CN116891668B - Epoxy resin antifouling paint based on double-strategy antibacterial property and preparation method thereof - Google Patents
Epoxy resin antifouling paint based on double-strategy antibacterial property and preparation method thereof Download PDFInfo
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- CN116891668B CN116891668B CN202310780103.3A CN202310780103A CN116891668B CN 116891668 B CN116891668 B CN 116891668B CN 202310780103 A CN202310780103 A CN 202310780103A CN 116891668 B CN116891668 B CN 116891668B
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- Prior art keywords
- epoxy resin
- antifouling
- curing agent
- agent
- antifouling paint
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- 230000003373 anti-fouling effect Effects 0.000 title claims abstract description 80
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 59
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 59
- 239000003973 paint Substances 0.000 title claims abstract description 54
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 78
- 239000000178 monomer Substances 0.000 claims abstract description 36
- 239000002519 antifouling agent Substances 0.000 claims abstract description 35
- 238000000576 coating method Methods 0.000 claims abstract description 22
- 239000011248 coating agent Substances 0.000 claims abstract description 20
- 229930014626 natural product Natural products 0.000 claims abstract description 17
- 239000011256 inorganic filler Substances 0.000 claims abstract description 16
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000012650 click reaction Methods 0.000 claims abstract description 10
- 239000003999 initiator Substances 0.000 claims abstract description 10
- -1 mercapto alkene Chemical class 0.000 claims abstract description 9
- 238000010526 radical polymerization reaction Methods 0.000 claims abstract description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002131 composite material Substances 0.000 claims description 28
- 239000004359 castor oil Substances 0.000 claims description 23
- 235000019438 castor oil Nutrition 0.000 claims description 23
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 18
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 16
- UFULAYFCSOUIOV-UHFFFAOYSA-N cysteamine Chemical compound NCCS UFULAYFCSOUIOV-UHFFFAOYSA-N 0.000 claims description 14
- 229960003151 mercaptamine Drugs 0.000 claims description 14
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 10
- 239000004593 Epoxy Substances 0.000 claims description 8
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 8
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 claims description 8
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 claims description 7
- 125000005395 methacrylic acid group Chemical group 0.000 claims description 7
- 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 5
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims description 5
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 5
- RBQRWNWVPQDTJJ-UHFFFAOYSA-N methacryloyloxyethyl isocyanate Chemical compound CC(=C)C(=O)OCCN=C=O RBQRWNWVPQDTJJ-UHFFFAOYSA-N 0.000 claims description 5
- 229920000570 polyether Polymers 0.000 claims description 5
- 239000011787 zinc oxide Substances 0.000 claims description 5
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 4
- 239000005751 Copper oxide Substances 0.000 claims description 4
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 4
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims description 4
- 229910000431 copper oxide Inorganic materials 0.000 claims description 4
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 4
- 229910001923 silver oxide Inorganic materials 0.000 claims description 4
- 238000005260 corrosion Methods 0.000 claims description 3
- 238000005286 illumination Methods 0.000 claims description 3
- QUSNBJAOOMFDIB-UHFFFAOYSA-N monoethyl amine Natural products CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 claims description 2
- OXBLVCZKDOZZOJ-UHFFFAOYSA-N 2,3-Dihydrothiophene Chemical compound C1CC=CS1 OXBLVCZKDOZZOJ-UHFFFAOYSA-N 0.000 claims description 2
- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-UHFFFAOYSA-N 0.000 claims description 2
- XSHISXQEKIKSGC-UHFFFAOYSA-N 2-aminoethyl 2-methylprop-2-enoate;hydron;chloride Chemical compound Cl.CC(=C)C(=O)OCCN XSHISXQEKIKSGC-UHFFFAOYSA-N 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 230000009471 action Effects 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 239000011259 mixed solution Substances 0.000 description 16
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 11
- 238000013329 compounding Methods 0.000 description 10
- 230000001678 irradiating effect Effects 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 238000001816 cooling Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 239000012299 nitrogen atmosphere Substances 0.000 description 9
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical compound C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 8
- REPVLJRCJUVQFA-UHFFFAOYSA-N (-)-isopinocampheol Natural products C1C(O)C(C)C2C(C)(C)C1C2 REPVLJRCJUVQFA-UHFFFAOYSA-N 0.000 description 8
- 239000003899 bactericide agent Substances 0.000 description 8
