CN116285568A - Degradable marine anti-corrosion coating and preparation method thereof - Google Patents
Degradable marine anti-corrosion coating and preparation method thereof Download PDFInfo
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- CN116285568A CN116285568A CN202310116399.9A CN202310116399A CN116285568A CN 116285568 A CN116285568 A CN 116285568A CN 202310116399 A CN202310116399 A CN 202310116399A CN 116285568 A CN116285568 A CN 116285568A
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- 238000000576 coating method Methods 0.000 title claims abstract description 75
- 239000011248 coating agent Substances 0.000 title claims abstract description 72
- 238000005260 corrosion Methods 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title description 13
- 229920001661 Chitosan Polymers 0.000 claims abstract description 69
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 37
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 37
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000002994 raw material Substances 0.000 claims abstract description 32
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 15
- 239000003822 epoxy resin Substances 0.000 claims abstract description 11
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 11
- 239000000945 filler Substances 0.000 claims abstract description 6
- 238000004132 cross linking Methods 0.000 claims abstract description 4
- 239000003973 paint Substances 0.000 claims description 42
- 239000000178 monomer Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 17
- -1 2, 3-epoxypropoxy Chemical group 0.000 claims description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- DZZWKUMHMSNBSG-UHFFFAOYSA-N 1,3-bis(prop-2-enyl)thiourea Chemical compound C=CCNC(=S)NCC=C DZZWKUMHMSNBSG-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical group [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 10
- 230000006196 deacetylation Effects 0.000 claims description 8
- 238000003381 deacetylation reaction Methods 0.000 claims description 8
- 239000003995 emulsifying agent Substances 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 8
- 239000002270 dispersing agent Substances 0.000 claims description 5
- 239000000049 pigment Substances 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 2
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- 239000002518 antifoaming agent Substances 0.000 claims description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 2
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 claims description 2
- 230000003373 anti-fouling effect Effects 0.000 abstract description 4
- 239000003518 caustics Substances 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 13
- 230000007797 corrosion Effects 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- 230000032683 aging Effects 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- 238000001914 filtration Methods 0.000 description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 238000010998 test method Methods 0.000 description 5
- 239000002966 varnish Substances 0.000 description 5
- 230000018109 developmental process Effects 0.000 description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 239000013535 sea water Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- JECYNCQXXKQDJN-UHFFFAOYSA-N 2-(2-methylhexan-2-yloxymethyl)oxirane Chemical compound CCCCC(C)(C)OCC1CO1 JECYNCQXXKQDJN-UHFFFAOYSA-N 0.000 description 1
- IVKNZCBNXPYYKL-UHFFFAOYSA-N 2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[4-(2,4,4-trimethylpentan-2-yl)phenoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethanol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(OCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO)C=C1 IVKNZCBNXPYYKL-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- HTKFORQRBXIQHD-UHFFFAOYSA-N allylthiourea Chemical compound NC(=S)NCC=C HTKFORQRBXIQHD-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000002207 metabolite Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
- C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
- C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
- C09D5/1637—Macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Biochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Paints Or Removers (AREA)
Abstract
The invention provides a degradable marine anti-corrosion coating which comprises the following raw materials in parts by weight: 40-60 parts of epoxy resin, 10-20 parts of modified acrylic resin, 15-20 parts of modified chitosan, 5-10 parts of curing agent, 10-15 parts of solvent and 20-30 parts of filler, wherein the modified chitosan is obtained by crosslinking 1, 5-bis (2, 3-glycidoxy) -2, 3, 4-hexafluoropentane with chitosan. The invention provides a degradable marine anti-corrosion coating which has excellent anti-corrosion and anti-fouling properties, and a coating prepared from the coating has a rough surface and low surface energy, and corrosive substances are difficult to stay on the surface of the coating.
Description
Technical Field
The invention relates to the technical field of coatings, in particular to a degradable marine anti-corrosion coating and a preparation method thereof.
