CN108034334B - Water-based organic silicon-fluorine modified graphene oxide/epoxy resin coating and preparation method thereof - Google Patents
Water-based organic silicon-fluorine modified graphene oxide/epoxy resin coating and preparation method thereof Download PDFInfo
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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
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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Abstract
The invention belongs to the technical field of coatings, and discloses a water-based organic silicon fluoride modified graphene oxide/epoxy resin coating and a preparation method thereof. The coating consists of a component A and a component B, wherein the component A comprises the following components in parts by weight: 30-70 parts of epoxy resin, 20-80 parts of hydrophilic polyether modified epoxy resin and 30-70 parts of water; the component B comprises the following components in parts by weight: 10-40 parts of a water-based epoxy curing agent, 0.1-10 parts of organic silicon fluorine modified graphene oxide, 1-10 parts of montmorillonite, 1-5 parts of zinc phosphate, 20-70 parts of water, 0.3-2 parts of a dispersing agent, 0.3-2 parts of an antifoaming agent, 0.3-2 parts of a wetting agent and 0.3-2 parts of a flatting agent; the weight ratio of the component A to the component B is 100: 40-60. The coating formed by the coating has good hardness, water resistance, acid and alkali resistance, ageing resistance, solvent resistance, salt spray resistance and the like, and has good corrosion resistance.
Description
Technical Field
The invention belongs to the technical field of coatings, and particularly relates to a water-based organic silicon fluoride modified graphene oxide/epoxy resin coating and a preparation method thereof.
Technical Field
The epoxy resin has excellent adhesion performance to the surfaces of metal and non-metal materials, and the cured coating has excellent hardness, chemical corrosion resistance, wear resistance, flexibility and other performances, so that the epoxy resin has wide application in the fields of corrosion prevention, transportation and the like.
Graphene is a 2D honeycomb planar carbon film material, has good properties of strength, flexibility, compactness, electrical conductivity, thermal conductivity and the like, and is widely applied to the fields of new materials, aerospace, new energy storage and the like.
The epoxy resin/graphene anticorrosive paint is a novel metal anticorrosive paint, and combines the performance characteristics of epoxy resin and graphene. Compared with the common traditional anticorrosive coatings such as antirust agents, antirust paints, synthetic resin anticorrosive coatings and the like, the epoxy resin/graphene anticorrosive coating not only has less solid component mixing amount, but also has excellent hardness, water resistance, acid and alkali resistance, salt resistance, solvent resistance, salt spray resistance and the like, and has better anticorrosive performance. However, since the graphene material is a sheet-layer thin-film material, the interlayer acting force is strong, so that graphene sheets are adsorbed together, which is not favorable for the graphene sheets to be uniformly dispersed in the epoxy resin.
In addition, the anticorrosive coatings currently used in the market are still mainly solvent-based coatings, and have great harm to the environment and human health. With the recent increase of environmental protection requirements, these coatings with high VOC emission will be eliminated by the market, and environmental-friendly water-based coatings will be the development trend of the future coating market. However, the performance of the water-based anticorrosive paint on the market is still far from that of the oil-soluble paint, and the development of an anticorrosive paint with excellent performance still has great difficulty. How to break through the technical difficulty of the water-based paint still needs to be studied deeply.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a water-based organic silicon fluoride modified graphene oxide/epoxy resin coating with good corrosion resistance and low or zero VOC (volatile organic compounds) emission and a preparation method thereof.
The purpose of the invention is realized by the following technical scheme:
the water-based organic silicon fluorine modified graphene oxide/epoxy resin coating consists of a component A and a component B, wherein:
the component A comprises the following components in parts by weight:
30-70 parts of epoxy resin
20-80 parts of modified epoxy resin containing hydrophilic polyether
20-70 parts of water;
the component B comprises the following components in parts by weight:
the weight ratio of the component A to the component B is 100: 40-60; when used, the A component is mixed with the B component.
The modified epoxy resin containing hydrophilic polyether is more than one of the following formulas I:
wherein m and n are integers, m is preferably 5-100, and n is preferably 0-50; r1The structure of (1) is as follows:
R2is-C6H4-, -CH-and-CH2CH2-at least one of;
R3is-CH2CH2CH2CH3or-CH3
R4Is H or CH3。
The modified epoxy resin containing hydrophilic polyether is more than one of formula I-1;
the epoxy resin is bisphenol A epoxy resin, F-type novolac epoxy resin or a mixture of the two.