- 229940116229 borneol Drugs 0.000 description 8
- CKDOCTFBFTVPSN-UHFFFAOYSA-N borneol Natural products C1CC2(C)C(C)CC1C2(C)C CKDOCTFBFTVPSN-UHFFFAOYSA-N 0.000 description 8
- DTGKSKDOIYIVQL-UHFFFAOYSA-N dl-isoborneol Natural products C1CC2(C)C(O)CC1C2(C)C DTGKSKDOIYIVQL-UHFFFAOYSA-N 0.000 description 8
- RRAFCDWBNXTKKO-UHFFFAOYSA-N eugenol Chemical compound COC1=CC(CC=C)=CC=C1O RRAFCDWBNXTKKO-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 230000002195 synergetic effect Effects 0.000 description 7
- 238000011160 research Methods 0.000 description 5
- NPBVQXIMTZKSBA-UHFFFAOYSA-N Chavibetol Natural products COC1=CC=C(CC=C)C=C1O NPBVQXIMTZKSBA-UHFFFAOYSA-N 0.000 description 4
- 239000005770 Eugenol Substances 0.000 description 4
- UVMRYBDEERADNV-UHFFFAOYSA-N Pseudoeugenol Natural products COC1=CC(C(C)=C)=CC=C1O UVMRYBDEERADNV-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229960002217 eugenol Drugs 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 241000589517 Pseudomonas aeruginosa Species 0.000 description 3
- 230000001580 bacterial effect Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 244000005700 microbiome Species 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 230000035882 stress Effects 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 241000233866 Fungi Species 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000003115 biocidal effect Effects 0.000 description 2
- 239000003139 biocide Substances 0.000 description 2
- 229960001777 castor oil Drugs 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000012745 toughening agent Substances 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004621 biodegradable polymer Substances 0.000 description 1
- 229920002988 biodegradable polymer Polymers 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229920006334 epoxy coating Polymers 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000013632 homeostatic process Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- 238000002464 physical blending Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
- C07C319/18—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by addition of thiols to unsaturated compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5006—Amines aliphatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
-
- 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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- 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
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
-
- 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
- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
- C09D5/1612—Non-macromolecular compounds
- C09D5/1625—Non-macromolecular compounds organic
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0806—Silver
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2248—Oxides; Hydroxides of metals of copper
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2286—Oxides; Hydroxides of metals of silver
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Plant Pathology (AREA)
- Epoxy Resins (AREA)
- Paints Or Removers (AREA)
Abstract
The invention belongs to the field of marine antifouling, and relates to an epoxy resin antifouling paint based on double-strategy antibacterial property and a preparation method thereof. The coating takes natural compounds and methacrylic acid monomers as raw materials, and prepares a novel antifouling agent by a free radical polymerization method under the action of an initiator. A toughening curing agent is prepared by adopting a mercapto alkene click reaction. Meanwhile, inorganic filler is added, and under the action of a compound curing agent, the antifouling agent is polymerized into an epoxy resin network, so that the environment-friendly antifouling paint with excellent antifouling performance is obtained. The marine antifouling paint prepared by the invention has excellent antifouling efficiency, and the cost of the raw materials selected by the invention is lower, thus the marine antifouling paint has wide market prospect. Simple steps, convenient operation and strong practicability.
Description
Technical Field
The invention relates to an epoxy resin paint applicable to the field of marine antifouling, in particular to a preparation method of an epoxy resin antifouling paint based on double-strategy antibacterial property.
Background
The disclosure of this background section is only intended to increase the understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art already known to those of ordinary skill in the art.
Marine biofouling can be one of the great challenges facing the shipping industry. The attachment of marine fouling organisms is a relatively complex interaction process, which is a process of poor attachment, growth and reproduction of microorganisms (bacteria, fungi, etc.) or animals and plants on the surface of marine equipment, which can bring about serious damage to large-scale equipment such as ships. For example, increasing the resistance of the fluid to slow down the speed of travel and increase fuel consumption; can cause biological intrusion thereby disrupting marine environmental homeostasis; can promote the aging of the ship surface and increase the maintenance times, the maintenance cost and the like.
