CN110591159A - Modified nano-silver particles and preparation method thereof, silane compound and preparation method thereof, antifouling coating and preparation method thereof - Google Patents
Modified nano-silver particles and preparation method thereof, silane compound and preparation method thereof, antifouling coating and preparation method thereof Download PDFInfo
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- CN110591159A CN110591159A CN201910964230.2A CN201910964230A CN110591159A CN 110591159 A CN110591159 A CN 110591159A CN 201910964230 A CN201910964230 A CN 201910964230A CN 110591159 A CN110591159 A CN 110591159A
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- 239000002245 particle Substances 0.000 title claims abstract description 117
- 230000003373 anti-fouling effect Effects 0.000 title claims abstract description 79
- -1 silane compound Chemical class 0.000 title claims abstract description 58
- 229910000077 silane Inorganic materials 0.000 title claims abstract description 49
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical class [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title abstract description 98
- 238000000576 coating method Methods 0.000 title abstract description 49
- 238000002360 preparation method Methods 0.000 title abstract description 33
- 239000011248 coating agent Substances 0.000 title abstract description 32
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000001263 FEMA 3042 Substances 0.000 claims abstract description 47
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 claims abstract description 47
- 229940033123 tannic acid Drugs 0.000 claims abstract description 47
- 235000015523 tannic acid Nutrition 0.000 claims abstract description 47
- 229920002258 tannic acid Polymers 0.000 claims abstract description 47
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 claims abstract description 46
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims abstract description 21
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims abstract description 19
- 239000003973 paint Substances 0.000 claims abstract description 16
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims abstract description 15
- 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 abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 51
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical class [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims description 49
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 44
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 30
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 23
- 150000001875 compounds Chemical class 0.000 claims description 16
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 16
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 16
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 16
- 239000006185 dispersion Substances 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 15
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 15
- 239000011258 core-shell material Substances 0.000 claims description 14
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 12
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 239000003960 organic solvent Substances 0.000 claims description 10
- 239000003999 initiator Substances 0.000 claims description 8
- 238000002390 rotary evaporation Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 235000012239 silicon dioxide Nutrition 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 4
- 230000000977 initiatory effect Effects 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000005543 nano-size silicon particle Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- 150000004756 silanes Chemical class 0.000 abstract description 21
- 239000004332 silver Substances 0.000 abstract description 14
- 229910052709 silver Inorganic materials 0.000 abstract description 14
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 239000011856 silicon-based particle Substances 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- 230000035484 reaction time Effects 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
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- 239000000758 substrate Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 231100000053 low toxicity Toxicity 0.000 description 3
- 244000005700 microbiome Species 0.000 description 3
- 229920000548 poly(silane) polymer Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 102100026735 Coagulation factor VIII Human genes 0.000 description 2
- 241000195493 Cryptophyta Species 0.000 description 2
- 101000911390 Homo sapiens Coagulation factor VIII Proteins 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 238000005411 Van der Waals force Methods 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 230000001464 adherent effect Effects 0.000 description 2
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- 230000015572 biosynthetic process Effects 0.000 description 2
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- 238000010586 diagram Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 239000003495 polar organic solvent Substances 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 2
- MTEZSDOQASFMDI-UHFFFAOYSA-N 1-trimethoxysilylpropan-1-ol Chemical compound CCC(O)[Si](OC)(OC)OC MTEZSDOQASFMDI-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 241000238586 Cirripedia Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 241000237852 Mollusca Species 0.000 description 1
- 241000180701 Nitzschia <flatworm> Species 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 238000004847 absorption spectroscopy Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000002519 antifouling agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical group CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 1
- 235000015170 shellfish Nutrition 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920001864 tannin Polymers 0.000 description 1
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- 238000010998 test method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 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
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
-
- 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
-
- 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
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
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- 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
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- 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
- C09D5/1668—Vinyl-type polymers
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- 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
- C09D5/1687—Use of special additives
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- 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
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- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Paints Or Removers (AREA)
Abstract
本发明提供一种改性纳米银粒子及其制备方法。所述改性纳米银粒子为树莓状结构，包括作为内核的纳米银粒子以及包覆在所述纳米银粒子外的单宁酸壳层，所述单宁酸壳层的表面负载纳米二氧化硅颗粒。本发明还提供一种硅烷类化合物及其制备方法。所述硅烷类化合物通过将甲基丙烯酸缩水甘油酯、甲基丙烯酸羟乙酯、γ‑甲基丙烯酰氧基丙基三甲氧基硅烷和(3‑氨丙基)三乙氧基硅烷在引发剂的引发下反应得到。本发明还提供一种防污涂料及其制备方法。所述防污涂料包括上述改性纳米银粒子和上述硅烷类化合物中的至少一种。改性纳米银粒子能够控制银离子的释放可控性，并改善银粒子与涂层的相容性，提高防污涂料的防污效果，减少对海洋环境的污染和破坏。The invention provides a modified nano-silver particle and a preparation method thereof. The modified nano-silver particle is a raspberry-like structure, including a nano-silver particle as an inner core and a tannic acid shell coated outside the nano-silver particle, and the surface of the tannic acid shell is loaded with nano-dioxide silicon particles. The invention also provides a silane compound and a preparation method thereof. The silane compound is induced by glycidyl methacrylate, hydroxyethyl methacrylate, γ-methacryloxypropyl trimethoxysilane and (3-aminopropyl) triethoxysilane The reaction is obtained under the trigger of the agent. The invention also provides an antifouling paint and a preparation method thereof. The antifouling paint includes at least one of the above-mentioned modified nano-silver particles and the above-mentioned silane compounds. The modified nano silver particles can control the controllability of the release of silver ions, improve the compatibility between the silver particles and the coating, improve the antifouling effect of the antifouling coating, and reduce the pollution and damage to the marine environment.
Description
技术领域technical field
本发明涉及纳米材料及涂层材料领域，具体地涉及改性纳米银材料及防污涂层材料领域。The invention relates to the fields of nanometer materials and coating materials, in particular to the fields of modified nano silver materials and antifouling coating materials.
背景技术Background technique
随着海洋产业的发展，建筑，船体，管道，石油平台和海洋传感器等海洋污损的问题日益明显。海洋污损主要是由于海洋动物，植物和微生物，如藤壶、藻类、菌类、贝类等在水下设施表面不良积累而引起的海洋生物污染，进而导致建筑表面的污垢不断积累，造成管道堵塞，增加船舶航行的阻力和燃油使用量，促进腐蚀的加剧等，这些都会给海事业带来巨大的经济损失和严重问题。With the development of the marine industry, the problem of marine fouling such as buildings, ship hulls, pipelines, oil platforms and marine sensors has become increasingly apparent. Marine fouling is mainly due to marine biological pollution caused by the undesirable accumulation of marine animals, plants and microorganisms, such as barnacles, algae, fungi, shellfish, etc. on the surface of underwater facilities, which in turn leads to the continuous accumulation of dirt on the surface of the building, causing pipeline Blockage, increase the resistance of the ship's navigation and fuel consumption, promote the intensification of corrosion, etc., all of which will bring huge economic losses and serious problems to the maritime industry.
防止海洋污垢的最有效和方便的方法是通过以可控速率释放有毒分子的涂层来实现，以减少或抑制粘附的生物如细菌，藻类和软体动物的生长。但是该方法极有可能会影响海洋环境污染，影响其他海洋生物的生长和生存，因此开发低毒有效的，环境友好型的防污剂显得极其重要。The most effective and convenient way to prevent marine fouling is through coatings that release toxic molecules at a controlled rate to reduce or inhibit the growth of adherent organisms such as bacteria, algae and molluscs. However, this method is very likely to affect marine environmental pollution and affect the growth and survival of other marine organisms. Therefore, it is extremely important to develop low-toxic, effective, and environmentally friendly antifouling agents.