The modified epoxy resin containing the hydrophilic polyether is prepared by the following method:
(S1) under the protection of inert gas, taking a solvent M as a reaction medium, and reacting organic dicarboxylic anhydride with modified polyether with hydroxyl at the tail end under the action of a catalyst A to obtain hydrophilic polyether with carboxyl at the tail end; the solvent M is an organic solvent, and the catalyst A is a catalyst capable of catalyzing a reaction;
(S2) taking a solvent N as a reaction medium, and reacting hydrophilic polyether with carboxyl at the tail end with epoxy resin under the action of a catalyst B to obtain modified epoxy resin containing hydrophilic polyether; the solvent N is an organic solvent, and the catalyst B is a catalyst capable of catalyzing reaction.
The reaction condition in the step (S1) is that the reaction is carried out for 6-9 h at 80-130 ℃; the reaction condition in the step (S2) is that the reaction is carried out for 8-12 h at 80-120 ℃.
In the step (S1), the mass ratio of the organic dicarboxylic anhydride, the modified polyether with the hydroxyl at the tail end, the solvent M and the catalyst A is (2-10): (30-75): (40-100): (1-4);
in the step (S2), the mass ratio of the organic dibasic acid anhydride, the epoxy resin, the solvent N and the catalyst B in the hydrophilic polyether with the carboxyl at the tail end is (2-10): (20-100): (40-150): (1-4).
After the reaction in steps (S1) and (S2) was completed, distillation under reduced pressure was carried out.
The organic dicarboxylic acid anhydride in the step (S1) is one or more, preferably any one of maleic anhydride, phthalic anhydride and succinic anhydride; the modified polyether with the hydroxyl at the tail end is at least one of polyoxyethylene monobutyl ether, polyoxyethylene monomethyl ether or polyoxyethylene polyoxypropylene monobutyl ether;
the relative molecular mass of the polyoxyethylene monobutyl ether (polyethylene glycol monobutyl ether) is 400-600; the relative molecular mass of the polyoxyethylene monomethyl ether is 2000-5000; the relative molecular mass of the polyoxyethylene polyoxypropylene monobutyl ether is 2000-5000;
the solvent N in the solvents M and (S2) in the step (S1) is at least one of toluene, dioxane, butanone, ethyl acetate, ethylene glycol dimethyl ether and N, N' -dimethylformamide; the solvent M is the same as or different from the solvent N; the same may mean that the solvent M and the solvent N are the same solvent, or that the solvents are the same type;
in the step (S1), the catalyst a is any one of p-toluenesulfonic acid, organotin, and triethylamine; the organic tin is preferably one or more of dibutyltin dilaurate, stannous octoate, dibutyltin bis (dodecyl sulfur), dibutyltin diacetate or dialkyltin dimaleate;
in the step (S2), the catalyst B is any one of triethylamine, quaternary ammonium salt and triphenylphosphine; the quaternary ammonium salt is more than one of benzyltriethylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium hydrogen sulfate, trioctylmethylammonium chloride, dodecyltrimethylammonium chloride and tetradecyltrimethylammonium chloride;
in the step (S2), the epoxy resin is one or more of an F-type novolac epoxy resin or a bisphenol a-type epoxy resin.
The organic silicon fluorine modified graphene oxide is obtained by organic silicon modified graphene oxide, and the organic silicon at least comprises fluorine-containing groups; the structure is formula II:
wherein R is the same or different and at least R is a fluorine-containing group; r is preferably-OH, - (CH)2)3NH2A fluorine-containing group; (the fluorine-containing group is preferably a group consisting of C, H, F or a group consisting of C, H, F, -CmHnFpOqWherein m, n, p and q are integersAnd m is 0 to 10, n is 0 to 12, p is 0 to 17, q is 0 to 1, m, n, p, q satisfy the bonding principle of each element or atom).