Prevention of marine biofouling has also become one of the key research directions for human marine activity, and among many protection means, brushing of antifouling paint is currently the most widely used, economical and effective antifouling technology. Along with the continuous improvement of human environmental awareness, requirements are also made on the use of marine antifouling paint and the environmental protection property of the marine antifouling paint. Therefore, development of an environmentally friendly antifouling paint has become a research hotspot. There is also a great deal of research done by researchers today on the development of marine antifouling paints and bactericides, wherein the antifouling paints mainly include: tin-free self-polishing antifouling material, amphiphilic polymer antifouling material, fouling release type antifouling material, biodegradable polymer-based antifouling material, bionic antifouling material and fouling resistance type antifouling material. Bactericides have also undergone a range of evolution from the original organotin bactericides to inorganic bactericides (silver, zinc, copper, titanium dioxide, etc.) to natural biological antifouling agents, and such natural bactericides have been of great interest to researchers.
Polydimethylsiloxane (PDMS) is one of the important role players in marine antifouling paints due to its low surface energy, low modulus, low adhesion to hard soil. But its poor adhesion to the substrate affects its antifouling life to some extent, thus affecting its use. In addition, the epoxy resin is also an important class of coating base materials, belongs to thermosetting resins, has the characteristics of high adhesive force, strong cohesiveness, good stability and insulativity and the like, and can be widely applied to industries such as marine heavy-duty anti-corrosion and antifouling paint and the like as a film forming substance. The bactericide is added into the epoxy resin matrix, so that microorganisms in the marine environment can be effectively killed through the bactericide, and the adhesion of the microorganisms is inhibited, thereby having an antifouling effect on marine equipment, but the bactericide has obvious defects: for example, direct physical blending of the biocide into the epoxy substrate can result in uncontrolled release of the biocide, thereby affecting the protective life of the anti-fouling coating.
Disclosure of Invention
The invention aims to overcome the defects in the existing materials and provide an epoxy resin antifouling paint based on double-strategy antibacterial property and a preparation method thereof. An antifouling agent is prepared by adopting a simple and convenient free radical polymerization method, and is polymerized in situ into an epoxy resin network, a toughening curing agent is prepared by adopting a mercapto ene click reaction, and an environment-friendly antifouling paint with excellent antifouling performance is prepared under the synergistic antibacterial effect of inorganic filler.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the invention provides a preparation method of an epoxy resin antifouling paint based on double-strategy antibacterial property, which comprises the following steps:
mixing a natural compound and a methacrylic monomer in a solvent, and performing free radical polymerization in the presence of a thermal initiator to obtain an antifouling agent;
Carrying out a sulfhydryl alkene click reaction on castor oil and a sulfhydryl ethylamine monomer under the existence of a photoinitiator through illumination to obtain a toughening curing agent;
mixing the toughening curing agent with a polyether amine curing agent to obtain a composite curing agent;
Mixing the antifouling agent, epoxy resin, inorganic filler and composite curing agent, and curing to obtain epoxy resin antifouling paint;
wherein the natural compound is one of eugenol, borneol and castor oil;
The mass ratio of the natural compound to the methacrylic acid monomer is 1-3: 1 to 2;
The mass ratio of the mercaptoethylamine to the castor oil is 3.3-3.6: 1 to 1.2.
The invention provides an epoxy resin antifouling paint utilizing a special surface structure of a polymer and a dual strategy of releasing sterilization and a preparation method thereof, wherein a natural compound is used as a raw material to prepare an environment-friendly antifouling agent, and the environment-friendly antifouling paint with excellent antifouling performance is prepared under the synergistic antibacterial effect of inorganic fillers.
In a second aspect of the invention, an epoxy anti-fouling coating prepared by the method described above is provided.
In a third aspect, the invention provides an application of the epoxy resin antifouling paint in preparing marine anti-corrosion, antifouling and antibacterial coatings.
Compared with the prior art, the invention has the following beneficial effects:
(1) Before the preparation, the antibacterial efficiency of the epoxy resin antifouling coating can reach 97% under the synergistic antibacterial effect of the antifouling agent and the inorganic filler by designing the synergistic antibacterial system of the 'attack and defense' fence, so that the method for solving the antifouling performance of the epoxy resin is provided in theory, and the method has profound research significance.
(2) The prepared anti-fouling agent fully utilizes the excellent characteristics of natural compounds, so that the prepared anti-fouling agent not only can provide antibacterial performance, but also can change the wettability of the coating.