纳米银具有低毒性及优异的抗菌和防污活性，但是，现阶段银离子的释放可控性及与涂层的相容性不能得到很好的控制与改善，导致纳米银运用于防污涂层中会对海洋环境造成污染破坏，从而限制了纳米银在防污涂层中的运用。Nano-silver has low toxicity and excellent antibacterial and antifouling activities. However, the controllability of the release of silver ions and the compatibility with the coating cannot be well controlled and improved at this stage, which leads to the application of nano-silver in antifouling coatings. The layer will cause pollution damage to the marine environment, thus limiting the application of nano-silver in antifouling coatings.
发明内容Contents of the invention
鉴于背景技术中存在的问题，本发明的目的在于提供一种改性纳米银粒子及其制备方法和防污涂料，其能够控制银离子的释放可控性，并改善银粒子与涂层的相容性，提高防污涂料的防污效果，减少对海洋环境的污染和破坏。In view of the problems existing in the background technology, the object of the present invention is to provide a modified nano-silver particle and its preparation method and antifouling coating, which can control the release controllability of silver ions, and improve the phase of the silver particle and the coating. Capacitance, improve the antifouling effect of antifouling coatings, and reduce pollution and damage to the marine environment.
为了达到上述目的，在本发明的一方面，本发明提供了一种改性纳米银粒子，所述改性纳米银粒子为树莓状结构，包括作为内核的纳米银粒子以及包覆在所述纳米银粒子外的单宁酸壳层，所述单宁酸壳层的表面负载纳米二氧化硅颗粒。In order to achieve the above object, in one aspect of the present invention, the present invention provides a modified nano-silver particle, the modified nano-silver particle is a raspberry-like structure, including the nano-silver particle as the inner core and the coated nano-silver particle. A tannic acid shell layer outside the nano silver particles, the surface of the tannic acid shell layer is loaded with nano silicon dioxide particles.
在本发明的另一方面，本发明提供了一种改性纳米银粒子的制备方法，用于制备上述改性纳米银粒子，包括以下步骤：步骤10，将硝酸银与聚乙烯吡咯烷酮在乙二醇中进行反应，得到纳米银粒子；步骤20，将步骤10得到的纳米银粒子分散于乙醇中，加入单宁酸的乙醇溶液进行反应，得到经单宁酸改性的具有核壳结构的纳米银粒子；步骤30，将步骤20得到的经单宁酸改性的具有核壳结构的纳米银粒子分散于乙醇中，加水后再加入正硅酸乙酯的乙醇溶液进行反应，得到所述改性纳米银粒子。In another aspect of the present invention, the present invention provides a kind of preparation method of modified nano-silver particle, is used for preparing above-mentioned modified nano-silver particle, comprises the following steps: Step 10, silver nitrate and polyvinylpyrrolidone are mixed in ethylene glycol react in alcohol to obtain nano-silver particles; step 20, disperse the nano-silver particles obtained in step 10 in ethanol, add the ethanol solution of tannic acid to react, and obtain the nano-silver particles with core-shell structure modified by tannic acid Silver particle; step 30, the nano-silver particle with core-shell structure modified by tannic acid obtained in step 20 is dispersed in ethanol, and the ethanol solution of ethyl tetrasilicate is added after adding water to react to obtain the modified Nano silver particles.
在本发明的又一方面，本发明提供了一种硅烷类化合物，通过将甲基丙烯酸缩水甘油酯、甲基丙烯酸羟乙酯、γ-甲基丙烯酰氧基丙基三甲氧基硅烷和(3-氨丙基)三乙氧基硅烷在引发剂的引发下反应得到。In yet another aspect of the present invention, the present invention provides a kind of silane compound, by glycidyl methacrylate, hydroxyethyl methacrylate, γ-methacryloxypropyl trimethoxysilane and ( 3-aminopropyl)triethoxysilane is obtained by reacting with an initiator.
在本发明的再一方面，本发明提供了一种硅烷类化合物的制备方法，用于制备上述硅烷类化合物，包括以下步骤：步骤40，将甲基丙烯酸缩水甘油酯、甲基丙烯酸羟乙酯和γ-甲基丙烯酰氧基丙基三甲氧基硅烷在引发剂的引发下进行反应，得到中间化合物；步骤50，将步骤40得到的中间化合物与 (3-氨丙基)三乙氧基硅烷进行反应，得到所述硅烷类化合物。In yet another aspect of the present invention, the present invention provides a method for preparing silane compounds, which is used to prepare the above-mentioned silane compounds, comprising the following steps: Step 40, glycidyl methacrylate, hydroxyethyl methacrylate and gamma-methacryloxypropyltrimethoxysilane react under the triggering of initiator to obtain intermediate compound; step 50, the intermediate compound obtained in step 40 and (3-aminopropyl) triethoxy The silane is reacted to obtain the silane compound.
在本发明的还一方面，本发明提供了一种防污涂料，包括上述改性纳米银粒子和上述硅烷类化合物中的至少一种。In yet another aspect of the present invention, the present invention provides an antifouling paint, comprising at least one of the above-mentioned modified nano-silver particles and the above-mentioned silane compounds.
在本发明的仍一方面，本发明提供了一种防污涂料的制备方法，用于制备上述防污涂料，包括以下步骤：步骤60，将所述改性纳米银粒子分散于液体分散剂中，得到改性纳米银粒子的分散液；步骤70，将所述硅烷类化合物溶于有机溶剂中，得到硅烷类化合物的溶液；步骤80，将步骤60得到的改性纳米银粒子的分散液与步骤70得到的硅烷类化合物的溶液混合并搅拌，旋蒸后得到浓缩透明液体，即为所述防污涂料。In still another aspect of the present invention, the present invention provides a method for preparing an antifouling coating, for preparing the above-mentioned antifouling coating, comprising the following steps: step 60, dispersing the modified nano-silver particles in a liquid dispersant , to obtain a dispersion of modified silver nanoparticles; step 70, dissolving the silane compound in an organic solvent to obtain a solution of the silane compound; step 80, mixing the dispersion of the modified silver nanoparticles obtained in step 60 with The solution of the silane compound obtained in step 70 is mixed and stirred, and the concentrated transparent liquid is obtained after rotary evaporation, which is the antifouling coating.