The preparation method of the organic silicon fluorine modified graphene oxide comprises the following steps:
hydrolyzing organosilane to obtain a hydrolysate; and reacting the hydrolysate with graphene oxide to obtain the organic silicon fluorine modified graphene oxide. The hydrolysis refers to the hydrolysis of organosilane in ethanol and water; the hydrolysis needs to be added with a catalyst; the hydrolysis condition is that the reaction is carried out for 2-5 h at 40-70 ℃; the reaction condition of the reaction of the hydrolysate and the graphene oxide is that the reaction lasts for 1-3 h at 40-70 ℃. And after the reaction is finished, cleaning and drying are required. The catalyst is one of ammonia water and acetic acid.
The mass ratio of the organosilane to the graphene oxide is (5-20): 5.
the organosilane is a mixture of organosilane containing a fluorine group or a mixture of organosilane containing a fluorine group and at least one of methyl orthosilicate, ethyl orthosilicate and gamma-aminopropyltriethoxysilane.
The organosilane containing the fluorine group is preferably one or more of trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, hexafluorobutylpropyltrimethoxysilane, dodecafluoroheptylpropyltrimethoxysilane, tridecafluorooctyltrimethoxysilane, tridecafluorooctyltriethoxysilane, heptadecafluorodecyltrimethoxysilane and heptadecafluorodecyltriethoxysilane.
The waterborne epoxy curing agent is a polyamide curing agent, a fatty amine curing agent and a phenolic amine curing agent, and is preferably one or more of isophorone diamine, a curing agent 540W60, a curing agent D230, a curing agent HSJ-1040, a curing agent 630W60, a curing agent GH-06 and a curing agent T31.
The defoaming agent is a mineral oil defoaming agent or a polysiloxane defoaming agent, preferably a modified silicon polydimethylsiloxane defoaming agent or PA-311.
The dispersing agent is polyacrylate, acrylate, sodium polycarboxylate or sodium carboxylate; HT-5040 or sodium polycarboxylate is preferred.
The wetting agent is Dow
CF-10, Touretn @ X-405, Kenin PE-100, or Bike BYK187 wetting agent.
The leveling agent is cellulose and/or siloxane dispersant, preferably cellulose acetate butyrate, polydimethylsiloxane and polyether polyester modified organic siloxane.
The preparation method of the water-based organic silicon fluorine modified graphene oxide/epoxy resin coating comprises the following steps:
(1) preparation of component A: uniformly mixing epoxy resin, modified epoxy resin containing hydrophilic polyether and water to obtain a component A; the uniform mixing refers to full dispersion at the speed of 3000-6000 r/min;
(2) preparation of the component B: uniformly mixing the water-based epoxy curing agent, water, a dispersing agent, a defoaming agent, a wetting agent and a flatting agent, adding the organic silicon fluorine modified graphene oxide, montmorillonite and zinc phosphate, and uniformly stirring to obtain a component B; uniformly mixing in the preparation of the component B refers to stirring for 5-20 min, and uniformly stirring refers to stirring for 0.5-1 h;
(3) and mixing the component A with the component B to obtain the water-based organic silicon fluorine modified graphene oxide/epoxy resin coating.
According to the water-based organic silicon fluorine modified graphene oxide/epoxy resin coating and the preparation method thereof, the graphene oxide is modified by the organic silicon component, and the obtained organic silicon fluorine modified graphene oxide not only can be used for simultaneously introducing organic silicon and graphene oxide into water-based epoxy resin, but also can be used for greatly promoting the dispersion of the graphene oxide in the epoxy resin, so that the hardness, water resistance, acid and alkali resistance, ageing resistance, solvent resistance, salt fog resistance and the like of the coating are greatly improved, and the coating has good corrosion resistance. The hydrophilic polyether modified epoxy resin is equivalent to an epoxy emulsifier, and can emulsify the epoxy resin, so that the epoxy resin has water solubility.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) according to the organic silicon fluorine modified graphene oxide, organic silicon and graphene oxide can be simultaneously introduced into aqueous epoxy resin, the dispersion of the graphene oxide in the epoxy resin is greatly promoted, the hardness, the water resistance, the acid and alkali resistance, the aging resistance, the solvent resistance, the salt mist resistance and the like of a coating are greatly improved, and the organic silicon fluorine modified graphene oxide has good corrosion resistance;
(2) the invention selects the hydrophilic polyether modified epoxy resin which is equivalent to an epoxy emulsifier and can emulsify the epoxy resin, so that the epoxy resin has water solubility.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1