(3) According to the invention, the inorganic filler is added to prepare the synergistic antibacterial antifouling paint, and the prepared antifouling paint not only has excellent antifouling effect, but also does not weaken the anticorrosion effect of the epoxy resin.
(4) The curing agent with toughening effect is prepared through click reaction, and can better improve the brittle fracture characteristic of the pure epoxy resin after being compounded with the commercially available curing agent.
(5) The preparation method provided by the invention is simple, low in cost, high in practicability and easy to popularize.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention.
FIG. 1 is a stress-strain diagram of an epoxy antifouling paint.
FIG. 2 is a graph of hardness of an epoxy antifouling paint.
Fig. 3 is a graph showing a change in contact angle of the epoxy resin antifouling paint.
FIG. 4 is a graph of the antimicrobial efficiency of an epoxy antifouling paint.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the invention. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
A preparation method of an epoxy resin antifouling paint based on double-strategy antibacterial comprises the following steps:
mixing a natural compound and a methacrylic monomer in a solvent, and performing free radical polymerization in the presence of a thermal initiator to obtain an antifouling agent;
Carrying out a sulfhydryl alkene click reaction on castor oil and a sulfhydryl ethylamine monomer under the existence of a photoinitiator through illumination to obtain a toughening curing agent;
mixing the toughening curing agent with a polyether amine curing agent to obtain a composite curing agent;
Mixing the antifouling agent, epoxy resin, inorganic filler and composite curing agent, and curing to obtain epoxy resin antifouling paint;
wherein the natural compound is one of eugenol, borneol and castor oil;
The mass ratio of the natural compound to the methacrylic acid monomer is 1-3: 1 to 2;
The mass ratio of the mercaptoethylamine to the castor oil is 3.3-3.6: 1 to 1.2.
The invention takes natural compounds and methacrylic acid monomers as raw materials, prepares an antifouling agent by a free radical polymerization method under the action of an initiator, and prepares a toughening curing agent by adopting a mercapto alkene click reaction. Meanwhile, inorganic filler is added, and under the action of a compound curing agent, the anti-fouling agent is polymerized into an epoxy resin network in situ, so that the environment-friendly anti-fouling paint with excellent anti-fouling performance is obtained.
In some embodiments, the methacrylic monomer is one of hydroxyethyl methacrylate, 2-aminoethyl methacrylate hydrochloride, glycidyl methacrylate, isocyanoethyl methacrylate, methacrylamide.
The application systematically analyzes and searches the performances of the existing natural compound and methacrylic monomer polymer, and discovers that: dissolving natural compounds borneol, isocyanoethyl methacrylate and a thermal initiator (ammonium persulfate) in tetrahydrofuran, and carrying out polymerization reaction (duration: 24 h) under the condition of heating (30-50 ℃) and stirring to obtain the antifouling agent with optimal antibacterial performance and coating wettability.
Meanwhile, the castor oil, the mercaptoethylamine and the photoinitiator (2, 2-dimethoxy-2-phenylacetophenone) are subjected to click reaction (the duration is 5-80 min) under the irradiation of ultraviolet light (250-420 nm), and the curing agent with better toughening effect is prepared.
In some embodiments, the thermal initiator is one of ammonium persulfate, azobisisobutyronitrile, N-dimethylaniline.
In some embodiments, the thermal initiator is added in an amount of 0.1% to 5% of the total mass of natural compounds and methacrylic monomers;
In some embodiments, the photoinitiator is one of 1-hydroxycyclohexyl phenyl ketone, 2-dimethoxy-2-phenyl acetophenone, 2, 4-dihydroxybenzophenone.
In some embodiments, the photoinitiator is added in an amount of 0.1% to 1% of the total mass of the monomers.
In some embodiments, the free radical polymerization conditions are heated to 30-50 ℃ and reacted under an inert atmosphere for 24-25 hours.
In some embodiments, the thiol-ene click reaction conditions are under ultraviolet light (250-420 nm) irradiation for 5-75 minutes.
In some embodiments, the mass ratio of the epoxy resin, the anti-fouling agent, and the inorganic filler is 5:0.1 to 0.3:0.1 to 0.3.
In some embodiments, the inorganic filler is one of silver nanoparticles, copper oxide, silver oxide, zinc oxide.
