CN104277664B - A kind of Marine Antifouling Paint - Google Patents
A kind of Marine Antifouling Paint Download PDFInfo
- Publication number
- CN104277664B CN104277664B CN201410557493.9A CN201410557493A CN104277664B CN 104277664 B CN104277664 B CN 104277664B CN 201410557493 A CN201410557493 A CN 201410557493A CN 104277664 B CN104277664 B CN 104277664B
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- China
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- parts
- modified
- agent
- antifouling paint
- epoxy resin
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- 239000003973 paint Substances 0.000 title claims abstract description 25
- 230000003373 anti-fouling effect Effects 0.000 title claims abstract description 23
- 239000003822 epoxy resin Substances 0.000 claims abstract description 37
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 37
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 31
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000000839 emulsion Substances 0.000 claims abstract description 20
- 239000002270 dispersing agent Substances 0.000 claims abstract description 18
- 239000002562 thickening agent Substances 0.000 claims abstract description 18
- 229920001661 Chitosan Polymers 0.000 claims abstract description 16
- 239000004814 polyurethane Substances 0.000 claims abstract description 15
- 229920002635 polyurethane Polymers 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 14
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000835 fiber Substances 0.000 claims abstract description 14
- 239000004593 Epoxy Substances 0.000 claims abstract description 13
- 239000013530 defoamer Substances 0.000 claims abstract description 13
- 239000000080 wetting agent Substances 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims description 34
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 24
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 12
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 10
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 8
- 229910000077 silane Inorganic materials 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 6
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 6
- 238000009413 insulation Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 5
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 5
- 229950000845 politef Drugs 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- 229960000892 attapulgite Drugs 0.000 claims description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 4
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 4
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 229910052625 palygorskite Inorganic materials 0.000 claims description 4
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 4
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 4
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 4
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 4
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 4
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 3
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 claims description 3
- -1 amino silicane Chemical compound 0.000 claims description 3
- 239000007822 coupling agent Substances 0.000 claims description 3
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 3
- 229920003063 hydroxymethyl cellulose Polymers 0.000 claims description 3
- 229940031574 hydroxymethyl cellulose Drugs 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims 1
- 238000010276 construction Methods 0.000 abstract description 5
- 238000000576 coating method Methods 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 8
- 230000007797 corrosion Effects 0.000 description 7
- 238000005260 corrosion Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 239000013535 sea water Substances 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229920006334 epoxy coating Polymers 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 description 1
- 150000008064 anhydrides Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
Classifications
-
- 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
- C09D5/08—Anti-corrosive paints
- C09D5/10—Anti-corrosive paints containing metal dust
-
- 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
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses a kind of Marine Antifouling Paint, its raw material includes following components by weight: aqueous epoxy resin emulsion 100 parts, aqueous polyurethane 5-16 part, modified pitch 1-2.5 part, aqueous epoxy curing agent 5-10 part, modified nano-titanium dioxide 10-30 part, modified carbon nano-tube 5-16 part, iron oxide red 5-15 part, zinc powder 3-5 part, fibre fluff 2-15 part, chitosan 0.9-2.5 part, coalescents 3-8 part, defoamer 0.5-1.3 part, wetting agent 0.3-1.5 part, dispersant 0.6-1.5 part, levelling agent 0.5-1.6 part, thickening agent 0.2-0.8 part, water 5-15 part.Marine Antifouling Paint of the present invention, its anticorrosive property is strong, good impact resistance, it is easy to construction, for long service life in oceanographic equipment.
Description
Technical field
The present invention relates to technical field of coatings, particularly relate to a kind of Marine Antifouling Paint.
Background technology
Marine anticorrosion is one of key technology of ocean engineering, and metal corrodes the stress corrosion fracture that causes in ocean, hydrogen embrittlement, corrosion fatigue, intercrystalline corrosion etc. can make ocean work steel construction that unexpected fracture occurs, and causes marine environment ecocatastrophe, brings about great losses.In recent years, both at home and abroad marine corrosion being paid attention to increasingly with protection, various seawater corrosion resistance materials are constantly released, and various Anticorrosion Construction technology also grow a lot, but still far from practical requirement.