(1) Preparing modified epoxy resin containing hydrophilic polyether:
to a container were added 5 parts of maleic anhydride, 54 parts of polyethylene glycol monomethyl ether ((CH)3O(CH2CH2O)nH) Relative molecular weight of 5000) and 60 parts of toluene, heating to 80 ℃, adding 1 part of p-toluenesulfonic acid, stirring and reacting for 7 hours, adding 25 parts of F-44 type novolac epoxy resin and 2 parts of benzyltriethylammonium chloride, heating to 100 ℃, stirring and reacting for 12 hours, and removing the solvent by reduced pressure distillation to obtain the modified epoxy resin containing hydrophilic polyether; the parts are parts by mass;
(2) preparing organic silicon fluorine modified graphene oxide:
adding 70 parts of ethanol, 15 parts of deionized water, 2 parts of gamma-aminopropyltriethoxysilane, 3 parts of ethyl orthosilicate and 5 parts of trifluoropropyltrimethoxysilane into a container, heating to 50 ℃, adding 5 parts of ammonia water, stirring for reaction for 2 hours, then adding 5 parts of graphene oxide, continuing to react for 1 hour, cooling to room temperature, filtering, washing a filter cake for 3 times by using deionized water, and drying in a vacuum oven to obtain organic silicon fluoride modified graphene oxide; the parts are parts by mass;
(3) preparing an organic silicon fluorine modified graphene oxide/epoxy resin coating:
(3-1) preparation of A component: adding 30 parts of epoxy resin E51, 20 parts of hydrophilic polyether modified epoxy resin and 50 parts of deionized water into a container, and fully and uniformly dispersing at the speed of 3000r/min to obtain a component A; the parts are parts by weight;
(3-2) preparation of component B: adding 10 parts of aqueous epoxy curing agent D230, 50 parts of deionized water, 1 part of dispersant sodium polycarboxylate, 1 part of defoamer PA-311, 1 part of wetting agent BYK187 and 1 part of flatting agent polydimethylsiloxane into a container, stirring for 5min, then sequentially adding 0.1 part of organic silicon fluorine modified graphene oxide prepared in the step (2), 10 parts of montmorillonite and 5 parts of zinc phosphate while stirring, and fully stirring for 30min to obtain a component B; the parts are parts by weight;
(3-3) mixing the component A and the component B according to the weight ratio of 100: 60 to obtain the aqueous organic silicon fluorine modified graphene oxide/epoxy resin coating, wherein the performance test results are shown in table 1.
Example 2
(1) Preparing modified epoxy resin containing hydrophilic polyether:
adding 10 parts of succinic anhydride, 30 parts of polyethylene glycol butyl ether (relative molecular mass is 600) and 40 parts of toluene into a container, heating to 80 ℃, adding 1 part of triethylamine, stirring for reaction for 7 hours, adding 25 parts of E-51 type epoxy resin and 2 parts of triphenylphosphine, heating to 100 ℃, stirring for reaction for 12 hours, and removing the solvent through reduced pressure distillation to obtain the modified epoxy resin containing the hydrophilic polyether; the parts are parts by mass;
(2) preparing organic silicon fluorine modified graphene oxide:
adding 70 parts of ethanol, 15 parts of deionized water, 2 parts of gamma-aminopropyltriethoxysilane, 3 parts of ethyl orthosilicate and 5 parts of hexafluorobutylpropyltrimethoxysilane into a container, heating to 50 ℃, adding 5 parts of ammonia water, stirring for reaction for 2 hours, then adding 5 parts of graphene oxide, continuing to react for 1 hour, cooling to room temperature, filtering, washing a filter cake for 3 times by using deionized water, and drying in a vacuum oven to obtain the organic silicon fluorine modified graphene oxide; the parts are parts by mass;
(3) preparing an organic silicon fluorine modified graphene oxide/epoxy resin coating:
(3-1) preparation of A component: adding 40 parts of epoxy resin E44, 20 parts of hydrophilic polyether modified epoxy resin and 40 parts of deionized water into a container, and fully and uniformly dispersing at the speed of 6000r/min to obtain a component A; the parts are parts by weight;
(3-2) preparation of component B: adding 20 parts of aqueous epoxy curing agent D230, 50 parts of deionized water, 0.5 part of dispersant sodium polycarboxylate, 0.5 part of defoamer PA-311, 0.5 part of wetting agent BYK187 and 0.5 part of flatting agent polydimethylsiloxane into a container, stirring for 5min, then sequentially adding 1 part of organic silicon fluorine modified graphene oxide, 5 parts of montmorillonite and 3 parts of zinc phosphate while stirring, and fully stirring for 30min to prepare a component B; the parts are parts by weight;
(3-3) mixing the component A and the component B according to the weight ratio of 100: 40 to obtain the aqueous organic silicon fluorine modified graphene oxide/epoxy resin coating, wherein the performance test results are shown in table 1.