The mass ratio of the toughening curing agent to the polyether amine curing agent is 1:1, a step of;
In some embodiments, the mass ratio of the composite curing agent to the anti-fouling agent is 0.25-30: 5 to 15.
In some embodiments, the temperature of the curing is 20 to 110 ℃.
The invention will now be described in further detail with reference to the following specific examples, which should be construed as illustrative rather than limiting.
In the following examples, the starting materials are commercially available, wherein polyetheramine D230 is available from Shanghai Ala Biotechnology Co., ltd.
Example 1:
Mixing borneol and isocyano ethyl methacrylate according to a mass ratio of 3:1 is mixed and dissolved in DMF solution, ammonium persulfate with the total mass percent of 0.2% of the monomers is added, the mixed solution is placed in a three-neck flask, and the mixed solution is stirred and reacted for 24 hours at 40 ℃ under the nitrogen atmosphere. Cooling to room temperature after the reaction is completed to obtain the antifouling agent. Castor oil and mercaptoethylamine in a molar ratio of 3.3:1.0, adding a photoinitiator (2, 2-dimethoxy-2-phenylacetophenone) with the total mass fraction of the monomers of 0.8%, and irradiating for 35min at 365nm of ultraviolet light to prepare the toughening curing agent. The toughening curing agent and polyetheramine D230 are mixed according to the mass ratio of 1:1, compounding to prepare a composite curing agent; epoxy resin: stain-proofing agent: zinc oxide: the mass ratio of the composite curing agent is 5:0.2:0.1: and 2.35, uniformly mixing by ultrasonic waves, and then placing the mixture at room temperature for curing reaction to obtain the epoxy resin antifouling paint.
Example 2:
Eugenol and glycidyl methacrylate are mixed according to the mass ratio of 2:1 is mixed and dissolved in DMAC solution, ammonium persulfate with the total mass percent of the monomers of 0.1 percent is added, the mixed solution is placed in a three-neck flask, and the mixed solution is stirred and reacted for 24 hours at 40 ℃ under the nitrogen atmosphere. Cooling to room temperature after the reaction is completed to obtain the antifouling agent. Castor oil and mercaptoethylamine in a molar ratio of 3.5:1.1, adding a photoinitiator (2, 2-dimethoxy-2-phenylacetophenone) with the total mass fraction of the monomers of 0.8%, and irradiating for 15min at 365nm of ultraviolet light to prepare the toughening curing agent. The toughening curing agent and polyetheramine D230 are mixed according to the mass ratio of 1:1, compounding to prepare a composite curing agent; epoxy resin: stain-proofing agent: silver nanoparticles: the mass ratio of the composite curing agent is 5:0.2:0.1: and 2.35, uniformly mixing by ultrasonic waves, and then placing the mixture at room temperature for curing reaction to obtain the epoxy resin antifouling paint.
Example 3:
Mixing borneol and glycidyl methacrylate according to the mass ratio of 1:2, mixing and dissolving in DMF solution, adding N, N-dimethylaniline with the total mass percent of the monomers, placing the mixed solution in a three-neck flask, and stirring and reacting for 24h at 40 ℃ under nitrogen atmosphere. Cooling to room temperature after the reaction is completed to obtain the antifouling agent. Castor oil and mercaptoethylamine in a molar ratio of 3.2:1.2, adding a photoinitiator (2, 2-dimethoxy-2-phenylacetophenone) with the total mass fraction of the monomers of 0.8%, and irradiating for 25min at 365nm of ultraviolet light to prepare the toughening curing agent. The toughening curing agent and polyetheramine D230 are mixed according to the mass ratio of 1:1, compounding to prepare a composite curing agent; epoxy resin: stain-proofing agent: silver oxide: the mass ratio of the composite curing agent is 5:0.2:0.2: and 2.35, uniformly mixing by ultrasonic, and then placing in a baking oven (70 ℃) for curing reaction to obtain the epoxy resin antifouling paint.