Marine Antifouling Paint refers to the anticorrosive coating used in marine environment, and it generally requires have following performance: have good physical property, and corrosive medium impermeability is good, and steel surface adhesive force is good；Having good mechanical property, sea water resistance washes away, the erosion of sea water resistance, salt spray resistance, oil resistant, chemicals-resistant, UV resistant etc.；Good with electrochemical protection system compatibility, splash zone and submerged zone coating to have resistance to cathodic disbonding；There is good workability, under various environmental conditions different structure can be carried out high-quality coating decoration；Meeting the requirement of health, environmental protection, safety, coating solids is high, and volatile organic compound content meets country or international standard requirement.
The Marine Antifouling Paint performance of China still suffers from a lot of defect, it is impossible to meet the needs of society, for instance service life is short, anticorrosive property is poor.
Summary of the invention
The present invention proposes a kind of Marine Antifouling Paint, and its anticorrosive property is strong, good impact resistance, it is easy to construction, for long service life in oceanographic equipment.
The present invention proposes a kind of Marine Antifouling Paint, its raw material includes following components by weight: aqueous epoxy resin emulsion 100 parts, aqueous polyurethane 5-16 part, modified pitch 1-2.5 part, aqueous epoxy curing agent 5-10 part, modified nano-titanium dioxide 10-30 part, modified carbon nano-tube 5-16 part, iron oxide red 5-15 part, zinc powder 3-5 part, fibre fluff 2-15 part, chitosan 0.9-2.5 part, coalescents 3-8 part, defoamer 0.5-1.3 part, wetting agent 0.3-1.5 part, dispersant 0.6-1.5 part, levelling agent 0.5-1.6 part, thickening agent 0.2-0.8 part, water 5-15 part.
Preferably, described aqueous epoxy resin emulsion is prepared according to following technique: be heated with stirring to 55-70 DEG C after 20-40 part epoxy resin and 70-100 part Polyethylene Glycol mix homogeneously by weight, stirring 20-50min, add 0.5-2 part Ammonium persulfate., heat to 160-175 DEG C, stirring reaction 4-6h, be cooled to 60-70 DEG C, add 60-80 part epoxy resin, after stirring insulation 1-1.6h, add 50-80 part deionized water.
Preferably, described modified nano-titanium dioxide is prepared according to following technique: be added drop-wise in 50-100 part dehydrated alcohol by 20-35 part butyl titanate by weight, and stirring 10-20min obtains solution A, and wherein, time for adding is 2-5min；20-35 part water and 10-15 part concentrated nitric acid is added in solution A, it is transferred in politef autoclave after stirring 15-25min, at 55-65 DEG C, 50-60h it is incubated after sealing, it is centrifuged after cooling, with after distilled water wash at 55-65 DEG C vacuum drying 1-3h, grind obtain nano titanium dioxide powder；The nano titanium dioxide powder obtained and 1-3 part silane coupler are joined in 20-50 part water, ultrasonic disperse 10-25min, filters, washing, dries.
Preferably, described silane coupler is amino silicane coupling agent.
Preferably, its raw material includes following components by weight: aqueous epoxy resin emulsion 100 parts, aqueous polyurethane 8-13 part, modified pitch 1.6-2.2 part, aqueous epoxy curing agent 7-9 part, modified nano-titanium dioxide 16-26 part, modified carbon nano-tube 9-13 part, iron oxide red 7-12 part, zinc powder 3.6-4.5 part, fibre fluff 9-12 part, chitosan 1.5-2.2 part, coalescents 3.6-6.8 part, defoamer 0.9-1.2 part, wetting agent 0.8-1.3 part, dispersant 0.9-1.2 part, levelling agent 0.9-1.4 part, thickening agent 0.3-0.6 part, water 7-13 part.