Background
With the development of the age and the progress of technology, the ocean economy is rapidly developed, and the ocean resources and the marine ship industry become important support columns which are indispensable in the world economy development. At present, china is in a key stage of intensive low-carbon economic transformation period, and is also a key period of implementation of ocean strategy, and the industries of ocean transportation, deep sea new energy development, coastal ports, ships and the like rapidly develop.
However, with the reciprocating impact of sea surface stormy waves and the like on metal members and the corrosion of sea water, marine organisms and their metabolites and the like on metal materials, the marine environment has become a very harsh corrosion-prone environment. The current applicable and economical ocean engineering protection method is to coat ocean paint for preventing seawater corrosion, and simultaneously, the country goes out a series of favorable policies for promoting environment-friendly paint and greatly promotes the development of environment-friendly paint.
Therefore, it is necessary to find an environment-friendly anticorrosive paint suitable for marine environments.
Disclosure of Invention
The invention aims to provide a degradable marine anti-corrosion coating and a preparation method thereof, so that the prepared coating has good anti-corrosion and anti-rust properties, is biodegradable and is environment-friendly.
According to a first aspect of the present invention, there is provided a degradable marine anticorrosive paint comprising the following raw materials in parts by weight: 40-60 parts of epoxy resin, 10-20 parts of acrylic resin, 15-20 parts of modified chitosan, 5-10 parts of curing agent, 10-15 parts of solvent and 20-30 parts of filler, wherein the modified chitosan is obtained by crosslinking 1, 5-bis (2, 3-glycidoxy) -2, 3, 4-hexafluoropentane with chitosan.
According to the invention, the modified chitosan is prepared by reacting chitosan with the fluorine-rich epoxy compound 1, 5-di (2, 3-glycidoxy) -2, 3, 4-hexafluoropentane, so that the degradable marine anticorrosive paint adopting the modified chitosan has excellent anticorrosive and antifouling properties, and the fluorine-rich epoxy compound is added into a paint system, so that the surface of a coating prepared by the paint is rough, the surface energy is low, the water contact angle is large, and corrosive substances are difficult to stay on the surface of the coating. And secondly, the prepared modified chitosan is used as a film forming substance of the coating, so that the prepared degradable marine anti-corrosion coating has antibacterial effect, also has biodegradability, and degradation products of the coating cannot cause harm to the environment. The surface of the coating prepared by the invention is gradually degraded and separated under the corrosion of seawater and microorganisms, so that the attached microorganisms and dirt are separated from the substrate and the coating, and the modified chitosan in the coating can migrate to the surface layer of the coating, thereby improving the corrosion resistance and the pollution resistance of the coating.
Preferably, the modified chitosan is prepared by the following steps: chitosan is dissolved in acetic acid solution and is uniformly mixed with 1, 5-di (2, 3-epoxypropoxy) -2, 3, 4-hexafluoropentane and an organotin catalyst, and the mixture is subjected to reflux reaction for 3.5 to 4.5 hours at the temperature of 35 to 45 ℃ so as to prepare the modified chitosan. The amino group of the chitosan and the epoxy group of the 1, 5-di (2, 3-epoxypropoxy) -2, 3, 4-hexafluoropentane are utilized to carry out ring-opening reaction, so that the prepared modified chitosan has a reticular cross-linking structure, the mechanical property of the coating can be improved, the toughness and the hardness of the coating are increased, and meanwhile, the salt-alkali resistance and the corrosion resistance of the coating are increased.
Preferably, in the raw material for preparing the modified chitosan, the molar ratio of chitosan to 1, 5-bis (2, 3-glycidoxy) -2, 3, 4-hexafluoropentane is 2:1.
Preferably, the organotin catalyst is stannous octoate, and the dosage of the stannous octoate is 0.2-0.8% of the mass of the chitosan.