Example 4:
Eugenol and hydroxyethyl methacrylate are mixed according to the mass ratio of 1:1 is mixed and dissolved in THF solution, azodiisobutyronitrile with the total mass percent of the monomers of 0.1 percent is added, the mixed solution is placed in a three-neck flask, and the mixed solution is stirred and reacted for 24 hours at 30 ℃ under nitrogen atmosphere. Cooling to room temperature after the reaction is completed to obtain the antifouling agent. Castor oil and mercaptoethylamine in a molar ratio of 3.3:1.2, adding a photoinitiator (2, 2-dimethoxy-2-phenylacetophenone) with the total mass fraction of the monomers of 0.8%, and irradiating for 5min at 365nm of ultraviolet light to prepare the toughening curing agent. The toughening curing agent and polyetheramine D230 are mixed according to the mass ratio of 1:1, compounding to prepare a composite curing agent; epoxy resin: stain-proofing agent: copper oxide: the mass ratio of the composite curing agent is 5:0.1:0.1:2.28, after being evenly mixed by ultrasonic, the mixture is placed in a baking oven (100 ℃) for curing reaction, and the epoxy resin antifouling paint is obtained.
Example 5:
The castor oil and the glycidyl methacrylate are mixed according to the mass ratio of 3:1 is mixed and dissolved in DMF solution, azodiisobutyronitrile with the total mass percent of the monomers of 0.3 percent is added, the mixed solution is placed in a three-neck flask, and the mixed solution is stirred and reacted for 24 hours at 50 ℃ under nitrogen atmosphere. Cooling to room temperature after the reaction is completed to obtain the antifouling agent. Castor oil and mercaptoethylamine in a molar ratio of 3.4:1.2, adding a photoinitiator (2, 2-dimethoxy-2-phenylacetophenone) with the total mass fraction of the monomers of 0.8%, and irradiating for 45min at 365nm of ultraviolet light to prepare the toughening curing agent. The toughening curing agent and polyetheramine D230 are mixed according to the mass ratio of 1:1, compounding to prepare a composite curing agent; epoxy resin: stain-proofing agent: zinc oxide: the mass ratio of the composite curing agent is 5:0.2:0.2: and 2.35, uniformly mixing by ultrasonic waves, and then placing the mixture at room temperature for curing reaction to obtain the epoxy resin antifouling paint.
Example 6:
Castor oil and hydroxyethyl methacrylate are mixed according to the mass ratio of 3:1 is mixed and dissolved in DMF solution, ammonium persulfate with the total mass percent of the monomers of 0.3 percent is added, the mixed solution is placed in a three-neck flask, and the mixed solution is stirred and reacted for 24 hours at 50 ℃ under the nitrogen atmosphere. Cooling to room temperature after the reaction is completed to obtain the antifouling agent. Castor oil and mercaptoethylamine in a molar ratio of 3.4:1.0, adding a photoinitiator (2, 2-dimethoxy-2-phenylacetophenone) with the total mass fraction of the monomers of 0.8%, and irradiating for 55min at 365nm of ultraviolet light to prepare the toughening curing agent. The toughening curing agent and polyetheramine D230 are mixed according to the mass ratio of 1:1, compounding to prepare a composite curing agent; epoxy resin: stain-proofing agent: silver nanoparticles: the mass ratio of the composite curing agent is 5:0.3:0.1:2.42, after being evenly mixed by ultrasonic, the mixture is placed in an oven (80 ℃) for curing reaction, and the epoxy resin antifouling paint is obtained.
Example 7:
The borneol and the methacrylamide are mixed according to the mass ratio of 3:1 is mixed and dissolved in acetone solution, and N, N-dimethylaniline with the total mass percent of 0.3 percent is added, the mixed solution is placed in a three-neck flask, and the mixed solution is stirred and reacted for 24 hours at 50 ℃ under nitrogen atmosphere. Cooling to room temperature after the reaction is completed to obtain the antifouling agent. Castor oil and mercaptoethylamine in a molar ratio of 3.4:1.1, adding a photoinitiator (2, 2-dimethoxy-2-phenylacetophenone) with the total mass fraction of the monomers of 0.8%, and irradiating for 65min at 365nm of ultraviolet light to prepare the toughening curing agent. The toughening curing agent and polyetheramine D230 are mixed according to the mass ratio of 1:1, compounding to prepare a composite curing agent; epoxy resin: stain-proofing agent: silver oxide: the mass ratio of the composite curing agent is 5:0.3:0.2:2.42, after being evenly mixed by ultrasonic, the mixture is placed at room temperature for curing reaction, and the epoxy resin antifouling paint is obtained.