Preferably, its raw material includes following components by weight: aqueous epoxy resin emulsion 100 parts, aqueous polyurethane 10 parts, modified pitch 2.1 parts, aqueous epoxy curing agent 7.8 parts, modified nano-titanium dioxide 22 parts, modified carbon nano-tube 12 parts, iron oxide red 10 parts, zinc powder 3.9 parts, fibre fluff 9.7 parts, chitosan 1.6 parts, coalescents 5.6 parts, defoamer 0.97 part, wetting agent 0.89 part, dispersant 0.96 part, levelling agent 1.32 parts, thickening agent 0.46 part, 12 parts of water.
Preferably, the modifying agent of described modified pitch is maleic anhydride.
Preferably, described coalescents is one or more the combination in ethylene glycol, butyl glycol ether, ethylene glycol, propylene glycol.
Preferably, described dispersant is one or more the combination in sodium tripolyphosphate, sodium tetrapolyphosphate, sodium hexameta phosphate.
Preferably, described thickening agent be one or more in carboxymethyl cellulose, hydroxymethyl cellulose, sodium polyacrylate, polyvinyl alcohol, hydroxyethyl cellulose, o-phthalic acid dibutyl ester, tricresyl phosphate, dibutyl phthalate with modified alta-mud, attapulgite modified in a kind of or combination of two kinds.
In the present invention, epoxy resin has the chemical resistance of excellence, numerous grounds is had splendid adhesive force, can solidify with multiple firming agent, and the compactness of film is good, and rigidity is strong, heat-resistant antifriction is good；But epoxy resin cured product fragility is high, and shock resistance is poor, and caking property is low；Add aqueous polyurethane, mutually run through between polyurethane segment and epoxy resin segment, defining interpenetrating polymer networks structure or semi-interpenetrating polymer network structure, two polymer networks have a kind of mutually collaborative effect, improve the performance of coating, impact strength is greatly improved, pliability strengthens, and caking property raises to some extent, improves in epoxy resin that to there is the fragility that causes big because of circulus, easily there is brittle fracture, the feature that caking property is low；The modifying agent of modified pitch is maleic anhydride, the carbon-carbon double bond contained in maleic anhydride has participation free radical and photochemically reactive ability, anhydride group can with some molecular reactions containing active hydrogen on the other hand, improve the compatibility of resin emulsion and Colophonium, the physics interlocking of both contact interfaces is strong, toughness reinforcing epoxy resin, improves its toughness, reduce further the shortcoming that matter is crisp；Nano titanium oxide is the excellent inorganic antibacterial material with photocatalysis, nontoxic, tasteless, non-stimulated, Heat stability is good, heat-resist, chitosan is a kind of natural antibacterial material, there is sterilizing rate height, the feature that safety is good, but its poor heat resistance, chitosan and modified nano-titanium dioxide have the good compatibility, after both coordinate, make both mutual supplement with each other's advantages, and it is effectively increased modified nano-titanium dioxide, the contact area of chitosan and epoxy resin, inhibit sea water in the diffusion within epoxy coating, increase the resistance of epoxy coating, improve the Corrosion Protection of coating；The iron oxide red of interpolation, modified nano-titanium dioxide, modified carbon nano-tube cooperate, improve coating surface roughness, in the process of paint solidification, reduce the shrinkage factor of paint film, maintain the adhesive force with matrix, shielding decreases water, oxygen, the passing through of ion, and coordinates with zinc powder, fibre fluff, improves the Corrosion Protection of coating.