本发明至少包括如下所述的有益效果：The present invention at least includes the following beneficial effects:
在本发明的改性纳米银粒子中，由单宁酸将纳米银粒子包覆起来形成纳米尺度的核壳结构，在纳米银粒子的表面接枝单宁酸能够改性纳米银粒子的表面，方便下一步二氧化硅的负载，此外由于单宁酸具有一定的抗蛋白和防污的性能，由于共轭效应能够进一步提高银粒子的防污效果；再在单宁酸壳层的表面负载纳米二氧化硅颗粒，能够降低银粒子在空气或者在少量水的情况下释放银离子的速率。同时，本发明将二氧化硅以颗粒形态负载于单宁酸壳层的表面形成树莓状结构，由于二氧化硅具有很好的热稳定性和物理化学稳定性，且以颗粒形态负载于单宁酸壳层的表面时具有高比表面积，可增加纳米银粒子的协同效应；最终得到的具有树莓状结构的改性纳米银粒子能够更好地发挥其防污效果，减小团聚现象的发生，并且降低银离子的释放速度。In the modified nano-silver particles of the present invention, the nano-silver particles are coated with tannic acid to form a nanoscale core-shell structure, and the surface of the nano-silver particles is grafted with tannic acid to modify the surface of the nano-silver particles. It is convenient for the loading of silica in the next step. In addition, because tannic acid has certain anti-protein and anti-fouling properties, the anti-fouling effect of silver particles can be further improved due to the conjugation effect; Silica particles, which can reduce the rate at which silver particles release silver ions in air or in the presence of small amounts of water. At the same time, the present invention loads silicon dioxide on the surface of the tannic acid shell in the form of particles to form a raspberry-like structure. Since silicon dioxide has good thermal stability and physical and chemical stability, and is loaded on the surface of the tannic acid shell in the form of particles The surface of the nitric acid shell layer has a high specific surface area, which can increase the synergistic effect of the nano-silver particles; the finally obtained modified nano-silver particles with a raspberry-like structure can better exert its antifouling effect and reduce the risk of agglomeration. Occurs and reduces the release rate of silver ions.
本发明的改性纳米银粒子通过单宁酸包覆纳米银粒子并通过二氧化硅颗粒负载后，防污效果更为显著，适用于防污涂料中，能够与涂料具有较佳的相容性，并提高防污涂料的防污性能；并且本发明的改性纳米银粒子具有较好的银离子释放可控性，使包含本发明的改性纳米银粒子的防污涂层具有安全低毒、对环境友好的优点。本发明的硅烷类化合物在固化后能够自交联后形成网络结构的聚硅烷类化合物，添加于防污涂料中，能够提高防污涂层的机械强度；并且本发明的硅烷类化合物具有一定的低表面能和蛋白质抗性，能够有效抑制海洋环境中微生物的吸附。当防污涂料中同时包含本发明的改性纳米银粒子和硅烷类化合物时，改性纳米银粒子和硅烷类化合物之间不是纳米粒子和涂层简单地复合，而是改性纳米银粒子和硅烷类化合物之间通过共价键和范德华力相互连接，结合效果更佳，特别适用于海洋防污的恶劣条件要求及环境友好要求。After the modified nano-silver particles of the present invention are coated with tannic acid and loaded with silica particles, the anti-fouling effect is more significant, and it is suitable for anti-fouling coatings, and can have better compatibility with coatings , and improve the antifouling performance of antifouling coatings; and the modified nano-silver particles of the present invention have better silver ion release controllability, so that the antifouling coatings comprising the modified nano-silver particles of the present invention have safety and low toxicity , The advantages of being friendly to the environment. The silane compound of the present invention can form the polysilane compound of network structure after self-crosslinking after solidification, is added in the antifouling coating, can improve the mechanical strength of antifouling coating; And the silane compound of the present invention has certain Low surface energy and protein resistance can effectively inhibit the adsorption of microorganisms in marine environments. When the antifouling paint contains the modified nano-silver particles and silane compounds of the present invention, the modified nano-silver particles and the silane compounds are not simple composites of nanoparticles and coatings, but modified nano-silver particles and silane compounds. The silane compounds are connected to each other through covalent bonds and van der Waals force, and the combination effect is better, which is especially suitable for the harsh conditions and environmental friendly requirements of marine antifouling.
附图说明Description of drawings
图1为实施例1制备过程中各产物的TEM透射图；其中，(a)为步骤10 制备得到的纳米银粒子的TEM透射图，(b)为步骤20制备得到的经单宁酸改性的具有核壳结构的纳米银粒子的TEM透射图，(c)为步骤30制备得到的改性纳米银粒子的TEM透射图。Fig. 1 is the TEM transmission figure of each product in the preparation process of embodiment 1; Wherein, (a) is the TEM transmission figure of the nano-silver particle that step 10 prepares, and (b) is the tannic acid modification that step 20 prepares (c) is a TEM transmission diagram of the modified silver nanoparticles prepared in step 30.
图2为实施例1制备过程中各产物的紫外-可见吸收光谱图；Fig. 2 is the ultraviolet-visible absorption spectrogram of each product in the preparation process of embodiment 1;
图3为实施例5制备过程中各产物和最终产物的聚合物的红外光谱图；Fig. 3 is the infrared spectrogram of each product and the polymer of final product in the preparation process of embodiment 5;
图4为实施例10-15制备得到的防污涂层的防污性能测试效果图。Fig. 4 is an effect diagram of the antifouling performance test of the antifouling coating prepared in Examples 10-15.
具体实施方式Detailed ways
本发明第一方面的改性纳米银粒子为树莓状结构，包括作为内核的纳米银粒子以及包覆在所述纳米银粒子外的单宁酸壳层，所述单宁酸壳层的表面负载纳米二氧化硅颗粒。The modified nano-silver particle in the first aspect of the present invention is a raspberry-like structure, including a nano-silver particle as an inner core and a tannic acid shell coated outside the nano-silver particle, and the surface of the tannic acid shell is Loaded with nano-silica particles.
在本发明的改性纳米银粒子中，由单宁酸将纳米银粒子包覆起来形成纳米尺度的核壳结构，在纳米银粒子的表面接枝单宁酸能够改性纳米银粒子的表面，方便下一步二氧化硅的负载，此外由于单宁酸具有一定的抗蛋白和防污的性能，由于共轭效应能够进一步提高银粒子的防污效果；再在单宁酸壳层的表面负载纳米二氧化硅颗粒，能够降低银粒子在空气或者在少量水的情况下释放银离子的速率。同时，本发明将二氧化硅以颗粒形态负载于单宁酸壳层的表面形成树莓状结构，由于二氧化硅具有很好的热稳定性和物理化学稳定性，且以颗粒形态负载于单宁酸壳层的表面时具有高比表面积，可增加纳米银粒子的协同效应；最终得到的具有树莓状结构的改性纳米银粒子能够更好地发挥其防污效果，减小团聚现象的发生，并且降低银离子的释放速度。In the modified nano-silver particles of the present invention, the nano-silver particles are coated with tannic acid to form a nanoscale core-shell structure, and the surface of the nano-silver particles is grafted with tannic acid to modify the surface of the nano-silver particles. It is convenient for the loading of silica in the next step. In addition, because tannic acid has certain anti-protein and anti-fouling properties, the anti-fouling effect of silver particles can be further improved due to the conjugation effect; Silica particles, which can reduce the rate at which silver particles release silver ions in air or in the presence of small amounts of water. At the same time, the present invention loads silicon dioxide on the surface of the tannic acid shell in the form of particles to form a raspberry-like structure. Since silicon dioxide has good thermal stability and physical and chemical stability, and is loaded on the surface of the tannic acid shell in the form of particles The surface of the nitric acid shell layer has a high specific surface area, which can increase the synergistic effect of the nano-silver particles; the finally obtained modified nano-silver particles with a raspberry-like structure can better exert its antifouling effect and reduce the risk of agglomeration. Occurs and reduces the release rate of silver ions.