Example 8:
The castor oil and the methacrylamide are mixed according to the mass ratio of 3:1, mixing and dissolving in ethanol solution, adding ammonium persulfate with the total mass percent of the monomers of 0.3%, placing the mixed solution into a three-neck flask, and stirring and reacting for 24 hours at 50 ℃ under nitrogen atmosphere. Cooling to room temperature after the reaction is completed to obtain the antifouling agent. Castor oil and mercaptoethylamine in a molar ratio of 3.6:1.2, adding a photoinitiator (2, 2-dimethoxy-2-phenylacetophenone) with the total mass fraction of the monomers of 0.8%, and irradiating for 75 minutes under 365nm ultraviolet light to prepare the toughening curing agent. The toughening curing agent and polyetheramine D230 are mixed according to the mass ratio of 1:1, compounding to prepare a composite curing agent; epoxy resin: stain-proofing agent: copper oxide: the mass ratio of the composite curing agent is 5:0.3:0.3:2.42, after being evenly mixed by ultrasonic, the mixture is placed in an oven (110 ℃) for curing reaction, and the epoxy resin antifouling paint is obtained.
Comparative example 1:
Mixing borneol and isocyano ethyl methacrylate according to a mass ratio of 3:1 is mixed and dissolved in DMF solution, ammonium persulfate with the total mass percent of 0.2% of the monomers is added, the mixed solution is placed in a three-neck flask, and the mixed solution is stirred and reacted for 24 hours at 40 ℃ under the nitrogen atmosphere. Cooling to room temperature after the reaction is completed to obtain the antifouling agent. Castor oil and mercaptoethylamine in a molar ratio of 3.3:1.0, adding a photoinitiator (2, 2-dimethoxy-2-phenylacetophenone) with the total mass fraction of the monomers of 0.8%, and irradiating for 35min at 365nm of ultraviolet light to prepare the toughening curing agent. The toughening curing agent and polyetheramine D230 are mixed according to the mass ratio of 1:1, compounding to prepare a composite curing agent; epoxy resin: stain-proofing agent: the mass ratio of the composite curing agent is 5:0.3:2.42, after being evenly mixed by ultrasonic, the mixture is placed at room temperature for curing reaction, and the epoxy resin antifouling paint is obtained.
Comparative example 2:
Castor oil and mercaptoethylamine in a molar ratio of 3.3:1.0, adding a photoinitiator (2, 2-dimethoxy-2-phenylacetophenone) with the total mass fraction of the monomers of 0.8%, and irradiating for 35min at 365nm of ultraviolet light to prepare the toughening curing agent. The toughening curing agent and polyetheramine D230 are mixed according to the mass ratio of 1:1, compounding to prepare a composite curing agent; epoxy resin: zinc oxide: the mass ratio of the composite curing agent is 5:0.3:2.2, after being evenly mixed by ultrasonic, the mixture is placed at room temperature for curing reaction, and the epoxy resin antifouling paint is obtained.
As shown in FIG. 1, a stress strain curve (according to GB/T1731-2020) is shown for an epoxy antifouling paint and a comparative example. As can be seen from the comparison of example 1 and comparative example 1, the addition of the inorganic filler increases the stress of the coating, and from the comparison of example 1 and comparative example 2, the addition of the anti-fouling agent increases the strain of the coating, so that the simultaneous addition of both results in a relatively balanced stress and strain of the coating.
As shown in FIG. 2, a bar graph of the hardness of the epoxy antifouling paint (tested according to GB 2411-78-1980) is shown. From the above, the addition of the anti-fouling agent and the toughening agent can increase the softness of the coating, while the addition of the inorganic filler can increase the hardness of the coating, and the addition of the anti-fouling agent and the toughening agent can lead the coating to have stronger hardness, which shows obvious advantages compared with the organosilicon coating.
As shown in fig. 3, the wettability of the coating changed more significantly (as seen by measuring the water contact angle of the coating) with the addition of the anti-fouling agent and the nanoparticles. It is known that epoxy coatings are inherently hydrophilic and, upon the synergistic effect of the two, the anti-fouling coating is transformed from hydrophilic to hydrophobic, which is mainly benefited by the steric structure of natural borneol.