In the present invention, by selecting suitable raw material, regulate the content of each raw material, make each material performance have complementary advantages, the Marine Antifouling Paint obtained, anticorrosive property is strong, good impact resistance, it is easy to construction, in oceanographic equipment, good combination property, long service life.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in detail; it is understood that; embodiment is served only for the present invention is described, rather than is used for limiting the invention, any make on basis of the present invention amendment, equivalent replacement etc. is all in protection scope of the present invention.
nullIn a particular embodiment，Marine Antifouling Paint of the present invention，In its raw material，The weight portion of aqueous epoxy resin emulsion is 100 parts，The weight portion of aqueous polyurethane can be 5.6、6、6.3、7、7.4、8.6、9、9.3、10.6、11、11.2、12、12.4、13.5、14、14.6、15、15.3 part，The weight portion of modified pitch can be 1.3、1.59、1.8、2.0、2.23、2.3、2.4、2.46 parts，The weight portion of aqueous epoxy curing agent can be 5.6、6、6.3、7.4、8、8.5、9.6 parts，The weight portion of modified nano-titanium dioxide can be 10.6、11、11.3、12、12.5、13、13.6、14、14.5、15、15.6、18、19、21.3、25、25.6、27、28.6、29、29.5 part、The weight portion of modified carbon nano-tube can be 5.9、6、6.6、7、7.5、8、8.6、9.8、10、10.5、11、11.3、12.5、13.4、14、14.6、15、15.6 part，The weight portion of iron oxide red can be 5.6、6、6.3、7.8、8、8.9、9、9.5、10.36、11、11.5、12.6、13、13.4、14、14.8 part，The weight portion of zinc powder can be 3.2、4、4.3、4.76 parts，The weight portion of fibre fluff can be 2.3、3、3.5、4、4.6、5、5.6、6、6.7、7、7.3、8、8.5、9.6、10、10.5、11、11.6、12.4、13、13.5、14、14.58 part，The weight portion of chitosan can be 0.96、1.0、1.1、1.23、1.4、1.58、1.7、1.8、1.86、1.9、1.94、2.0、2.1、2.23、2.3、2.34、2.4、2.46 parts，The weight portion of coalescents can be 4、4.5、5、6、6.3、7、7.8 parts，The weight portion of defoamer can be 0.56、0.7、0.86、0.95、1.0、1.05、1.1、1.23 parts，The weight portion of wetting agent can be 0.36、0.4、0.45、0.5、0.56、0.6、0.7、0.85、0.9、0.96、1.0、1.09、1.2、1.36、1.4、1.48 parts，The weight portion of dispersant can be 0.69、0.75、0.8、0.86、1.0、1.26、1.3、1.34、1.4、1.48 parts，The weight portion of levelling agent can be 0.56、0.6、0.67、0.7、0.78、0.8、0.86、0.94、1.0、1.23、1.3、1.35、1.59 parts，The weight portion of thickening agent can be 0.26、0.34、0.4、0.5、0.53、0.67、0.7、0.75 part，The weight portion of water can be 5.6、6、6.8、7、7.3、8、8.5、9、9.6、10、10.3、11、11.4、12、12.5、13、13.4、14、14.3 part.
Embodiment 1
Marine Antifouling Paint of the present invention, its raw material includes following components by weight: aqueous epoxy resin emulsion 100 parts, aqueous polyurethane 5 parts, modified pitch 2.5 parts, aqueous epoxy curing agent 10 parts, modified nano-titanium dioxide 30 parts, modified carbon nano-tube 5 parts, iron oxide red 5 parts, zinc powder 3 parts, fibre fluff 15 parts, chitosan 0.9 part, coalescents 8 parts, defoamer 0.5 part, wetting agent 1.5 parts, dispersant 0.6 part, levelling agent 1.6 parts, thickening agent 0.2 part, 5 parts of water.
Embodiment 2
Marine Antifouling Paint of the present invention, its raw material includes following components by weight: aqueous epoxy resin emulsion 100 parts, aqueous polyurethane 16 parts, modified pitch 1 part, aqueous epoxy curing agent 5 parts, modified nano-titanium dioxide 10 parts, modified carbon nano-tube 16 parts, iron oxide red 15 parts, zinc powder 5 parts, fibre fluff 2 parts, chitosan 2.5 parts, coalescents 3 parts, defoamer 1.3 parts, wetting agent 0.3 part, dispersant 1.5 parts, levelling agent 0.5 part, thickening agent 0.8 part, 15 parts of water；
Wherein, described aqueous epoxy resin emulsion is prepared according to following technique: be heated with stirring to 70 DEG C after 20 parts of epoxy resin and 100 parts of Polyethylene Glycol mix homogeneously by weight, stirring 20min, add 2 parts of Ammonium persulfate .s, heat to 160 DEG C, stirring reaction 6h, be cooled to 60 DEG C, add 80 parts of epoxy resin, after stirring insulation 1h, add 80 parts of deionized waters.