Example 3
(1) Preparing modified epoxy resin containing hydrophilic polyether:
adding 10 parts of phthalic anhydride, 40 parts of polyethylene glycol monomethyl ether (relative molecular mass of 2000) and 50 parts of toluene into a container, heating to 80 ℃, adding 1 part of dibutyltin dilaurate, stirring for reaction for 7 hours, adding 25 parts of F-51 type novolac epoxy resin and 2 parts of triethylamine, heating to 100 ℃, stirring for reaction for 12 hours, and removing the solvent by reduced pressure distillation to obtain the modified epoxy resin containing hydrophilic polyether; the parts are parts by mass;
(2) preparing organic silicon fluorine modified graphene oxide:
adding 70 parts of ethanol, 15 parts of deionized water, 2 parts of gamma-aminopropyltriethoxysilane, 3 parts of ethyl orthosilicate and 5 parts of hexafluorobutylpropyltrimethoxysilane into a container, heating to 60 ℃, adding 5 parts of acetic acid, stirring for reaction for 2 hours, then adding 5 parts of graphene oxide, continuing to react for 1 hour, cooling to room temperature, filtering, washing a filter cake for 3 times by using deionized water, and drying in a vacuum oven to obtain organic silicon fluoride modified graphene oxide; the parts are parts by mass;
(3) preparing an organic silicon fluorine modified graphene oxide/epoxy resin coating:
(3-1) preparation of A component: adding 40 parts of epoxy resin E51, 20 parts of hydrophilic polyether modified epoxy resin and 40 parts of deionized water into a container, and fully and uniformly dispersing at the speed of 6000r/min to obtain a component A; the parts are parts by weight;
(3-2) preparation of component B:
adding 20 parts of aqueous epoxy curing agent D230, 50 parts of deionized water, 0.5 part of dispersant sodium polycarboxylate, 0.5 part of defoaming agent PA-311, 0.5 part of wetting agent BYK187 and 0.5 part of flatting agent polydimethylsiloxane into a container, stirring for 5min, then sequentially adding 5 parts of organic silicon fluorine modified graphene oxide, 5 parts of montmorillonite and 3 parts of zinc phosphate while stirring, and fully stirring for 30min to obtain a component B; the parts are parts by weight;
(3-3) mixing the component A and the component B according to the weight ratio of 100: 50, and the performance test results of the aqueous organic silicon fluoride modified graphene oxide/epoxy resin coating are shown in Table 1.
Example 4
(1) Preparing modified epoxy resin containing hydrophilic polyether:
adding 5 parts of phthalic anhydride, 55 parts of polyethylene glycol monomethyl ether (relative molecular mass of 5000) and 60 parts of toluene into a container, heating to 80 ℃, adding 1 part of p-toluenesulfonic acid, stirring for reaction for 7 hours, adding 25 parts of E-44 type epoxy resin and 2 parts of tetrabutylammonium bromide, heating to 100 ℃, stirring for reaction for 12 hours, and removing the solvent by reduced pressure distillation to obtain the modified epoxy resin containing hydrophilic polyether; the parts are parts by mass;
(2) preparing organic silicon fluorine modified graphene oxide:
adding 70 parts of ethanol, 15 parts of deionized water, 2 parts of gamma-aminopropyltriethoxysilane, 3 parts of ethyl orthosilicate and 5 parts of dodecafluoroheptyl propyl trimethoxysilane into a container, heating to 50 ℃, adding 5 parts of acetic acid, stirring for reaction for 2 hours, then adding 5 parts of graphene oxide, continuing to react for 1 hour, cooling to room temperature, filtering, washing a filter cake for 3 times by using deionized water, and drying in a vacuum oven to obtain the organic silicon fluorine modified graphene oxide; the parts are parts by mass;
(3) preparing an organic silicon fluorine modified graphene oxide/epoxy resin coating:
(3-1) preparation of A component: adding 40 parts of epoxy resin E51, 20 parts of hydrophilic polyether modified epoxy resin and 40 parts of deionized water into a container, and fully and uniformly dispersing at the speed of 5000r/min to obtain a component A; the parts are parts by weight;
(3-2) preparation of component B: adding 40 parts of aqueous epoxy curing agent D230, 40 parts of deionized water, 0.5 part of dispersant sodium polycarboxylate, 0.5 part of defoamer PA-311, 0.5 part of wetting agent BYK187 and 0.5 part of flatting agent polydimethylsiloxane into a container, stirring for 5min, then sequentially adding 10 parts of organic silicon fluorine modified graphene oxide, 5 parts of montmorillonite and 3 parts of zinc phosphate while stirring, and fully stirring for 30min to obtain a component B; the parts are parts by weight;
(3-3) mixing the component A and the component B according to the weight ratio of 100: 40, and the performance test results of the aqueous organic silicon fluoride modified graphene oxide/epoxy resin coating are shown in table 1.