在根据本发明第一方面所述的改性纳米银粒子中，所述改性纳米银粒子通过将纳米银粒子与单宁酸、正硅酸乙酯反应得到；其中，所述纳米银粒子通过将硝酸银与聚乙烯吡咯烷酮在乙二醇中反应得到；其中，所述硝酸银与所述聚乙烯吡咯烷酮、所述乙二醇、所述单宁酸、所述正硅酸乙酯的质量比为0.1-2：0.05-10：10-500：0.1-2：0.005-0.20；优选为0.5-2：0.1-10：50-250： 0.5-1.5：0.015-0.06。In the modified silver nanoparticles according to the first aspect of the present invention, the modified silver nanoparticles are obtained by reacting the silver nanoparticles with tannic acid and ethyl tetrasilicate; wherein, the silver nanoparticles are obtained by It is obtained by reacting silver nitrate and polyvinylpyrrolidone in ethylene glycol; wherein, the mass ratio of the silver nitrate to the polyvinylpyrrolidone, the ethylene glycol, the tannic acid, and the tetraethyl orthosilicate 0.1-2: 0.05-10: 10-500: 0.1-2: 0.005-0.20; preferably 0.5-2: 0.1-10: 50-250: 0.5-1.5: 0.015-0.06.
在本发明的改性纳米银粒子中，通过合理地控制硝酸银、聚乙烯吡咯烷酮、单宁酸、正硅酸乙酯的质量比，能够高效制备改性纳米银粒子并提高制备得到的改性纳米银粒子的防污性能。In the modified nano-silver particles of the present invention, by reasonably controlling the mass ratio of silver nitrate, polyvinylpyrrolidone, tannic acid, and tetraethyl orthosilicate, the modified nano-silver particles can be efficiently prepared and the prepared modified silver particles can be improved. Antifouling properties of silver nanoparticles.
本发明第二方面的改性纳米银粒子的制备方法，包括以下步骤：The preparation method of the modified nano-silver particle of the second aspect of the present invention, comprises the following steps:
步骤10，将硝酸银与聚乙烯吡咯烷酮在乙二醇中进行反应，得到纳米银粒子；Step 10, reacting silver nitrate and polyvinylpyrrolidone in ethylene glycol to obtain silver nanoparticles;
步骤20，将步骤10得到的纳米银粒子分散于乙醇中，加入单宁酸的乙醇溶液进行反应，得到经单宁酸改性的具有核壳结构的纳米银粒子；Step 20, dispersing the nano-silver particles obtained in step 10 in ethanol, adding an ethanol solution of tannic acid to react, and obtaining nano-silver particles with a core-shell structure modified by tannic acid;
步骤30，将步骤20得到的经单宁酸改性的具有核壳结构的纳米银粒子分散于乙醇中，加水后再加入正硅酸乙酯的乙醇溶液进行反应，得到所述改性纳米银粒子。Step 30, dispersing the nano-silver particles with a core-shell structure modified by tannic acid obtained in step 20 in ethanol, adding water and then adding an ethanol solution of tetraethyl orthosilicate to react to obtain the modified nano-silver particle.
在改性纳米银粒子的制备方法中，将硝酸银、聚乙烯吡咯烷酮、乙二醇一起加入反应体系中进行反应；其中，聚乙烯吡咯烷酮能够用于稳定和分散纳米银粒子，减少纳米银粒子团聚现象的发生，还能够便于乙二醇的进一步改性；乙二醇能够用于改性纳米银粒子的表面，以便于单宁酸在纳米银离子表面接枝；单宁酸接枝于纳米银粒子的表面，既能够提高纳米银粒子的防污效果，还能够为下一步二氧化硅的接枝做准备。In the preparation method of modified nano-silver particles, silver nitrate, polyvinylpyrrolidone, and ethylene glycol are added to the reaction system for reaction; among them, polyvinylpyrrolidone can be used to stabilize and disperse nano-silver particles and reduce nano-silver particle agglomeration The occurrence of phenomenon can also facilitate the further modification of ethylene glycol; ethylene glycol can be used to modify the surface of nano-silver particles, so that tannic acid is grafted on the surface of nano-silver ions; tannic acid is grafted to nano-silver The surface of the particles can not only improve the antifouling effect of the nano-silver particles, but also prepare for the next step of silica grafting.
在本发明第二方面的改性纳米银粒子的制备方法中，步骤10中，所述硝酸银与所述聚乙烯吡咯烷酮在乙二醇中的反应温度为100-200℃，反应时间为0.5-48h；优选为，步骤10中，所述硝酸银与所述聚乙烯吡咯烷酮在乙二醇中的反应温度为100-150℃，反应时间为6-24h。In the preparation method of modified nano-silver particles according to the second aspect of the present invention, in step 10, the reaction temperature of the silver nitrate and the polyvinylpyrrolidone in ethylene glycol is 100-200°C, and the reaction time is 0.5- 48h; Preferably, in step 10, the reaction temperature of the silver nitrate and the polyvinylpyrrolidone in ethylene glycol is 100-150°C, and the reaction time is 6-24h.
在本发明第二方面的改性纳米银粒子的制备方法中，步骤10中，向硝酸银与聚乙烯吡咯烷酮的反应产物中加入有机溶剂，经离心、超声洗涤后得到所述纳米银粒子。其中，所述有机溶剂为极性溶剂；优选地，所述有机溶剂选自丙酮或异丙醇中的任意一种。In the method for preparing modified silver nanoparticles according to the second aspect of the present invention, in step 10, an organic solvent is added to the reaction product of silver nitrate and polyvinylpyrrolidone, and the silver nanoparticles are obtained after centrifugation and ultrasonic washing. Wherein, the organic solvent is a polar solvent; preferably, the organic solvent is selected from any one of acetone or isopropanol.
在本发明第二方面的改性纳米银粒子的制备方法中，步骤20中，所述纳米银粒子与所述单宁酸的反应在pH＝8-10的反应体系中进行，反应温度为 23-25℃，反应时间为6-48h；优选为，步骤20中，所述纳米银粒子与所述单宁酸的反应在pH＝9的反应体系中进行，反应温度为23-25℃，反应时间为 12-24h。In the preparation method of the modified silver nanoparticles in the second aspect of the present invention, in step 20, the reaction between the silver nanoparticles and the tannic acid is carried out in a reaction system with pH=8-10, and the reaction temperature is 23 -25°C, the reaction time is 6-48h; preferably, in step 20, the reaction of the silver nanoparticles and the tannic acid is carried out in a reaction system with pH=9, the reaction temperature is 23-25°C, and the reaction The time is 12-24h.
在本发明第二方面的改性纳米银粒子的制备方法中，步骤30中，所述经单宁酸改性的具有核壳结构的纳米银粒子与所述正硅酸乙酯的反应在 pH＝8-10的反应体系中进行，反应温度为23-25℃，反应时间为6-48h；优选为，步骤30中，所述经单宁酸改性的具有核壳结构的纳米银粒子与所述正硅酸乙酯的反应在pH＝9的反应体系中进行，反应温度为23-25℃，反应时间为12-24h。In the preparation method of the modified nano-silver particles of the second aspect of the present invention, in step 30, the reaction between the tannic acid-modified nano-silver particles with a core-shell structure and the tetraethyl orthosilicate is at pH =8-10 in the reaction system, the reaction temperature is 23-25 ° C, the reaction time is 6-48h; preferably, in step 30, the nano-silver particles with a core-shell structure modified by tannic acid and The reaction of tetraethyl orthosilicate is carried out in a reaction system with pH=9, the reaction temperature is 23-25°C, and the reaction time is 12-24h.
本发明的第三方面的硅烷类化合物通过将甲基丙烯酸缩水甘油酯、甲基丙烯酸羟乙酯、γ-甲基丙烯酰氧基丙基三甲氧基硅烷和(3-氨丙基)三乙氧基硅烷在引发剂的引发下反应得到。The silane compound of the third aspect of the present invention is obtained by combining glycidyl methacrylate, hydroxyethyl methacrylate, γ-methacryloxypropyl trimethoxysilane and (3-aminopropyl) triethyl Oxysilane is obtained by reacting under the initiation of an initiator.