Embodiment 3
Marine Antifouling Paint of the present invention, its raw material includes following components by weight: aqueous epoxy resin emulsion 100 parts, aqueous polyurethane 9 parts, modified pitch 2.46 parts, aqueous epoxy curing agent 6.3 parts, modified nano-titanium dioxide 13 parts, modified carbon nano-tube 6.6 parts, iron oxide red 9.5 parts, zinc powder 4.76 parts, fibre fluff 12.4 parts, chitosan 2.23 parts, coalescents 7.8 parts, defoamer 1.1 parts, wetting agent 1.36 parts, dispersant 1.26 parts, levelling agent 0.78 part, thickening agent 0.26 part, 11 parts of water；
Wherein, described coalescents is that butyl glycol ether, ethylene glycol, propylene glycol are by weight for the combination of 1:2:3；Described dispersant is sodium tripolyphosphate；Described thickening agent is carboxymethyl cellulose is the combination of 1:3 by weight with modified alta-mud；
Described aqueous epoxy resin emulsion is prepared according to following technique: be heated with stirring to 55 DEG C after 40 parts of epoxy resin and 70 parts of Polyethylene Glycol mix homogeneously by weight, stirring 50min, add 0.5 part of Ammonium persulfate., heating is to 175 DEG C, stirring reaction 4h, it is cooled to 70 DEG C, adds 60 parts of epoxy resin, after stirring insulation 1.6h, add 50 parts of deionized waters；
Described modified nano-titanium dioxide is prepared according to following technique: be added drop-wise in 50 parts of dehydrated alcohol by 20 parts of butyl titanates by weight, and stirring 20min obtains solution A, and wherein, time for adding is 2min；35 parts of water and 10 parts of concentrated nitric acids are added in solution A, it is transferred in politef autoclave after stirring 15min, at 55 DEG C, after sealing, is incubated 60h, centrifugal after cooling, with after distilled water wash at 55 DEG C vacuum drying 3h, grind obtain nano titanium dioxide powder；The nano titanium dioxide powder obtained and 1 part of silane coupler are joined in 50 parts of water, ultrasonic disperse 10min, filters, washing, dries；Described silane coupler is amino silicane coupling agent.
Embodiment 4
Marine Antifouling Paint of the present invention, its raw material includes following components by weight: aqueous epoxy resin emulsion 100 parts, aqueous polyurethane 8 parts, modified pitch 1.6 parts, aqueous epoxy curing agent 8.67 parts, modified nano-titanium dioxide 19 parts, modified carbon nano-tube 13 parts, iron oxide red 12 parts, zinc powder 4.3 parts, fibre fluff 7 parts, chitosan 2.38 parts, coalescents 4.8 parts, defoamer 1.19 parts, wetting agent 0.89 part, dispersant 1.23 parts, levelling agent 1.42 parts, thickening agent 0.36 part, 7 parts of water；
Wherein, the modifying agent of described modified pitch is maleic anhydride；Described coalescents is ethylene glycol；Described dispersant is that sodium tetrapolyphosphate, sodium hexameta phosphate are by weight for the combination of 1:4；Described thickening agent is sodium polyacrylate and modified alta-mud, the attapulgite modified combination that ratio is 1:2:5 by weight；
Described aqueous epoxy resin emulsion is prepared according to following technique: be heated with stirring to 63 DEG C after 33 parts of epoxy resin and 79 parts of Polyethylene Glycol mix homogeneously by weight, stirring 46min, add 1.6 parts of Ammonium persulfate .s, heating is to 167 DEG C, stirring reaction 5.4h, it is cooled to 63 DEG C, adds 72 parts of epoxy resin, after stirring insulation 1.35h, add 70 parts of deionized waters；
Described modified nano-titanium dioxide is prepared according to following technique: be added drop-wise in 100 parts of dehydrated alcohol by 35 parts of butyl titanates by weight, and stirring 10min obtains solution A, and wherein, time for adding is 5min；20 parts of water and 15 parts of concentrated nitric acids are added in solution A, it is transferred in politef autoclave after stirring 25min, at 65 DEG C, after sealing, is incubated 50h, centrifugal after cooling, with after distilled water wash at 65 DEG C vacuum drying 1h, grind obtain nano titanium dioxide powder；The nano titanium dioxide powder obtained and 3 parts of silane couplers are joined in 20 parts of water, ultrasonic disperse 25min, filters, washing, dries.
