mixture solution was heated to a temperature of 70℃under a nitrogen atmosphere at a stirring speed of 300 rpm; when the reaction system generates blue light, dripping the rest oily acrylic monomer solution and the water-based monomer solution at the temperature within 1h, then reducing the temperature to 70 ℃ and keeping the temperature for 1h;
Next, the initiator was added in an amount of 0.01% by weight based on the total mass of all the monomers, and the mixture was kept at 70℃for 0.5 hours and cooled to room temperature to give a milky aqueous emulsion self-polishing antifouling resin, which was designated as MA40.
The infrared spectrum of the milky aqueous emulsion self-polishing antifouling resin was examined according to the method described in the present specification, and the results are shown in FIG. 1a.
Example 6: preparation of the aqueous self-polishing antifouling resin
The implementation of this example is as follows:
A. preparation of oily acrylic monomer mixture
Methyl methacrylate hard oil acrylic monomer, butyl acrylate soft oil acrylic monomer and methacryloxy triisopropyl silane self-polishing monomer are mixed according to the molar ratio of 20:60:5, mixing to obtain the oily acrylic acid monomer mixture;
B. preparing unsaturated organic acid aqueous solution
Uniformly mixing 6% of unsaturated organic acid of acrylic acid based on the mol of oily acrylic acid monomer and 150% of water based on the mol of unsaturated organic acid, adding 89% of sodium hydroxide based on the mol of unsaturated organic acid, dissolving, and uniformly mixing to obtain the unsaturated organic acid aqueous solution;
C. preparing aqueous monomer solution
According to the mol ratio of the oily acrylic monomer to the aqueous monomer of 85:15, adding an acrylamide aqueous monomer into the unsaturated organic acid aqueous solution obtained in the step B, and adding an initiator accounting for 1% of the total mass of the oily acrylic monomer and the aqueous monomer, wherein the initiator is an azo-diisobutylamidine hydrochloride water-soluble initiator and an azo-diisobutyronitrile oil-soluble initiator according to a mass ratio of 90:9, obtaining the aqueous monomer solution;
D. preparation of aqueous self-polishing antifouling resin
Adding a mixed solvent which is 140% of the total mass of the oily acrylic acid monomer and the aqueous monomer and consists of deionized water and ethanol into a four-neck flask provided with a stirrer, a condenser pipe and a thermometer, wherein the ethanol is 14% of the total mass of the mixed solvent, adding the oily acrylic acid monomer solution obtained in the step A and the aqueous monomer solution obtained in the step C, wherein the addition amounts of the oily acrylic acid monomer solution and the aqueous monomer solution are 10% of the respective volumes, and uniformly mixing to obtain a monomer mixture solution;
then, the monomer mixture solution was heated to a temperature of 70℃under a nitrogen atmosphere at a stirring speed of 300 rpm; when the reaction system generates blue light, dripping the rest oily acrylic monomer solution and the water-based monomer solution at the temperature within 1h, then reducing the temperature to 70 ℃ and keeping the temperature for 1h;
Next, the initiator was added in an amount of 0.01% by weight based on the total mass of all the monomers, and the mixture was kept at 70℃for 0.5 hours and cooled to room temperature to obtain a milky aqueous emulsion self-polishing antifouling resin, designated TSi5.
The infrared spectrum of the milky aqueous emulsion self-polishing antifouling resin was examined according to the method described in the present specification, and the results thereof are shown in FIG. 1b.