Preferably, the chitosan has a degree of deacetylation of not less than 85%. The deacetylation degree of the chitosan influences the reactivity of the chitosan, and the higher the deacetylation degree of the chitosan is, the higher the reactivity with 1, 5-bis (2, 3-glycidoxy) -2, 3, 4-hexafluoropentane is, but the corresponding cost is increased, so that the modified reactivity of the chitosan can be ensured by selecting the chitosan with the deacetylation degree of not less than 85%, and the economic benefit of the coating can be improved.
Preferably, the acrylic resin is modified acrylic resin, and the raw materials for preparing the modified acrylic resin comprise the following components in parts by weight: 60-80 parts of acrylic monomer, 5-12 parts of 1, 3-diallyl-2-thiourea, 30-50 parts of organosilicon monomer, 10-20 parts of emulsifier, 5-10 parts of initiator and 60-80 parts of water. According to the modified acrylic resin disclosed by the invention, the prepared coating and the substrate are tightly adhered by adding the 1, 3-diallyl-2-thiourea, and the thiourea and the ether are migrated to the surface attached to the substrate by introducing the thiourea and the ether into a coating system and relying on Van der Waals force and hydrogen bond acting force, so that the adhesive strength is increased, and the firm adhesion between the coating and the surface of the substrate is ensured. And secondly, after the 1, 3-diallyl-2-thiourea is emulsified and crosslinked with acrylic monomers and organosilicon monomers, the prepared modified acrylic resin can enable the coating to have rust resistance and strong weather resistance.
Preferably, the modified acrylic resin is prepared by the steps of: the organosilicon monomer, acrylic ester monomer, 1, 3-diallyl-2-thiourea, initiator, deionized water and emulsifier are mixed uniformly, and the mixture formed by the steps is reacted for 3 to 5 hours at the temperature of between 70 and 90 ℃ to prepare the modified acrylic resin. By adjusting the reaction temperature and the reaction time, the occurrence of side reactions is reduced, and the shape of the final product is controlled.
Preferably, the acrylic monomer is composed of butyl acrylate, glycidyl acrylate and hydroxyethyl methacrylate according to a molar ratio of 1:1:1. When the acrylic monomer meets the above conditions, the prepared modified acrylic resin has good compatibility with the formula, so that the degradable marine anticorrosive paint has good wear resistance, flexibility, hardness and dispersibility.
Preferably, the organosilicon monomer is selected from at least one of epoxy trimethoxysilane, vinyl triethoxysilane, gamma-methacryloxypropyl trimethoxysilane.
Preferably, the emulsifier is a persulfate.
Preferably, the initiator is at least one of OP-10, sodium dodecyl sulfate, sodium dodecyl sulfonate and sodium dodecyl benzene sulfonate.
Preferably, the composition further comprises the following raw materials in parts by weight: 3 to 8 parts of pigment, 1 to 2 parts of dispersing agent, 0.5 to 2 parts of defoaming agent, 0.5 to 1 part of leveling agent and 1 to 2 parts of anti-settling agent.
Preferably, the solvent is at least one selected from methanol, ethanol, acetone, butanone, acetylacetone, toluene, xylene, diethyl ether, petroleum ether, diethyl ether.
According to another aspect of the present invention, there is provided a method for preparing the above degradable marine anti-corrosive paint, comprising the steps of: and uniformly mixing the solvent, the epoxy resin and the acrylic resin to obtain a coating intermediate, and uniformly mixing the coating intermediate with the rest raw materials to obtain the degradable marine anti-corrosion coating. The degradable marine anti-corrosion coating provided by the scheme is simple in preparation process, convenient to operate and good in economic benefit.
Detailed Description
In order that those skilled in the art will better understand the present invention, a technical solution of the embodiments of the present invention will be clearly and completely described below, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments.
Example 1
The degradable marine anticorrosive paint prepared by the embodiment comprises the following raw materials in parts by weight: 40 parts of epoxy resin, 10 parts of modified acrylic resin, 15 parts of modified chitosan, 5 parts of curing agent, 10 parts of solvent and 20 parts of filler. Preparing materials according to the raw material formula, and preparing the degradable marine anti-corrosion coating according to the following steps: and uniformly mixing the solvent, the epoxy resin and the modified acrylic resin to obtain a coating intermediate, and uniformly mixing the coating intermediate with the rest raw materials to obtain the degradable marine anti-corrosion coating.