Embodiment 5
Marine Antifouling Paint of the present invention, its raw material includes following components by weight: aqueous epoxy resin emulsion 100 parts, aqueous polyurethane 10 parts, modified pitch 2.1 parts, aqueous epoxy curing agent 7.8 parts, modified nano-titanium dioxide 22 parts, modified carbon nano-tube 12 parts, iron oxide red 10 parts, zinc powder 3.9 parts, fibre fluff 9.7 parts, chitosan 1.6 parts, coalescents 5.6 parts, defoamer 0.97 part, wetting agent 0.89 part, dispersant 0.96 part, levelling agent 1.32 parts, thickening agent 0.46 part, 12 parts of water；
Wherein, described coalescents is that ethylene glycol, butyl glycol ether, ethylene glycol, propylene glycol are by the combination of any weight ratio；Described dispersant is that sodium tripolyphosphate, sodium tetrapolyphosphate, sodium hexameta phosphate are by the combination of any weight ratio；Described thickening agent is carboxymethyl cellulose, hydroxymethyl cellulose, sodium polyacrylate, polyvinyl alcohol, hydroxyethyl cellulose, o-phthalic acid dibutyl ester, tricresyl phosphate, dibutyl phthalate and modified alta-mud, the attapulgite modified combination by any weight ratio；
Described aqueous epoxy resin emulsion is prepared according to following technique: be heated with stirring to 58 DEG C after 33 parts of epoxy resin and 95 parts of Polyethylene Glycol mix homogeneously by weight, stirring 26min, add 0.98 part of Ammonium persulfate., heating is to 173 DEG C, stirring reaction 5.3h, it is cooled to 62 DEG C, adds 65 parts of epoxy resin, after stirring insulation 1.36h, add 59 parts of deionized waters.
Described modified nano-titanium dioxide is prepared according to following technique: be added drop-wise in 86 parts of dehydrated alcohol by 27 parts of butyl titanates by weight, and stirring 16min obtains solution A, and wherein, time for adding is 2.8min；33 parts of water and 12 parts of concentrated nitric acids are added in solution A, it is transferred in politef autoclave after stirring 19min, at 57 DEG C, after sealing, is incubated 58h, centrifugal after cooling, with after distilled water wash at 62 DEG C vacuum drying 1.8h, grind obtain nano titanium dioxide powder；The nano titanium dioxide powder obtained and 1.9 parts of silane couplers are joined in 43 parts of water, ultrasonic disperse 22min, filters, washing, dries.
The above; it is only the present invention preferably detailed description of the invention; but protection scope of the present invention is not limited thereto; any those familiar with the art is in the technical scope that the invention discloses; it is equal to replacement according to technical scheme and inventive concept thereof or is changed, all should be encompassed within protection scope of the present invention.