Example 5
(1) Preparing modified epoxy resin containing hydrophilic polyether:
adding 5 parts of maleic anhydride, 54 parts of polyethylene glycol monomethyl ether (the relative molecular mass is 2000) and 60 parts of toluene into a container, heating to 80 ℃, adding 1 part of p-toluenesulfonic acid, stirring for reaction for 7 hours, adding 25 parts of novolac epoxy resin F-48 and 2 parts of tetrabutylammonium bromide, heating to 100 ℃, stirring for reaction for 12 hours, and removing the solvent by reduced pressure distillation to obtain the modified epoxy resin containing hydrophilic polyether; the fractions are parts by mass;
(2) preparing organic silicon fluorine modified graphene oxide:
adding 70 parts of ethanol, 15 parts of deionized water, 2 parts of gamma-aminopropyltriethoxysilane, 3 parts of ethyl orthosilicate and 5 parts of dodecafluoroheptyl propyl trimethoxysilane into a container, heating to 50 ℃, adding 5 parts of acetic acid, stirring for reaction for 2 hours, then adding 5 parts of graphene oxide, continuing to react for 1 hour, cooling to room temperature, filtering, washing a filter cake for 3 times by using deionized water, and drying in a vacuum oven to obtain the organic silicon fluorine modified graphene oxide; the parts are parts by mass;
(3) preparing an organic silicon fluorine modified graphene oxide/epoxy resin coating:
(3-1) preparation of A component: adding 50 parts of epoxy resin E51, 30 parts of modified epoxy resin containing hydrophilic polyether and 20 parts of deionized water into a container, and fully and uniformly dispersing at the speed of 4000r/min to obtain a component A; the parts are parts by weight;
(3-2) preparation of component B: adding 40 parts of aqueous epoxy curing agent D230, 40 parts of deionized water, 0.5 part of dispersant sodium polycarboxylate, 0.5 part of defoaming agent PA-311, 1 part of wetting agent BYK187 and 0.5 part of flatting agent polydimethylsiloxane into a container, stirring for 5min, then sequentially adding 10 parts of organic silicon fluorine modified graphene oxide, 10 parts of montmorillonite and 3 parts of zinc phosphate while stirring, and fully stirring for 30min to prepare a component B; the parts are parts by weight;
(3-3) mixing the component A and the component B according to the weight ratio of 100: 40 to obtain the aqueous organic silicon fluorine modified graphene oxide/epoxy resin coating, wherein the performance test results are shown in table 1.