Example 7: preparation of the aqueous self-polishing antifouling resin
The implementation of this example is as follows:
A. preparation of oily acrylic monomer mixture
Methyl methacrylate hard oil acrylic monomer, butyl acrylate soft oil acrylic monomer and methacryloxy triisopropyl silane self-polishing monomer are mixed according to the molar ratio of 20:55:10, mixing to obtain the oily acrylic monomer mixture;
B. preparing unsaturated organic acid aqueous solution
Uniformly mixing 6% of unsaturated organic acid of acrylic acid based on the mol of oily acrylic acid monomer and 150% of water based on the mol of unsaturated organic acid, adding 89% of sodium hydroxide based on the mol of unsaturated organic acid, dissolving, and uniformly mixing to obtain the unsaturated organic acid aqueous solution;
C. preparing aqueous monomer solution
According to the mol ratio of the oily acrylic monomer to the aqueous monomer of 85:15, adding an acrylamide aqueous monomer into the unsaturated organic acid aqueous solution obtained in the step B, and adding an initiator accounting for 1% of the total mass of the oily acrylic monomer and the aqueous monomer, wherein the initiator is an azo-diisobutylamidine hydrochloride water-soluble initiator and an azo-diisobutyronitrile oil-soluble initiator according to a mass ratio of 90:9, obtaining the aqueous monomer solution;
D. preparation of aqueous self-polishing antifouling resin
Adding a mixed solvent which is 140% of the total mass of the oily acrylic acid monomer and the aqueous monomer and consists of deionized water and ethanol into a four-neck flask provided with a stirrer, a condenser pipe and a thermometer, wherein the ethanol is 14% of the total mass of the mixed solvent, adding the oily acrylic acid monomer solution obtained in the step A and the aqueous monomer solution obtained in the step C, wherein the addition amounts of the oily acrylic acid monomer solution and the aqueous monomer solution are 10% of the respective volumes, and uniformly mixing to obtain a monomer mixture solution;
then, the monomer mixture solution was heated to a temperature of 70℃under a nitrogen atmosphere at a stirring speed of 300 rpm; when the reaction system generates blue light, dripping the rest oily acrylic monomer solution and the water-based monomer solution at the temperature within 1h, then reducing the temperature to 70 ℃ and keeping the temperature for 1h;
Next, the initiator was added in an amount of 0.01% by weight based on the total mass of all the monomers, and the mixture was kept at 70℃for 0.5 hours and cooled to room temperature to obtain a milky aqueous emulsion self-polishing antifouling resin, designated TSi10.
The infrared spectrum of the milky aqueous emulsion self-polishing antifouling resin was examined according to the method described in the present specification, and the results thereof are shown in FIG. 1b.
Example 8: preparation of the aqueous self-polishing antifouling resin
The implementation of this example is as follows:
A. preparation of oily acrylic monomer mixture
Methyl methacrylate hard oil acrylic monomer, butyl acrylate soft oil acrylic monomer and methacryloxy triisopropyl silane self-polishing monomer are mixed according to the molar ratio of 20:50:15, mixing to obtain the oily acrylic monomer mixture;
B. preparing unsaturated organic acid aqueous solution
Uniformly mixing 6% of unsaturated organic acid of acrylic acid based on the mol of oily acrylic acid monomer and 150% of water based on the mol of unsaturated organic acid, adding 89% of sodium hydroxide based on the mol of unsaturated organic acid, dissolving, and uniformly mixing to obtain the unsaturated organic acid aqueous solution;
C. preparing aqueous monomer solution
According to the mol ratio of the oily acrylic monomer to the aqueous monomer of 85:15, adding an acrylamide aqueous monomer into the unsaturated organic acid aqueous solution obtained in the step B, and adding an initiator accounting for 1% of the total mass of the oily acrylic monomer and the aqueous monomer, wherein the initiator is an azo-diisobutylamidine hydrochloride water-soluble initiator and an azo-diisobutyronitrile oil-soluble initiator according to a mass ratio of 90:9, obtaining the aqueous monomer solution;
D. preparation of aqueous self-polishing antifouling resin
Adding a mixed solvent which is 140% of the total mass of the oily acrylic acid monomer and the aqueous monomer and consists of deionized water and ethanol into a four-neck flask provided with a stirrer, a condenser pipe and a thermometer, wherein the ethanol is 14% of the total mass of the mixed solvent, adding the oily acrylic acid monomer solution obtained in the step A and the aqueous monomer solution obtained in the step C, wherein the addition amounts of the oily acrylic acid monomer solution and the aqueous monomer solution are 10% of the respective volumes, and uniformly mixing to obtain a monomer mixture solution;
then, the monomer mixture solution was heated to a temperature of 70℃under a nitrogen atmosphere at a stirring speed of 300 rpm; when the reaction system generates blue light, dripping the rest oily acrylic monomer solution and the water-based monomer solution at the temperature within 1h, then reducing the temperature to 70 ℃ and keeping the temperature for 1h;
Next, the initiator was added in an amount of 0.01% by weight based on the total mass of all the monomers, and the mixture was kept at 70℃for 0.5 hours and cooled to room temperature to give a milky aqueous emulsion self-polishing antifouling resin, designated TSi15.