本发明的第三方面的硅烷类化合物取其反应物甲基丙烯酸缩水甘油酯 GMA、甲基丙烯酸羟乙酯HEMA、γ-甲基丙烯酰氧基丙基三甲氧基硅烷 MPS和(3-氨丙基)三乙氧基硅烷KH-550的首字母命名为GHMK。The silane compound of the third aspect of the present invention takes its reactant glycidyl methacrylate GMA, hydroxyethyl methacrylate HEMA, γ-methacryloxypropyltrimethoxysilane MPS and (3-amino The initials of propyl)triethoxysilane KH-550 are named GHMK.
本发明的硅烷类化合物采用用甲基丙烯酸缩水甘油酯、甲基丙烯酸羟乙酯、γ-甲基丙烯酰氧基丙基三甲氧基硅烷和(3-氨丙基)三乙氧基硅烷合成，用于合成产物的单体价钱低廉，合成的硅烷类化合物GHMK能够在固化后自交联形成网络结构的聚硅烷类化合物PGHMK，具有较高的机械强度。The silane compounds of the present invention are synthesized by using glycidyl methacrylate, hydroxyethyl methacrylate, γ-methacryloxypropyl trimethoxysilane and (3-aminopropyl) triethoxysilane , The monomers used to synthesize the product are cheap, and the synthesized silane compound GHMK can self-crosslink to form a polysilane compound PGHMK with a network structure after curing, which has high mechanical strength.
在根据本发明第三方面所述的硅烷类化合物中，所述甲基丙烯酸缩水甘油酯、所述甲基丙烯酸羟乙酯、所述γ-甲基丙烯酰氧基丙基三甲氧基硅烷、所述(3-氨丙基)三乙氧基硅烷的摩尔比为1-9：1-9：1-6：1-3；优选为1-6： 1-3：2-4：1-2。In the silane compound according to the third aspect of the present invention, the glycidyl methacrylate, the hydroxyethyl methacrylate, the γ-methacryloxypropyltrimethoxysilane, The molar ratio of (3-aminopropyl)triethoxysilane is 1-9:1-9:1-6:1-3; preferably 1-6:1-3:2-4:1- 2.
在本发明的硅烷类化合物中，通过合理地控制甲基丙烯酸缩水甘油酯、甲基丙烯酸羟乙酯、γ-甲基丙烯酰氧基丙基三甲氧基硅烷和(3-氨丙基)三乙氧基硅烷的摩尔比，能够提高反应效率和反应完全度；并且，通过该摩尔比例制备得到的硅烷类化合物添加于防污涂料中，具有较佳的成膜效果，成膜后无气泡，成膜厚度适中、附着力好。In the silane compounds of the present invention, by rationally controlling glycidyl methacrylate, hydroxyethyl methacrylate, γ-methacryloxypropyl trimethoxysilane and (3-aminopropyl) trimethoxysilane The molar ratio of ethoxysilane can improve the reaction efficiency and reaction completeness; and the silane compound prepared by this molar ratio is added to the antifouling coating, which has a better film-forming effect, no bubbles after film formation, Moderate film thickness and good adhesion.
在根据本发明第三方面所述的硅烷类化合物中，所述引发剂为偶氮二异丁腈；按质量百分比计，所述偶氮二异丁腈在反应体系中的质量占比为 0.01-10wt％；优选为，所述偶氮二异丁腈在反应体系中的质量占比为 0.1-5wt％。In the silane compound according to the third aspect of the present invention, the initiator is azobisisobutyronitrile; in terms of mass percentage, the mass proportion of the azobisisobutyronitrile in the reaction system is 0.01 -10wt%; Preferably, the mass proportion of the azobisisobutyronitrile in the reaction system is 0.1-5wt%.
本发明的第四方面的硅烷类化合物的制备方法包括以下步骤：The preparation method of the silane compound of the fourth aspect of the present invention comprises the following steps:
步骤40，将甲基丙烯酸缩水甘油酯、甲基丙烯酸羟乙酯和γ-甲基丙烯酰氧基丙基三甲氧基硅烷在引发剂的引发下进行反应，得到中间化合物；Step 40, reacting glycidyl methacrylate, hydroxyethyl methacrylate and γ-methacryloxypropyltrimethoxysilane under the trigger of an initiator to obtain an intermediate compound;
步骤50，将步骤40得到的中间化合物与(3-氨丙基)三乙氧基硅烷进行反应，得到所述硅烷类化合物。Step 50, reacting the intermediate compound obtained in Step 40 with (3-aminopropyl)triethoxysilane to obtain the silane compound.
本发明的硅烷类化合物的制备方法具有合成方法简单、合成过程低VOC 的优点。The preparation method of the silane compound of the invention has the advantages of simple synthesis method and low VOC in the synthesis process.
在根据本发明第四方面所述的硅烷类化合物的制备方法中，步骤40得到的中间化合物取其反应物甲基丙烯酸缩水甘油酯GMA、甲基丙烯酸羟乙酯HEMA、γ-甲基丙烯酰氧基丙基三甲氧基硅烷MPS的首字母命名为 GHM。In the preparation method of silane compounds according to the fourth aspect of the present invention, the intermediate compound obtained in step 40 may be its reactant glycidyl methacrylate GMA, hydroxyethyl methacrylate HEMA, γ-methacryloyl The acronym of oxypropyltrimethoxysilane MPS is named GHM.
在根据本发明第四方面所述的硅烷类化合物的制备方法中，步骤40中，所述甲基丙烯酸缩水甘油酯、甲基丙烯酸羟乙酯和γ-甲基丙烯酰氧基丙基三甲氧基硅烷的反应在极性有机溶剂中进行；优选地，所述极性有机溶剂选自甲醇或异丙醇。In the preparation method of silane compounds according to the fourth aspect of the present invention, in step 40, the glycidyl methacrylate, hydroxyethyl methacrylate and γ-methacryloxypropyl trimethoxy The reaction of the base silane is carried out in a polar organic solvent; preferably, the polar organic solvent is selected from methanol or isopropanol.
在根据本发明第四方面所述的硅烷类化合物的制备方法中，步骤40中，所述甲基丙烯酸缩水甘油酯、甲基丙烯酸羟乙酯和γ-甲基丙烯酰氧基丙基三甲氧基硅烷的反应温度为60-120℃，反应时间为0.5-12h；优选为，步骤40 中，所述甲基丙烯酸缩水甘油酯、甲基丙烯酸羟乙酯和γ-甲基丙烯酰氧基丙基三甲氧基硅烷的反应温度为60-90℃，反应时间为1-6h。In the preparation method of silane compounds according to the fourth aspect of the present invention, in step 40, the glycidyl methacrylate, hydroxyethyl methacrylate and γ-methacryloxypropyl trimethoxy The reaction temperature of base silane is 60-120°C, and the reaction time is 0.5-12h; preferably, in step 40, the glycidyl methacrylate, hydroxyethyl methacrylate and γ-methacryloxypropyl The reaction temperature of trimethoxysilane is 60-90°C, and the reaction time is 1-6h.