The modified chitosan is prepared by the following steps: dissolving chitosan in 2% (v/v) acetic acid solution, uniformly mixing the chitosan with 1, 5-bis (2, 3-epoxypropoxy) -2, 3, 4-hexafluoropentane and stannous octoate, carrying out reflux reaction for 4.5 hours at 35 ℃, filtering the solution while the solution is hot after the reaction is finished, concentrating the filtrate under reduced pressure until the solvent is removed, and carrying out vacuum drying to obtain the modified chitosan. Wherein the molar ratio of the chitosan to the 1, 5-bis (2, 3-glycidoxy) -2, 3, 4-hexafluoropentane is 2:1; the consumption of stannous octoate is 0.2% of the mass of chitosan; the degree of deacetylation of chitosan was 85%. Wherein, 1, 5-bis (2, 3-epoxypropoxy) -2, 3, 4-hexafluoropentane is purchased from Shaanxi Congress pharmaceutical chemical Co.
The modified acrylic resin is prepared by the following steps: mixing 30 parts of organic silicon monomer with 60 parts of acrylic ester monomer, 8 parts of 1, 3-diallyl-2-thiourea, 5 parts of initiator, 60 parts of deionized water and 10 parts of emulsifier uniformly, stirring at 70 ℃ for reaction for 5 hours, cooling to room temperature, regulating the pH value to be neutral, filtering, and discharging to obtain the modified acrylic resin.
In this embodiment, pigments, dispersants, defoamers, leveling agents, anti-settling agents may be added as appropriate according to the actual situation.
Example 2
The degradable marine anticorrosive paint prepared by the embodiment comprises the following raw materials in parts by weight: 50 parts of epoxy resin, 15 parts of modified acrylic resin, 18 parts of modified chitosan, 8 parts of curing agent, 12 parts of solvent and 25 parts of filler. Preparing materials according to the raw material formula, and preparing the degradable marine anti-corrosion coating according to the following steps: and uniformly mixing the solvent, the epoxy resin and the modified acrylic resin to obtain a coating intermediate, and uniformly mixing the coating intermediate with the rest raw materials to obtain the degradable marine anti-corrosion coating.
The modified chitosan is prepared by the following steps: dissolving chitosan in 2% (v/v) acetic acid solution, uniformly mixing the chitosan with 1, 5-di (2, 3-epoxypropoxy) -2, 3, 4-hexafluoropentane and stannous octoate, carrying out reflux reaction for 4 hours at 40 ℃, filtering the solution while the solution is hot after the reaction is finished, concentrating the filtrate under reduced pressure until the solvent is removed, and carrying out vacuum drying to obtain the modified chitosan. Wherein the molar ratio of the chitosan to the 1, 5-bis (2, 3-glycidoxy) -2, 3, 4-hexafluoropentane is 2:1; the consumption of stannous octoate is 0.5% of the mass of chitosan; the degree of deacetylation of chitosan was 85%. Wherein, 1, 5-bis (2, 3-epoxypropoxy) -2, 3, 4-hexafluoropentane is purchased from Shaanxi Congress pharmaceutical chemical Co.
The modified acrylic resin is prepared by the following steps: uniformly mixing 40 parts of organic silicon monomer with 70 parts of acrylic ester monomer, 10 parts of 1, 3-diallyl-2-thiourea, 8 parts of initiator, 70 parts of deionized water and 15 parts of emulsifier, stirring at 80 ℃ for reaction for 4 hours, cooling to room temperature, regulating the pH value to be neutral, and filtering to obtain the modified acrylic resin.
In this embodiment, pigments, dispersants, defoamers, leveling agents, anti-settling agents may be added as appropriate according to the actual situation.