The infrared spectrum of the milky aqueous emulsion self-polishing antifouling resin was examined according to the method described in the present specification, and the results thereof are shown in FIG. 1b.
Example 9: preparation of the aqueous self-polishing antifouling resin
The implementation of this example is as follows:
A. preparation of oily acrylic monomer mixture
Methyl methacrylate hard oil acrylic monomer, butyl acrylate soft oil acrylic monomer and methacryloxy triisopropyl silane self-polishing monomer are mixed according to the molar ratio of 20:45:20, mixing to obtain the oily acrylic monomer mixture;
B. preparing unsaturated organic acid aqueous solution
Uniformly mixing 6% of unsaturated organic acid of acrylic acid based on the mol of oily acrylic acid monomer and 150% of water based on the mol of unsaturated organic acid, adding 89% of sodium hydroxide based on the mol of unsaturated organic acid, dissolving, and uniformly mixing to obtain the unsaturated organic acid aqueous solution;
C. preparing aqueous monomer solution
According to the mol ratio of the oily acrylic monomer to the aqueous monomer of 85:15, adding an acrylamide aqueous monomer into the unsaturated organic acid aqueous solution obtained in the step B, and adding an initiator accounting for 1% of the total mass of the oily acrylic monomer and the aqueous monomer, wherein the initiator is an azo-diisobutylamidine hydrochloride water-soluble initiator and an azo-diisobutyronitrile oil-soluble initiator according to a mass ratio of 90:9, obtaining the aqueous monomer solution;
D. preparation of aqueous self-polishing antifouling resin
Adding a mixed solvent which is 140% of the total mass of the oily acrylic acid monomer and the aqueous monomer and consists of deionized water and ethanol into a four-neck flask provided with a stirrer, a condenser pipe and a thermometer, wherein the ethanol is 14% of the total mass of the mixed solvent, adding the oily acrylic acid monomer solution obtained in the step A and the aqueous monomer solution obtained in the step C, wherein the addition amounts of the oily acrylic acid monomer solution and the aqueous monomer solution are 10% of the respective volumes, and uniformly mixing to obtain a monomer mixture solution;
then, the monomer mixture solution was heated to a temperature of 70℃under a nitrogen atmosphere at a stirring speed of 300 rpm; when the reaction system generates blue light, dripping the rest oily acrylic monomer solution and the water-based monomer solution at the temperature within 1h, then reducing the temperature to 70 ℃ and keeping the temperature for 1h;
Next, the initiator was added in an amount of 0.01% by weight based on the total mass of all the monomers, and the mixture was kept at 70℃for 0.5 hours and cooled to room temperature to obtain a milky aqueous emulsion self-polishing antifouling resin, designated as TSi20.
The infrared spectrum of the milky aqueous emulsion self-polishing antifouling resin was examined according to the method described in the present specification, and the results thereof are shown in FIG. 1b.