在根据本发明第四方面所述的硅烷类化合物的制备方法中，步骤50中，所述中间化合物与(3-氨丙基)三乙氧基硅烷的反应温度为40-60℃，反应时间为0.5-10h；优选为，步骤50中，所述中间化合物与(3-氨丙基)三乙氧基硅烷的反应温度为45-55℃，反应时间为2-5h。In the method for preparing silane compounds according to the fourth aspect of the present invention, in step 50, the reaction temperature between the intermediate compound and (3-aminopropyl)triethoxysilane is 40-60°C, and the reaction time is 0.5-10 h; preferably, in step 50, the reaction temperature of the intermediate compound and (3-aminopropyl)triethoxysilane is 45-55° C., and the reaction time is 2-5 h.
在根据本发明第四方面所述的硅烷类化合物的制备方法中，步骤50中，将中间化合物与(3-氨丙基)三乙氧基硅烷的反应产物冷却到室温，旋蒸掉多余的反应液后，将旋蒸后得到的浓缩液滴入有机溶剂中，洗涤多次后得到白色透明液状物，将所述白色透明液状物旋蒸后得到浓缩液体，即为所述硅烷类化合物。其中，所述有机溶剂为极性溶剂；优选地，所述有机溶剂选自正己烷或者丙酮中的任意一种。In the method for preparing silane compounds according to the fourth aspect of the present invention, in step 50, the reaction product of the intermediate compound and (3-aminopropyl)triethoxysilane is cooled to room temperature, and the excess After the reaction solution, the concentrated solution obtained after rotary evaporation is dropped into an organic solvent, and after washing for many times, a white transparent liquid is obtained. After the white transparent liquid is rotary evaporated, a concentrated liquid is obtained, which is the silane compound. Wherein, the organic solvent is a polar solvent; preferably, the organic solvent is selected from any one of n-hexane or acetone.
本发明的第五方面的防污涂料包括所述改性纳米银粒子和所述硅烷类化合物中的至少一种。The antifouling paint according to the fifth aspect of the present invention includes at least one of the modified nano-silver particles and the silane compound.
本发明的改性纳米银粒子通过单宁酸包覆纳米银粒子并通过二氧化硅颗粒负载后，防污效果更为显著，适用于防污涂料中，能够与涂料具有较佳的相容性，并提高防污涂料的防污性能；并且本发明的改性纳米银粒子具有较好的银离子释放可控性，使包含本发明的改性纳米银粒子的防污涂层具有安全低毒、对环境友好的优点。本发明的硅烷类化合物在固化后能够自交联后形成网络结构的聚硅烷类化合物，添加于防污涂料中，能够提高防污涂层的机械强度；并且本发明的硅烷类化合物具有一定的低表面能和蛋白质抗性，能够有效抑制海洋环境中微生物的吸附。当防污涂料中同时包含本发明的改性纳米银粒子和硅烷类化合物时，改性纳米银粒子和硅烷类化合物之间不是纳米粒子和涂层简单地复合，而是改性纳米银粒子和硅烷类化合物之间通过共价键和范德华力相互连接，结合效果更佳，特别适用于海洋防污的恶劣条件要求及环境友好要求。After the modified nano-silver particles of the present invention are coated with tannic acid and loaded with silica particles, the anti-fouling effect is more significant, and it is suitable for anti-fouling coatings, and can have better compatibility with coatings , and improve the antifouling performance of antifouling coatings; and the modified nano-silver particles of the present invention have better silver ion release controllability, so that the antifouling coatings comprising the modified nano-silver particles of the present invention have safety and low toxicity , The advantages of being friendly to the environment. The silane compound of the present invention can form the polysilane compound of network structure after self-crosslinking after solidification, is added in the antifouling coating, can improve the mechanical strength of antifouling coating; And the silane compound of the present invention has certain Low surface energy and protein resistance can effectively inhibit the adsorption of microorganisms in marine environments. When the antifouling paint contains the modified nano-silver particles and silane compounds of the present invention, the modified nano-silver particles and the silane compounds are not simple composites of nanoparticles and coatings, but modified nano-silver particles and silane compounds. The silane compounds are connected to each other through covalent bonds and van der Waals force, and the combination effect is better, which is especially suitable for the harsh conditions and environmental friendly requirements of marine antifouling.
在根据本发明第五方面所述的防污涂料中，所述改性纳米银粒子与所述硅烷类化合物的质量比为0.001-0.05：0.5-5；优选为0.004-0.032：1-4.5。In the antifouling paint according to the fifth aspect of the present invention, the mass ratio of the modified silver nanoparticles to the silane compound is 0.001-0.05:0.5-5; preferably 0.004-0.032:1-4.5.
本发明的第六方面的防污涂料的制备方法包括以下步骤：The preparation method of the antifouling paint of the sixth aspect of the present invention comprises the following steps:
步骤60，将所述改性纳米银粒子分散于液体分散剂中，得到改性纳米银粒子的分散液；Step 60, dispersing the modified nano-silver particles in a liquid dispersant to obtain a dispersion of modified nano-silver particles;
步骤70，将所述硅烷类化合物溶于有机溶剂中，得到硅烷类化合物的溶液；Step 70, dissolving the silane compound in an organic solvent to obtain a solution of the silane compound;
步骤80，将步骤60得到的改性纳米银粒子的分散液与步骤70得到的硅烷类化合物的溶液混合并搅拌，旋蒸后得到浓缩透明液体，即为所述防污涂料。Step 80, mixing and stirring the dispersion of the modified nano-silver particles obtained in step 60 and the solution of the silane compound obtained in step 70, and then rotary evaporating to obtain a concentrated transparent liquid, which is the antifouling coating.
本发明的防污涂料的制备方法为低VOC过程，具有环境友好的优点；且制备得到的防污涂层具有较优异的防污性能。The preparation method of the antifouling coating of the invention is a low-VOC process and has the advantage of being environmentally friendly; and the prepared antifouling coating has relatively excellent antifouling performance.
在根据本发明第六方面所述的防污涂料的制备方法中，步骤60中，所述液体分散剂选自乙醇或甲醇中的任意一种。In the preparation method of the antifouling paint according to the sixth aspect of the present invention, in step 60, the liquid dispersant is selected from any one of ethanol or methanol.
在根据本发明第六方面所述的防污涂料的制备方法中，步骤60中，在所述改性纳米银粒子的分散液中，改性纳米银粒子的质量浓度为0.02mg/mL。In the preparation method of the antifouling paint according to the sixth aspect of the present invention, in step 60, in the dispersion of the modified silver nanoparticles, the mass concentration of the modified silver nanoparticles is 0.02 mg/mL.
在根据本发明第六方面所述的防污涂料的制备方法中，步骤70中，所述有机溶剂优选为甲醇。In the preparation method of the antifouling paint according to the sixth aspect of the present invention, in step 70, the organic solvent is preferably methanol.
在根据本发明第六方面所述的防污涂料的制备方法中，步骤80中，所述改性纳米银粒子的分散液与所述硅烷类化合物的溶液在25-100℃的温度下搅拌2-48h；优选为，步骤70中，所述改性纳米银粒子的分散液与所述硅烷类化合物的溶液在30-60℃的温度下搅拌2-24h。In the preparation method of the antifouling coating according to the sixth aspect of the present invention, in step 80, the dispersion of the modified silver nanoparticles and the solution of the silane compound are stirred at a temperature of 25-100°C for 2 -48h; Preferably, in step 70, the dispersion of the modified nano-silver particles and the solution of the silane compound are stirred at a temperature of 30-60°C for 2-24h.