Example 3
The degradable marine anticorrosive paint prepared by the embodiment comprises the following raw materials in parts by weight: 60 parts of epoxy resin, 20 parts of modified acrylic resin, 20 parts of modified chitosan, 10 parts of curing agent, 15 parts of solvent and 30 parts of filler. Preparing materials according to the raw material formula, and preparing the degradable marine anti-corrosion coating according to the following steps: and uniformly mixing the solvent, the epoxy resin and the modified acrylic resin to obtain a coating intermediate, and uniformly mixing the coating intermediate with the rest raw materials to obtain the degradable marine anti-corrosion coating.
The modified chitosan is prepared by the following steps: dissolving chitosan in 2% (v/v) acetic acid solution, uniformly mixing the chitosan with 1, 5-bis (2, 3-epoxypropoxy) -2, 3, 4-hexafluoropentane and stannous octoate, carrying out reflux reaction for 3.5 hours at 45 ℃, filtering the solution while the solution is hot after the reaction is finished, concentrating the filtrate under reduced pressure until the solvent is removed, and carrying out vacuum drying to obtain the modified chitosan. Wherein the molar ratio of the chitosan to the 1, 5-bis (2, 3-glycidoxy) -2, 3, 4-hexafluoropentane is 2:1; the consumption of stannous octoate is 0.8% of the mass of chitosan; the degree of deacetylation of chitosan was 85%. Wherein, 1, 5-bis (2, 3-epoxypropoxy) -2, 3, 4-hexafluoropentane is purchased from Shaanxi Congress pharmaceutical chemical Co.
The modified acrylic resin is prepared by the following steps: 50 parts of organic silicon monomer, 80 parts of acrylic ester monomer, 12 parts of 1, 3-diallyl-2-thiourea, 10 parts of initiator, 80 parts of deionized water and 20 parts of emulsifier are uniformly mixed, stirred at 90 ℃ for reaction for 3 hours, cooled to room temperature, pH value is regulated to be neutral, and the modified acrylic resin is obtained after filtration.
In this embodiment, pigments, dispersants, defoamers, leveling agents, anti-settling agents may be added as appropriate according to the actual situation.
Example 4
This example refers to the method for preparing a degradable marine anticorrosive paint provided in example 2, and a degradable marine anticorrosive paint is prepared, and this example differs from example 2 in that: in the preparation of the modified acrylic resin, equal mass of N-allylthiourea was used instead of 1, 3-diallyl-2-thiourea in the raw material used in example 2. The proportions of the other raw materials and the preparation method are strictly consistent with those of the embodiment 2.
Example 5
This example refers to the method for preparing a degradable marine anticorrosive paint provided in example 2, and a degradable marine anticorrosive paint is prepared, and this example differs from example 2 in that: in the preparation of the modified acrylic resin, equal mass of deionized water was used instead of 1, 3-diallyl-2-thiourea in the raw material used in example 2. The proportions of the other raw materials and the preparation method are strictly consistent with those of the embodiment 2.
Example 6
This example refers to the method for preparing a degradable marine anticorrosive paint provided in example 2, and a degradable marine anticorrosive paint is prepared, and this example differs from example 2 in that: in the process of preparing the degradable marine anticorrosive paint, the modified acrylic resin is replaced by common acrylic resin with the brand of ROSF-5007, which is produced by Guangzhou Luo Sifu new material Co., ltd. The proportions of the other raw materials and the preparation method are strictly consistent with those of the embodiment 2.
Comparative example 1
This comparative example, which is different from example 2 in that a degradable marine anticorrosive paint was prepared with reference to the method for preparing a degradable marine anticorrosive paint provided in example 2: in the process of preparing the modified chitosan, example was replaced by equal mass of 2- [ (2, 3-pentafluoropropoxy) methyl ] oxirane 2, 1, 5-bis (2, 3-epoxypropoxy) -2, 3, 4-hexafluoropentane in the raw materials adopted. The proportions of the other raw materials and the preparation method are strictly consistent with those of the embodiment 2.