Example 10: preparation of the aqueous self-polishing antifouling resin
The implementation of this example is as follows:
A. preparation of oily acrylic monomer mixture
Methyl methacrylate hard oil acrylic monomer, butyl acrylate soft oil acrylic monomer and methacryloxy triisopropyl silane self-polishing monomer are mixed according to the molar ratio of 20:40:25, mixing to obtain the oily acrylic monomer mixture;
B. preparing unsaturated organic acid aqueous solution
Uniformly mixing 6% of unsaturated organic acid of acrylic acid based on the mol of oily acrylic acid monomer and 150% of water based on the mol of unsaturated organic acid, adding 89% of sodium hydroxide based on the mol of unsaturated organic acid, dissolving, and uniformly mixing to obtain the unsaturated organic acid aqueous solution;
C. preparing aqueous monomer solution
According to the mol ratio of the oily acrylic monomer to the aqueous monomer of 85:15, adding an acrylamide aqueous monomer into the unsaturated organic acid aqueous solution obtained in the step B, and adding an initiator accounting for 1% of the total mass of the oily acrylic monomer and the aqueous monomer, wherein the initiator is an azo-diisobutylamidine hydrochloride water-soluble initiator and an azo-diisobutyronitrile oil-soluble initiator according to a mass ratio of 90:9, obtaining the aqueous monomer solution;
D. preparation of aqueous self-polishing antifouling resin
Adding a mixed solvent which is 140% of the total mass of the oily acrylic acid monomer and the aqueous monomer and consists of deionized water and ethanol into a four-neck flask provided with a stirrer, a condenser pipe and a thermometer, wherein the ethanol is 14% of the total mass of the mixed solvent, adding the oily acrylic acid monomer solution obtained in the step A and the aqueous monomer solution obtained in the step C, wherein the addition amounts of the oily acrylic acid monomer solution and the aqueous monomer solution are 10% of the respective volumes, and uniformly mixing to obtain a monomer mixture solution;
then, the monomer mixture solution was heated to a temperature of 70℃under a nitrogen atmosphere at a stirring speed of 300 rpm; when the reaction system generates blue light, dripping the rest oily acrylic monomer solution and the water-based monomer solution at the temperature within 1h, then reducing the temperature to 70 ℃ and keeping the temperature for 1h;
Next, the initiator was added in an amount of 0.01% by weight based on the total mass of all the monomers, and the mixture was kept at 70℃for 0.5 hours and cooled to room temperature to obtain a milky aqueous emulsion self-polishing antifouling resin, designated TSi25.
The infrared spectrum of the milky aqueous emulsion self-polishing antifouling resin was examined according to the method described in the present specification, and the results thereof are shown in FIG. 1b.
Application example 1: the performance test of the aqueous self-polishing antifouling resin emulsion of the invention
The implementation of this application example is as follows:
the emulsion aqueous self-polishing antifouling resin prepared in examples 1 to 10 was immediately visually observed to record the apparent state of color, transparency, uniformity, blue light and the like. Then, they were put into a sample bottle and stored at room temperature for 6 months in a sealed manner, and the emulsion delamination, aggregation, solid precipitation and the like were observed in the same manner, and the stability thereof was analyzed.
It was observed that the aqueous self-polishing antifouling resin prepared in examples 1 to 5 was a milky emulsion having a uniform and stable appearance, and the emulsion did not show delamination, agglomeration, etc. after storage at room temperature for 6 months, and had slight latex particles precipitated at the bottom of the emulsion, but could be uniformly shaken. The aqueous self-polishing antifouling resin prepared in examples 6 to 10 was a uniform and stable milky white blue-transmitting emulsion in which the emulsions prepared in examples 6 and 7 did not undergo delamination, agglomeration, etc. after storage at room temperature for 6 months, whereas the aqueous self-polishing antifouling resin emulsions prepared in other examples had latex particles settled at the bottom and were uniform and stable throughout.
Application example 2: adhesion performance test of the aqueous self-polishing antifouling resin of the present invention
The implementation of this application example is as follows:
test sample: the aqueous self-polishing antifouling resins prepared in examples 1-10;
test substrate: acrylonitrile/butadiene/styrene copolymer (ABS) panels having dimensions of 50X 1mm 3 ；
Pretreatment of test substrates: the ABS plate used in the test is uniformly polished by using 80-mesh sand paper, and is respectively cleaned by ethanol and water in sequence, and is dried to constant weight at normal temperature.
The coating mode is as follows: the aqueous self-polishing antifouling resin of the invention is uniformly coated on an ABS plate by adopting a conventional coating method, and the coating amount is 300 mug;
the adhesion performance test is based on: determination of salt tolerance of marine coatings-salt and Hot salt impregnation method (GB/T10834-2008);
specifically, the adhesion properties of the aqueous self-polishing antifouling resin of the present invention were first tested by the static sea water bubble plate method, and the test results are shown in FIG. 2.
As can be seen from FIG. 2a, the aqueous self-polishing antifouling resin prepared in examples 1-5 is not fallen off in a static bubble plate experiment for 300 days, and has good adhesion performance. With the increase of the content of hard oil acrylic acid monomer, the water-based self-polishing antifouling resin has poor water resistance, is more easily corroded by water, has more surface layer peeling phenomenon, and still has good adhesion performance on a substrate.
As can be seen from FIG. 2b, the aqueous self-polishing antifouling resins prepared in examples 6 to 10 were not peeled off in the static bubble plate test 300d, were excellent in adhesion property, and were free from the surface layer peeling phenomenon. The introduction of methacryloxy triisopropyl silane can be seen to improve the water resistance of the resin.