本发明还提供了一种防污涂层，所述防污涂层通过将所述防污涂料施覆在基材的至少部分表面后经固化形成；优选地，所述固化在40-150℃的温度下进行，所述固化的持续时间为12-72h；更优选地，所述固化在60-120℃的温度下进行，所述固化的持续时间为24-48h。The present invention also provides an antifouling coating, which is formed by applying the antifouling coating on at least part of the surface of a substrate and then curing; preferably, the curing is performed at 40-150°C The curing is carried out at a temperature of 12-72 hours; more preferably, the curing is carried out at a temperature of 60-120° C., and the curing time is 24-48 hours.
下面结合实施例，进一步阐述本申请。应理解，这些实施例仅用于说明本申请而不用于限制本申请的范围。Below in conjunction with embodiment, further elaborate the present application. It should be understood that these examples are only used to illustrate the present application and are not intended to limit the scope of the present application.
实施例1Example 1
改性纳米银粒子的制备方法具体如下：The preparation method of modified silver nanoparticles is as follows:
步骤10，称取0.50g硝酸银和1.50g聚乙烯吡咯烷酮于500mL单口烧瓶中，加入400mL乙二醇，加热至130℃，搅拌30-60min，停止搅拌，持续加热46h，然后冷却到室温，加入500mL丙酮，经离心、乙醇洗涤后，得到纳米银粒子，结果见图1(a)；Step 10, weigh 0.50g of silver nitrate and 1.50g of polyvinylpyrrolidone into a 500mL single-necked flask, add 400mL of ethylene glycol, heat to 130°C, stir for 30-60min, stop stirring, continue heating for 46h, then cool to room temperature, add 500mL of acetone was centrifuged and washed with ethanol to obtain silver nanoparticles. The results are shown in Figure 1(a);
步骤20，将步骤10得到的纳米银粒子分散于10mL乙醇中，得到纳米银粒子的乙醇分散液，向其中加入80mL的乙醇和20mL蒸馏水，并用氨水调节分散液pH＝9；将0.125g单宁酸溶于10mL乙醇中，逐滴加入纳米银粒子的乙醇分散液中，并在室温下反应24h，经离心、超声洗涤后，得到经单宁酸改性的具有核壳结构的纳米银粒子，结果见图1(b)；Step 20, disperse the nano-silver particles obtained in step 10 in 10mL ethanol to obtain an ethanol dispersion of nano-silver particles, add 80mL of ethanol and 20mL distilled water to it, and adjust the pH of the dispersion to 9 with ammonia water; 0.125g of tannin The acid was dissolved in 10mL of ethanol, and added dropwise to the ethanol dispersion of silver nanoparticles, and reacted at room temperature for 24 hours. After centrifugation and ultrasonic washing, silver nanoparticles with a core-shell structure modified by tannic acid were obtained. The results are shown in Figure 1(b);
步骤30，将步骤20得到的经单宁酸改性的具有核壳结构的纳米银粒子分散于200mL乙醇中，向其中加入50mL蒸馏水，用氨水调节pH＝9；然后将55μL正硅酸乙酯溶于10mL乙醇中，逐滴加入经单宁酸改性的具有核壳结构的纳米银粒子的分散液中，并在室温下反应24h，经离心、乙醇洗涤后，得到所述改性纳米银粒子，结果见图1(c)。Step 30, disperse the nano-silver particles with a core-shell structure modified by tannic acid obtained in step 20 in 200mL of ethanol, add 50mL of distilled water to it, and adjust the pH=9 with ammonia water; then 55 μL of ethyl orthosilicate Dissolved in 10mL of ethanol, added dropwise to the dispersion of silver nanoparticles with a core-shell structure modified by tannic acid, and reacted at room temperature for 24h, after centrifugation and washing with ethanol, the modified silver nanoparticles were obtained. Particles, the results are shown in Figure 1(c).
从图1(a)中可以看到，纳米银粒子的表面有一层薄的有机层；从图1(b) 中可以看到，在接枝单宁酸(TA)后纳米银粒表面的有机层的厚度增加，形成单宁酸壳层；从图1(c)中可以看到，在加入正硅酸乙酯后，单宁酸壳层的表面负载二氧化硅颗粒，改性纳米银粒子整体形成树莓状结构。It can be seen from Figure 1(a) that there is a thin organic layer on the surface of the silver nanoparticles; as can be seen from Figure 1(b), the organic layer on the surface of the silver nanoparticles after grafting The thickness of the layer increases to form a tannic acid shell; as can be seen from Figure 1 (c), after adding orthosilicate, the surface of the tannic acid shell is loaded with silica particles, and the modified nano-silver particles The whole forms a raspberry-like structure.
同时，对步骤10、步骤20和步骤30得到的产物进行紫外可见吸收光谱法分析，从图2的紫外-可见吸收光谱图可以看到，经步骤10制备得到的纳米银粒子(图2中命名为Ag)的最大吸收波长在432nm，经步骤20单宁酸改性后得到经单宁酸改性的具有核壳结构的纳米银粒子(图2中命名为 Ag@TA)的最大吸收波长在453nm，经步骤30正硅酸乙酯改性后得到改性纳米银粒子(图2中命名为Ag@TA-SiO2)的最大吸收波长在467nm。Simultaneously, the product that step 10, step 20 and step 30 obtains is carried out ultraviolet-visible absorption spectrometry analysis, as can be seen from the ultraviolet-visible absorption spectrogram of Fig. 2, the nano-silver particle that prepares through step 10 (named in Fig. 2 The maximum absorption wavelength of Ag) is at 432nm, and the maximum absorption wavelength of the nano-silver particles with core-shell structure (named as Ag@TA in Fig. 453nm, the maximum absorption wavelength of the modified nano-silver particles (named as Ag@TA-SiO 2 in FIG. 2 ) obtained after modification with tetraethyl orthosilicate in step 30 is 467nm.
实施例2-4Example 2-4
实施例2-4的制备方法基本同实施例1，但不同之处在于，实施例2-4 中硝酸银、聚乙烯吡咯烷酮、乙二醇、单宁酸、正硅酸乙酯的含量如表1所示。The preparation method of embodiment 2-4 is substantially the same as embodiment 1, but the difference is that the content of silver nitrate, polyvinylpyrrolidone, ethylene glycol, tannic acid, orthosilicate in embodiment 2-4 is as shown in the table 1.
实施例5Example 5
硅烷类化合物GHMK的制备方法具体如下：The preparation method of silane compound GHMK is as follows:
步骤40，取0.018mol甲基丙烯酸缩水甘油酯、0.009mol甲基丙烯酸羟乙酯和0.003molγ-甲基丙烯酰氧基丙基三甲氧基硅烷于三口烧瓶中，加入 120mL甲醇，并加入偶氮二异丁腈，除氧，在氮气条件下80℃反应8h，得到中间化合物GHM；Step 40, take 0.018mol of glycidyl methacrylate, 0.009mol of hydroxyethyl methacrylate and 0.003mol of γ-methacryloxypropyltrimethoxysilane in a three-necked flask, add 120mL of methanol, and add azo Diisobutyronitrile, deoxygenated, reacted at 80°C for 8 hours under nitrogen to obtain the intermediate compound GHM;
步骤50，将步骤40得到的中间化合物GHM的温度降至50℃，然后向其中加入0.006mol(3-氨丙基)三乙氧基硅烷，保持50℃持续搅拌反应6h，反应结束后，冷却到室温，旋蒸掉多余的反应液后，将旋蒸后得到的浓缩液滴入正己烷中，洗涤多次，得到白色透明液状物，旋蒸后得到浓缩液体，即为所述硅烷类化合物GHMK。Step 50, lower the temperature of the intermediate compound GHM obtained in step 40 to 50°C, then add 0.006mol (3-aminopropyl)triethoxysilane to it, keep stirring at 50°C for 6h, after the reaction, cool After reaching room temperature, the excess reaction solution is evaporated by rotary evaporation, and the concentrated solution obtained after rotary evaporation is dropped into n-hexane, washed several times to obtain a white transparent liquid, and the concentrated liquid is obtained after rotary evaporation, which is the silane compound GHMK.