Comparative example 2
This comparative example, which is different from example 2 in that a degradable marine anticorrosive paint was prepared with reference to the method for preparing a degradable marine anticorrosive paint provided in example 2: in the process of preparing the degradable marine anticorrosive paint, the modified chitosan in the raw materials adopted in the example 2 is replaced by the common unmodified chitosan with equal quality. The proportions of the other raw materials and the preparation method are strictly consistent with those of the embodiment 2.
Comparative example 3
This comparative example, which is different from example 2 in that a degradable marine anticorrosive paint was prepared with reference to the method for preparing a degradable marine anticorrosive paint provided in example 2: in the process of preparing the degradable marine anti-corrosion coating, modified chitosan is not added. The proportions of the other raw materials and the preparation method are strictly consistent with those of the embodiment 2.
Test case
A reference subject: the degradable marine anticorrosive paint provided in examples 1 to 6 and comparative examples 1 to 3 is a coating prepared from the degradable marine anticorrosive paint.
Test items:
(1) Hardness: the test method of paint film hardness is measured by referring to GB/T6739-2006 paint and varnish pencil method.
(2) Corrosion resistance: reference is made to the test method of GB/T1771-2007 determination of neutral salt spray resistance of paints and varnishes.
(3) Aging resistance: reference is made to the test method of GB/T1766-2008 paint and varnish, rating method for ageing of coating.
(4) Adhesion to substrate: reference is made to the test methods of the cross-hatch test of GB/T9286-1998 color paint and varnish film.
(5) Water resistance: reference is made to the test method of GB/T5209-1985 method for determining the water resistance of paints and varnishes.
Test results: as shown in table 1.
TABLE 1 test results of various properties of the coatings prepared from the degradable marine anticorrosive coatings
Note that: the meaning of "2400 hours" in salt spray resistance test in table 1 is "no cracking of paint film within 2400 hours, no bubbles", and so on; the meaning of "2300 hours" in the aging resistance test is "2300 hours in which the coating layer is not cracked and does not bulge", and so on; the meaning of "1440 hours" in the water resistance test is "1440 hours" without foaming, without wrinkling, without rust, without discoloration, without falling off.
From the test results in table 1, the test results of examples 1 to 6 are better than the test results of comparative examples 1 to 3, which indicate that the degradable marine anticorrosive paint prepared by using the modified acrylic resin and the modified chitosan has better comprehensive properties, wherein the hardness, salt spray resistance and aging resistance of the prepared coating are particularly excellent. Wherein, the best combination property is the coating corresponding to the embodiment 1-3, and the bonding strength, the water resistance, the corrosion resistance and the aging resistance are all the best.
Comparing the test results of comparative example 3 with those of example 2, the corrosion resistance and the salt and alkali resistance of comparative example 3 are obviously lower, and it can be seen that the degradable marine anti-corrosion coating added with the modified chitosan not only has excellent corrosion resistance and antifouling performance, but also ensures that corrosive substances are difficult to stay on the surface of the coating, and the coating has biodegradability, thereby meeting the environmental protection requirement. From the test results in table 1 of example 2 and comparative example 2, it is known that the coating prepared by using the unmodified chitosan has biodegradability as well, but the corrosion resistance and water resistance of the coating are obviously reduced, which indicates that the coating prepared by adding the modified chitosan is suitable for marine environment and has high corrosion resistance, rust resistance, water resistance and aging resistance. Comparing the test results of example 2 with those of comparative example 1, comparative example 1 uses 2- [ (2, 3-pentafluoropropoxy) methyl ] oxirane, and the corrosion resistance and the salt and alkali resistance of the coating layer prepared in example 1 are reduced, the method has the advantages that the chitosan is modified by adopting 1, 5-di (2, 3-glycidoxy) -2, 3, 4-hexafluoropentane, so that the anti-corrosion and anti-fouling performance of the coating can be improved.