Application example 3: self-polishing performance study of the aqueous self-polishing antifouling resin
The implementation of this application example is as follows:
test sample: the aqueous self-polishing antifouling resins prepared in examples 1-10;
test substrate: ABS plate with size of 350X 100X 3mm 3 ；
The coating mode is as follows: the coating amount of the conventional coating method is 400 mug;
ABS panels coated with an aqueous self-polishing coating were dry weighed (M 1 ) The sample plate is fixed on a dynamic paddle accelerating simulation device and then immersed in seawater to perform dynamic rotation in a cycle taking 10 days as a soaking period. After one cycle of soaking, the template was removed and the surface of the template was rinsed with deionized water, then the sample was dried in an oven at 40 ℃ for two days, and the dry weight (M t ) And putting the sample plate back into the seawater for continuous soaking. The temperature of the seawater was room temperature, the rotating speed of the drum was 80rpm, and the radius of the apparatus was 60cm.
The self-polishing abrasion rate (N) is calculated as:
wherein: m is M i Drying the mass of the aqueous self-polishing coating for the last period, wherein M is the first period i Initial mass M for drying aqueous self-polishing coating 1 ，M t For the mass of the aqueous self-polishing coating dried in this cycle, S is the area occupied by the aqueous self-polishing coating.
Test results: as can be seen from FIG. 3a, the aqueous self-polishing resins prepared in examples 1 to 5 have substantially uniform self-polishing abrasion rate, and at the initial stage of soaking (10 d), the self-polishing abrasion rate of the resin is the largest and the mass loss is the fastest due to the rapid dissolution of the residual solvent and unreacted monomer in seawater; with the extension of the soaking time (20-50 d), the self-polishing abrasion rate of the resin becomes smaller gradually and is stabilized at 5 multiplied by 10 gradually -4 ～3×10 -3 g · cm -2 Between them.
As can be seen from FIG. 3b, the aqueous self-polishing resins prepared in examples 6 to 10 had the highest self-polishing abrasion rate at the initial stage of soaking (10 d), and the self-polishing abrasion rate of the resin gradually decreased and stabilized at 1X 10 with the increase of the soaking time -3 ～2×10 -3 g · cm -2 The self-polishing rates of the aqueous self-polishing antifouling resins prepared in examples 6 to 10 were shown to be more stable than those of examples 1 to 5, and stable uniform polishing could be achieved after a certain period of time. The aqueous self-polishing resins prepared in examples 6-10 have a more stable self-polishing abrasion rate and good self-polishing performance, and the introduction of methacryloxy triisopropyl silane increases the self-polishing rate of the resin.
Application example 4: the invention relates to an algae inhibition performance research of a water-based self-polishing antifouling resin
The implementation of this application example is as follows:
test sample: the aqueous self-polishing antifouling resins prepared in examples 1-10;
test substrate: ABS plate, ABS plate size is 50×50×1mm 3 ；
The coating mode is as follows: the coating amount is 300 mug by a conventional coating method;
the experimental basis is as follows: an evaluation method described in the literature "algae cell count method comparison in algae growth inhibition experiments";
the experimental method for inhibiting algae adsorption is as follows: the filtered, sterilized and cooled seawater is taken, added with vitamin, sodium nitrate, sodium phosphate, sodium silicate and trace elements according to a certain proportion to prepare a nutrient solution, and then the nutrient solution is prepared with the crescent diamond algae cultivated to the exponential growth period to prepare an algae solution with the absorbance value of 0.09 at 680nm of ultraviolet absorption wavelength. The aqueous self-polishing antifouling resin prepared in examples 1 to 10 was painted on an ABS plate, placed face up on the bottom of a 10cm diameter petri dish, followed by the addition of 40mL of algae solution. The dishes are placed in an intelligent artificial climate box, and are cultivated under the conditions of 4000lux light intensity, 14:10 light-shade ratio and 21 ℃ temperature, and the algae liquid is shaken at the same time every day. And 5d, taking out the sample plate, washing the surface of the coating with nutrient solution, measuring the absorbance of the washing solution at 680nm by using an ultraviolet spectrophotometer, and then calculating the concentration of algae according to a standard curve.