对步骤40得到的中间化合物GHM、步骤50得到的产物硅烷类化合物 GHMK以及步骤50所得到的产物固化后聚合物PGHMK进行红外光谱发分析，分析结果如图3所示。The intermediate compound GHM obtained in step 40, the product silane compound GHMK obtained in step 50, and the cured polymer PGHMK obtained in step 50 were analyzed by infrared spectroscopy, and the analysis results are shown in FIG. 3 .
实施例6-8Example 6-8
实施例6-8的制备方法基本同实施例5，但不同之处在于，实施例6-8 中甲基丙烯酸缩水甘油酯、甲基丙烯酸羟乙酯、γ-甲基丙烯酰氧基丙基三甲氧基硅烷、(3-氨丙基)三乙氧基硅烷的含量如表1所示。The preparation method of embodiment 6-8 is basically the same as embodiment 5, but the difference is that glycidyl methacrylate, hydroxyethyl methacrylate, gamma-methacryloxypropyl The contents of trimethoxysilane and (3-aminopropyl)triethoxysilane are shown in Table 1.
实施例9Example 9
防污涂料的制备方法具体如下：The preparation method of antifouling coating is specifically as follows:
步骤60，将实施例1中步骤30制备得到的改性纳米银粒子取0.01g分散于乙醇中，得到改性纳米银粒子的乙醇分散液；Step 60, taking 0.01 g of the modified silver nanoparticles prepared in step 30 of Example 1 and dispersing them in ethanol to obtain an ethanol dispersion of the modified silver nanoparticles;
步骤70，将实施例5中步骤50制备得到的硅烷类化合物GHMK取3.0g 溶于甲醇中，得到硅烷类化合物GHMK的甲醇溶液；Step 70, taking 3.0 g of the silane compound GHMK prepared in step 50 of Example 5 and dissolving it in methanol to obtain a methanol solution of the silane compound GHMK;
步骤80，将步骤60得到的改性纳米银粒子的乙醇分散液和步骤70得到的硅烷类化合物GHMK的甲醇溶液于40-50℃搅拌12-24h，旋蒸后得到浓缩液体，即为所述防污涂料。Step 80, stirring the ethanol dispersion of the modified nano-silver particles obtained in step 60 and the methanol solution of the silane compound GHMK obtained in step 70 at 40-50°C for 12-24h, and obtaining a concentrated liquid after rotary evaporation, which is the Antifouling paint.
将制备得到的防污涂料采用旋涂方法施覆在干净基材上；然后于 80-120℃烘箱中固化6h，得到施覆在基材上的防污涂层。The prepared antifouling coating is applied on a clean substrate by spin coating; and then cured in an oven at 80-120°C for 6 hours to obtain an antifouling coating applied on the substrate.
实施例10-15Examples 10-15
实施例10-15的制备方法基本同实施例9，但不同之处在于，实施例10-12 中改性纳米银粒子、硅烷类化合物的含量如表1所示。The preparation method of Examples 10-15 is basically the same as that of Example 9, but the difference is that the contents of modified nano-silver particles and silane compounds in Examples 10-12 are shown in Table 1.
为了便于说明，在下述表1中使用符号表示物质：For ease of explanation, substances are represented using symbols in Table 1 below:
A1：硝酸银A 1 : Silver nitrate
A2：聚乙烯吡咯烷酮A 2 : polyvinylpyrrolidone
A3：乙二醇A 3 : Ethylene glycol
A4：单宁酸A 4 : Tannic acid
A5：正硅酸乙酯A 5 : ethyl orthosilicate
B1：甲基丙烯酸缩水甘油酯B 1 : glycidyl methacrylate
B2：甲基丙烯酸羟乙酯B 2 : Hydroxyethyl methacrylate
B3：γ-甲基丙烯酰氧基丙基三甲氧基硅烷B 3 : γ-methacryloxypropyltrimethoxysilane
B4：(3-氨丙基)三乙氧基硅烷B 4 : (3-aminopropyl)triethoxysilane
C1：改性纳米银粒子C 1 : Modified nano-silver particles
C2：硅烷类化合物C 2 : Silane compounds
接下来说明对防污涂层的测试过程和测试结果。Next, the test procedure and test results for the antifouling coating will be described.
1)测试过程1) Test process
以干净玻璃片作为防污涂料的施覆基材。Clean glass flakes are used as substrates for antifouling coatings.
将实施例10-15制备得到的防污涂料采用旋涂方法施覆在干净基材上形成涂料层，然后于80-120℃烘箱中固化6h，得到具有不同防污涂层的干净玻璃片，作为实验组1-7。同时，以不施覆任何防污涂料的干净玻璃片作为对照组。The antifouling coatings prepared in Examples 10-15 were applied on a clean substrate by spin coating to form a coating layer, and then cured in an oven at 80-120° C. for 6 hours to obtain clean glass sheets with different antifouling coatings. As experimental groups 1-7. At the same time, a clean glass sheet without any antifouling coating was used as a control group.
将实验组1-7和对照组的玻璃片放入小星月菱形藻(3×105cell/mL)中，在模拟海洋环境下培养8天后，除去未在玻璃片和防污涂层表面附着的小星月菱形藻，用染色剂染色，PBS洗涤后，在荧光显微镜下进行观察。Put the glass slices of the experimental group 1-7 and the control group into Nitzcerella asterinae (3×10 5 cell/mL), culture them in a simulated ocean environment for 8 days, and remove the untreated glass slices and anti-fouling coating surface. The adherent Nitzschia asterinae was stained with a dye, washed with PBS, and observed under a fluorescent microscope.
2)测试结果2) Test results
观察结果如图4所示，其中，图4(a)为对照组的测试结果，图4(b)-(h) 依次为实验组1-7的测试结果。可以看到，施覆有本发明的防污涂料在玻璃片表面固化形成防污涂层后具有明显的防污效果。其中，实验组1未添加改性纳米银粒子时防污效果虽然优于对照组，但远不及添加了改性纳米银粒子的实验组2-7。由图4(c)-(h)与图4(b)的对比可以看到，虽然仅添加了极少量的改性纳米银粒子，但防污涂层的防污性能显著增强，说明改性纳米银粒子的加入对PGHMK具有协同复合作用；并且，随着改性纳米银粒子含量的增加，防污效果变好。The observation results are shown in Fig. 4, wherein Fig. 4(a) is the test result of the control group, and Fig. 4(b)-(h) are the test results of the experimental groups 1-7 in turn. It can be seen that the antifouling coating of the present invention has an obvious antifouling effect after the surface of the glass sheet is cured to form an antifouling coating. Among them, although the antifouling effect of experimental group 1 without modified nano-silver particles was better than that of the control group, it was far inferior to that of experimental groups 2-7 with modified nano-silver particles added. From the comparison of Figure 4(c)-(h) and Figure 4(b), it can be seen that although only a very small amount of modified nano-silver particles is added, the antifouling performance of the antifouling coating is significantly enhanced, indicating that the modification The addition of nano-silver particles has a synergistic composite effect on PGHMK; and, with the increase of the content of modified nano-silver particles, the antifouling effect becomes better.
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