Comparing the test results of example 6 with those of example 2, example 6 uses a commercially available common acrylic resin in the process of preparing the coating, which gives a coating with significantly poorer overall properties. Comparison of the test results of example 2 with example 5 demonstrates that the introduction of thiourea groups into the coating results in a close adhesion of the corresponding coating to the substrate and an increase in the adhesion of the coating to the substrate. Comparing the test results of example 2 with the test results of example 4, the method is that 1, 3-diallyl-2-thiourea is adopted as a raw material for introducing thiourea groups, the raw material is emulsified and crosslinked with acrylic monomers and organosilicon monomers, and the prepared modified acrylic resin is used for preparing the anticorrosive paint, so that a coating formed by the anticorrosive paint has anticorrosive and antirust properties and strong weather resistance and aging resistance.
The above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted without departing from the spirit and scope of the technical solution of the present invention.
Claims (10)
1. The degradable marine anticorrosive paint is characterized by comprising the following raw materials in parts by weight: 40-60 parts of epoxy resin, 10-20 parts of acrylic resin, 15-20 parts of modified chitosan, 5-10 parts of curing agent, 10-15 parts of solvent and 20-30 parts of filler, wherein the modified chitosan is obtained by crosslinking 1, 5-bis (2, 3-glycidoxy) -2, 3, 4-hexafluoropentane with chitosan.
2. The degradable marine anti-corrosion coating of claim 1, wherein the modified chitosan is prepared by the steps of: and dissolving the chitosan in acetic acid solution, uniformly mixing the chitosan with the 1, 5-di (2, 3-epoxypropoxy) -2, 3, 4-hexafluoropentane and an organotin catalyst, and carrying out reflux reaction for 3.5-4.5 hours at the temperature of 35-45 ℃ to prepare the modified chitosan.
3. The degradable marine anti-corrosive coating of claim 2, wherein the molar ratio of said chitosan to said 1, 5-bis (2, 3-glycidoxy) -2, 3, 4-hexafluoropentane in the raw materials used to prepare said modified chitosan is 2:1.
4. The degradable marine anti-corrosion coating of claim 2, wherein the organotin catalyst is stannous octoate, and the stannous octoate is used in an amount of 0.2-0.8% of the mass of chitosan.
5. A degradable marine anti-corrosive coating as claimed in claim 3, wherein the chitosan has a degree of deacetylation of not less than 85%.
6. The degradable marine anti-corrosive coating of claim 1, wherein:
the acrylic resin is modified acrylic resin, and the raw materials for preparing the modified acrylic resin comprise the following components in parts by weight: 60-80 parts of acrylic monomer, 5-12 parts of 1, 3-diallyl-2-thiourea, 30-50 parts of organosilicon monomer, 10-20 parts of emulsifier, 5-10 parts of initiator and 60-80 parts of water.
7. The degradable marine anti-corrosive coating of claim 6, wherein said modified acrylic resin is prepared by: and uniformly mixing the organosilicon monomer with the acrylic ester monomer, the 1, 3-diallyl-2-thiourea, the initiator, the water and the emulsifier, and reacting the mixture at 70-90 ℃ for 3-5 hours to prepare the modified acrylic resin.
8. The degradable marine anti-corrosion coating according to claim 6, wherein the acrylic monomer is composed of butyl acrylate, glycidyl acrylate and hydroxyethyl methacrylate according to a molar ratio of 1:1:1.
9. The degradable marine anti-corrosive paint of claim 1, further comprising the following raw materials in parts by weight: 3 to 8 parts of pigment, 1 to 2 parts of dispersing agent, 0.5 to 2 parts of defoaming agent, 0.5 to 1 part of leveling agent and 1 to 2 parts of anti-settling agent.
10. A method for preparing a degradable marine anti-corrosive paint according to any one of claims 1 to 9, comprising the steps of: and uniformly mixing the solvent, the epoxy resin and the acrylic resin to obtain a coating intermediate, and uniformly mixing the coating intermediate with the rest raw materials to obtain the degradable marine anti-corrosion coating.
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