The epoxy resin antifouling paints prepared in example 1 and comparative examples 1 and 2 were tested for antibacterial efficiency. The sample was sterilized under an ultraviolet lamp of 20w,253.7nm for 30min, and the bacterial liquid (Pseudomonas aeruginosa) was diluted to 108CFU/mL by LB liquid medium, placed in a petri dish, and the diluted bacterial liquid (10 mL) was added. The dishes containing the samples and bacterial solutions were placed in a constant temperature incubator and incubated at 37℃for 12h. After the incubation was completed, the sample was serially diluted 103-fold with LB, 10. Mu.L of the diluted liquid medium sample was scraped uniformly onto LB solid medium, and incubated at 37℃for 24 hours. The number of adhering colonies of the epoxy resin antifouling paints of example 1 and comparative examples 1 and 2 was measured by a plate count method. The number of colonies grown on the solid medium was designated as N 1. The colony count of the control group was designated as N 2.
The antibacterial ratio (AE) of the epoxy resin antifouling paint is calculated according to formula (1):
As shown in FIG. 4, the antibacterial effect of the coating was investigated using Pseudomonas aeruginosa as a fungus study object. Under the synergistic antibacterial effect of the antifouling agent and the inorganic filler, the antibacterial efficiency of the epoxy resin antifouling coating prepared in the embodiment 1 on pseudomonas aeruginosa can reach 97%, which opens up a new road for the epoxy resin in the marine antifouling field and has deeper research significance.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. The preparation method of the double-strategy antibacterial epoxy resin antifouling paint is characterized by comprising the following steps of:
mixing a natural compound and a methacrylic monomer in a solvent, and performing free radical polymerization in the presence of a thermal initiator to obtain an antifouling agent;
Carrying out a sulfhydryl alkene click reaction on castor oil and a sulfhydryl ethylamine monomer under the existence of a photoinitiator through illumination to obtain a toughening curing agent;
mixing the toughening curing agent with a polyether amine curing agent to obtain a composite curing agent;
Mixing the antifouling agent, epoxy resin, inorganic filler and composite curing agent, and curing to obtain epoxy resin antifouling paint;
wherein the natural compound is castor oil;
the mass ratio of the natural compound to the methacrylic acid monomer is 1-3: 1-2;
the mass ratio of the mercaptoethylamine to the castor oil is 1.2:3.6;
The mass ratio of the epoxy resin to the antifouling agent to the inorganic filler is 5:0.1 to 0.3:0.1 to 0.3;
the inorganic filler is one of silver nano particles, copper oxide, silver oxide and zinc oxide;
The mass ratio of the toughening curing agent to the polyether amine curing agent is 1:1, a step of;
The mass ratio of the composite curing agent to the antifouling agent is 2.42:0.3;
The curing temperature is 20-110 ℃.
2. The method for preparing the dual-policy antibacterial epoxy resin antifouling paint according to claim 1, wherein the methacrylic monomer is one of hydroxyethyl methacrylate, 2-amino ethyl methacrylate hydrochloride, glycidyl methacrylate, isocyano ethyl methacrylate and methacrylamide.
3. The method for preparing the dual-strategy antibacterial-based epoxy resin antifouling paint according to claim 1, wherein the thermal initiator is one of ammonium persulfate, azodiisobutyronitrile and N, N-dimethylaniline;
Or, the addition amount of the thermal initiator is 0.1% -5% of the total mass of the natural compound and the methacrylic acid monomer;
Or the photoinitiator is one of 1-hydroxycyclohexyl phenyl ketone, 2-dimethoxy-2-phenyl acetophenone and 2, 4-dihydroxybenzophenone;
or the addition amount of the photoinitiator is 0.1% -1% of the total mass of the monomers.
4. The preparation method of the dual-strategy antibacterial-based epoxy resin antifouling paint according to claim 1, wherein the condition of free radical polymerization is heating to 30-50 ℃, and reacting for 24-25 h under inert atmosphere.
5. The method for preparing the dual-strategy antibacterial epoxy resin antifouling paint according to claim 1, wherein the condition of the thiol-ene click reaction is that the reaction is carried out for 5-75min under the irradiation of ultraviolet light of 250-420 nm.
6. An epoxy anti-fouling coating prepared by the method of any one of claims 1 to 5.
7. The use of the epoxy resin antifouling paint of claim 6 in preparing marine anti-corrosion, anti-fouling and antibacterial coatings.
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