Test results: as can be seen from FIG. 4a, as the content of methyl acrylate in the resin increases, the concentration of algae liquid (Chlorella and Chlorella) adsorbed on the surface of the aqueous self-polishing antifouling resin coating prepared in examples 1 to 5 gradually decreases, and the algae adsorption inhibition ability of the resin is stronger.
As can be seen from FIG. 4b, the concentrations of algae adsorbed on the surfaces of the aqueous self-polishing antifouling resin coatings prepared in examples 6 to 10 are generally low, and it can be seen that the introduction of methacryloxy triisopropyl silane increases the antifouling performance of the resin.
Application example 5: real sea hanging plate research of antifouling paint with water-based self-polishing antifouling resin as film forming material
The implementation of this application example is as follows:
test sample: aqueous self-polishing antifouling resin MA20 prepared in example 3 and aqueous self-polishing antifouling resin TSi5 prepared in example 6;
the implementation of this application example is as follows:
at room temperature, 35g of the aqueous self-polishing antifouling resin MA20 obtained in example 3, 1.5g of a film-forming auxiliary polyethylene glycol 3000, 25g of an inorganic antifouling agent Cu 2 O,10g of antifouling agent TMTD and 4.5g ZnO,3.0g TiO 2 ，3.0g Fe 2 O 3 3.0g of talcum powder and 0.7g of active carbon are put into a grinding cup, and are ground and dispersed for 30min by a coating quick dispersion testing machine at a rotating speed of 3000rpm, so as to obtain the water-based self-polishing anti-fouling coating M1, the fineness of a sample is measured, and when the fineness is smaller than 50 mu M, the requirements are met, and the sample is packaged for later use. Cu can also be prepared by the method 2 The amounts of O, TMTD and chlorothalonil were adjusted as shown in the following table:
test substrate: PVC plate with dimensions of 900X 300X 3mm 3 Blank plate was used as control;
pretreatment of test substrates: the PVC plate used in the test is uniformly polished by using 80-mesh sand paper, and is respectively cleaned by ethanol and water in sequence, and is dried to constant weight at normal temperature.
The coating mode is as follows: the coating amount is 8000 mug by the conventional coating method;
the antifouling performance test is based on: test methods for shallow sea impregnating coating templates (GB/T5370-2007);
the implementation method comprises the following steps: at room temperature, the anti-fouling paint obtained by the method is respectively coated on a treated PVC plate, dried in the room for 2 days, and dried in an oven at 40 ℃ for 2 days to respectively obtain the paint anti-fouling paint with the water-based self-polishing anti-fouling resin MA20 and TSi5 as film forming materials for standby. At month 12 of 2022, experiments were conducted in the sea area near the Qingdao harbor of China, with the template submerged at a depth of 1.5 meters below sea level. After a certain period of time, the template is removed from the sea and the surface of the template is lightly rinsed with seawater. After checking the template and taking a picture, the template is put back in place as soon as possible so as not to influence the growth of fouling organisms on the surface of the template. The antifouling performance of the aqueous self-polishing antifouling coating was evaluated by observing the amount of fouling and the type of fouling organisms on the surface of the sample.
Test results: as can be seen in FIG. 5, all of the aqueous self-polishing antifouling paint does not fall off and no fouling organisms are attached to the surface of the marine pegboard 90 d. Since the time of the offshore hanging plate is 12 months, the growth and development of organisms are slow, and therefore, the blank sample plate is only attached by a small amount of fouling organisms.