Claims (7)
1. a Marine Antifouling Paint, it is characterized in that, its raw material includes following components by weight: aqueous epoxy resin emulsion 100 parts, aqueous polyurethane 5-16 part, modified pitch 1-2.5 part, aqueous epoxy curing agent 5-10 part, modified nano-titanium dioxide 10-30 part, modified carbon nano-tube 5-16 part, iron oxide red 5-15 part, zinc powder 3-5 part, fibre fluff 2-15 part, chitosan 0.9-2.5 part, coalescents 3-8 part, defoamer 0.5-1.3 part, wetting agent 0.3-1.5 part, dispersant 0.6-1.5 part, levelling agent 0.5-1.6 part, thickening agent 0.2-0.8 part, water 5-15 part；
Described aqueous epoxy resin emulsion is prepared according to following technique: be heated with stirring to 55-70 DEG C after 20-40 part epoxy resin and 70-100 part Polyethylene Glycol mix homogeneously by weight, stirring 20-50min, add 0.5-2 part Ammonium persulfate., heating is to 160-175 DEG C, stirring reaction 4-6h, it is cooled to 60-70 DEG C, adds 60-80 part epoxy resin, after stirring insulation 1-1.6h, add 50-80 part deionized water；
Described modified nano-titanium dioxide is prepared according to following technique: be added drop-wise in 50-100 part dehydrated alcohol by 20-35 part butyl titanate by weight, and stirring 10-20min obtains solution A, and wherein, time for adding is 2-5min；20-35 part water and 10-15 part concentrated nitric acid is added in solution A, it is transferred in politef autoclave after stirring 15-25min, at 55-65 DEG C, 50-60h it is incubated after sealing, it is centrifuged after cooling, with after distilled water wash at 55-65 DEG C vacuum drying 1-3h, grind obtain nano titanium dioxide powder；The nano titanium dioxide powder obtained and 1-3 part silane coupler are joined in 20-50 part water, ultrasonic disperse 10-25min, filters, washing, dries；
The modifying agent of described modified pitch is maleic anhydride.
2. Marine Antifouling Paint according to claim 1, it is characterised in that described silane coupler is amino silicane coupling agent.
3. Marine Antifouling Paint according to any one of claim 1-2, it is characterized in that, its raw material includes following components by weight: aqueous epoxy resin emulsion 100 parts, aqueous polyurethane 8-13 part, modified pitch 1.6-2.2 part, aqueous epoxy curing agent 7-9 part, modified nano-titanium dioxide 16-26 part, modified carbon nano-tube 9-13 part, iron oxide red 7-12 part, zinc powder 3.6-4.5 part, fibre fluff 9-12 part, chitosan 1.5-2.2 part, coalescents 3.6-6.8 part, defoamer 0.9-1.2 part, wetting agent 0.8-1.3 part, dispersant 0.9-1.2 part, levelling agent 0.9-1.4 part, thickening agent 0.3-0.6 part, water 7-13 part.
4. Marine Antifouling Paint according to claim 3, it is characterized in that, its raw material includes following components by weight: aqueous epoxy resin emulsion 100 parts, aqueous polyurethane 10 parts, modified pitch 2.1 parts, aqueous epoxy curing agent 7.8 parts, modified nano-titanium dioxide 22 parts, modified carbon nano-tube 12 parts, iron oxide red 10 parts, zinc powder 3.9 parts, fibre fluff 9.7 parts, chitosan 1.6 parts, coalescents 5.6 parts, defoamer 0.97 part, wetting agent 0.89 part, dispersant 0.96 part, levelling agent 1.32 parts, thickening agent 0.46 part, 12 parts of water.
5. Marine Antifouling Paint according to claim 1, it is characterised in that described coalescents is one or more the combination in ethylene glycol, butyl glycol ether, ethylene glycol, propylene glycol.
6. Marine Antifouling Paint according to claim 1, it is characterised in that described dispersant is one or more the combination in sodium tripolyphosphate, sodium tetrapolyphosphate, sodium hexameta phosphate.
7. Marine Antifouling Paint according to claim 1, it is characterized in that, described thickening agent be one or more in carboxymethyl cellulose, hydroxymethyl cellulose, sodium polyacrylate, polyvinyl alcohol, hydroxyethyl cellulose, dioctyl phthalate, tricresyl phosphate, dibutyl phthalate with modified alta-mud, attapulgite modified in a kind of or combination of two kinds.
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