Claims (10)
1. The preparation method of the water-based self-polishing antifouling resin is characterized by comprising the following preparation steps of:
A. preparation of oily acrylic monomer mixture
The hard oil acrylic monomer and the soft oil acrylic monomer and the self-polishing monomer are mixed according to the mole ratio of 0 to 30: 20-70: mixing 0-30 to obtain the oily acrylic acid monomer mixture;
B. preparing unsaturated organic acid aqueous solution
Uniformly mixing 3-20% of unsaturated organic acid based on the mol of oily acrylic acid monomer and 30-200% of water based on the mol of unsaturated organic acid, adding 10-100% of sodium hydroxide based on the mol of unsaturated organic acid, dissolving, and uniformly mixing to obtain an unsaturated organic acid aqueous solution;
C. preparing aqueous monomer solution
According to the mole ratio of the oily acrylic monomer to the aqueous monomer of 80-95: 5-25, adding one or more aqueous monomers into the unsaturated organic acid aqueous solution obtained in the step B, and then adding an initiator accounting for 0.1-1.5% of the total mass of the oily acrylic acid monomer and the aqueous monomers to obtain the aqueous monomer solution;
D. Preparation of aqueous self-polishing antifouling resin
Adding a mixed solvent consisting of deionized water and alcohol accounting for 100-300% of the total mass of oily acrylic acid monomers and water-based monomers into a four-neck flask provided with a stirrer, a condenser pipe and a thermometer, adding the oily acrylic acid monomer solution obtained in the step A and the water-based monomer solution obtained in the step C, wherein the addition amounts of the oily acrylic acid monomer solution and the water-based monomer solution are respectively 5-10% of the volumes of the oily acrylic acid monomer solution and the water-based monomer solution, and uniformly mixing to obtain a monomer mixture solution;
then, heating the monomer mixture solution to 70-85 ℃ under the conditions of nitrogen atmosphere and stirring speed of 50-500 rpm; when the reaction system generates blue light, dripping or adding the rest oily acrylic acid monomer solution and the water-based monomer solution in batches at the temperature within 0.5-1.5 h, then reducing the temperature to 60-70 ℃ and keeping the temperature for 0.8-1.2 h;
then, the initiator accounting for 0.01 to 0.02 percent of the total mass of all monomers is added, and the mixture is kept at the temperature of 60 to 70 ℃ for 0.4 to 0.6 hour and cooled to room temperature, thus obtaining the milky aqueous emulsion self-polishing antifouling resin.
2. The method according to claim 1, wherein in the step a, the hard oil acrylic monomer is methyl acrylate, methyl methacrylate, ethyl acrylate or a mixture thereof; the soft oil acrylic monomer is propyl acrylate, butyl acrylate, isoamyl acrylate, dodecyl acrylate, stearyl acrylate or a mixture thereof; the self-polishing monomer is acryloxytriisopropyl silane, methacryloxytriisopropyl silane, gamma-methacryloxypropyl trimethoxysilane or a mixture thereof.
3. The process according to claim 1, wherein in step B, the unsaturated organic acid is acrylic acid, methacrylic acid, methylen succinic acid or a mixture thereof.
4. The method of claim 1, wherein in step C, the aqueous monomer is acrylamide, hydroxyacrylamide, vinylpyrrolidone, hydroxyacrylate, or a mixture thereof.
5. The process according to claim 4, wherein the hydroxyacrylamide is N-methylolacrylamide, N-hydroxyethyl acrylamide or N-hydroxypropyl acrylamide; the hydroxy acrylic ester is hydroxyethyl acrylate, hydroxypropyl acrylate or 4-hydroxy butyl acrylate or a mixture thereof.
6. The preparation method according to claim 1, wherein in the step C, the initiator is a water-soluble initiator and an oil-soluble initiator in a mass ratio of 70-95: 0 to 10.
7. The process according to claim 6, wherein the aqueous initiator is one or more initiators selected from the group consisting of azobisiso Ding Mi hydrochloride, azobisiso imidazoline, azobisiso butylamidine hydrochloride, potassium persulfate and ammonium persulfate; the oily initiator is one or more initiators selected from azodiisobutyronitrile, azodiisoheptonitrile, benzoyl peroxide tert-butyl ester or methyl ethyl ketone peroxide.
8. The process according to claim 1, wherein in the step D, the alcohol is one or more alcohols selected from methanol, ethanol, ethylene glycol or glycerol, and the amount of the alcohol is 3 to 20% by volume of the mixed solvent.
9. An aqueous self-polishing antifouling resin prepared by the method according to any one of claims 1 to 8.
10. Use of the aqueous self-polishing antifouling resin according to claim 9 in the field of marine biofouling control.
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| CN202311157272.8A CN117447641A (en) | 2023-09-08 | 2023-09-08 | Water-based self-polishing antifouling resin, preparation method and application thereof |
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| CN202311157272.8A CN117447641A (en) | 2023-09-08 | 2023-09-08 | Water-based self-polishing antifouling resin, preparation method and application thereof |
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