Example 6
(1) Preparing modified epoxy resin containing hydrophilic polyether:
adding 5 parts of maleic anhydride, 54 parts of polyethylene glycol monomethyl ether (the relative molecular mass is 2000) and 60 parts of toluene into a container, heating to 80 ℃, adding 1 part of p-toluenesulfonic acid, stirring and reacting for 7 hours, adding 15 parts of epoxy resin E51, 10 parts of novolac epoxy resin F-51 and 2 parts of tetrabutylammonium bromide, heating to 100 ℃, stirring and reacting for 12 hours, and removing the solvent by reduced pressure distillation to obtain the modified epoxy resin containing hydrophilic polyether; the parts are parts by mass;
(2) preparing organic silicon fluorine modified graphene oxide:
adding 70 parts of ethanol, 15 parts of deionized water, 2 parts of gamma-aminopropyltriethoxysilane, 3 parts of ethyl orthosilicate and 5 parts of dodecafluoroheptyl propyl trimethoxysilane into a container, heating to 50 ℃, adding 5 parts of acetic acid, stirring for reaction for 2 hours, then adding 5 parts of graphene oxide, continuing to react for 1 hour, cooling to room temperature, filtering, washing a filter cake for 3 times by using deionized water, and drying in a vacuum oven to obtain organic silicon fluorine modified graphene oxide; the parts are parts by mass;
(3) preparing an organic silicon fluorine modified graphene oxide/epoxy resin coating:
(3-1) preparation of A component: adding 50 parts of epoxy resin E51, 30 parts of hydrophilic polyether modified epoxy resin and 20 parts of deionized water into a container, and fully and uniformly dispersing at the speed of 4000r/min to obtain a component A; the parts are parts by weight;
(3-2) preparation of component B:
adding 30 parts of aqueous epoxy curing agent D230, 40 parts of deionized water, 1 part of dispersant sodium polycarboxylate, 1 part of defoamer PA-311, 1 part of wetting agent BYK187 and 1 part of flatting agent polydimethylsiloxane into a container, stirring for 5min, then sequentially adding 10 parts of organic silicon fluorine modified graphene oxide, 10 parts of montmorillonite and 5 parts of zinc phosphate while stirring, and fully stirring for 30min to obtain a component B; the parts are parts by weight;
(3-3) mixing the component A and the component B according to the weight ratio of 100: 50 to prepare the aqueous organic silicon fluorine modified graphene oxide/epoxy resin coating, wherein the performance test results are shown in table 1.
Performance testing
The component A and the component B in the embodiments 1-6 are mixed according to the corresponding weight ratio, deionized water is used for diluting until the spraying viscosity is 40-50S (T-4 cup), standard tinplate is phosphorized or polished, the thickness of the tinplate is controlled to be 20-30 mu m, after 48 hours of complete drying, a comprehensive performance test is carried out, the thickness of a type test dry plate is controlled to be 60-90 mu m, and after 7 days of complete drying, the type test is carried out. The toughness is in accordance with GB/T1731, the adhesion is in accordance with GB/T1720, the neutral salt fog resistance is in accordance with GB/T1771, the impact resistance is in accordance with GB/T1732, and the chemical resistance is in accordance with GB/T9274. The results are shown in table 1 below.
TABLE 1 Performance test results of organosilicon-fluorine modified graphene oxide/epoxy resin coatings
Claims (10)
1. A water-based organic silicon fluorine modified graphene oxide/epoxy resin coating is characterized in that: consists of a component A and a component B, wherein:
the component A comprises the following components in parts by weight:
30-70 parts of epoxy resin
20-80 parts of modified epoxy resin containing hydrophilic polyether
20-70 parts of water;
the component B comprises the following components in parts by weight:
the weight ratio of the component A to the component B is 100: 40-60;
the modified epoxy resin containing hydrophilic polyether is more than one of the following formulas I:
wherein m and n are integers;
R1the structure of (1) is as follows:
or
R1In the structure (1), n is an integer;
R2is-C6H4-, -CH-and-CH2CH2-one of the above;
R3is-CH2CH2CH2CH3or-CH3；
R4Is H or CH3；
The organic silicon fluorine modified graphene oxide is obtained by organic silicon modified graphene oxide, and the organic silicon at least comprises fluorine-containing groups.
2. The aqueous organosilicon fluorine modified graphene oxide/epoxy resin coating according to claim 1, wherein: the modified epoxy resin containing the hydrophilic polyether is prepared by the following method:
(S1) under the protection of inert gas, taking a solvent M as a reaction medium, and reacting organic dicarboxylic anhydride with modified polyether with hydroxyl at the tail end under the action of a catalyst A to obtain hydrophilic polyether with carboxyl at the tail end; the solvent M is an organic solvent, and the catalyst A is a catalyst capable of catalyzing a reaction;
(S2) taking a solvent N as a reaction medium, and reacting hydrophilic polyether with carboxyl at the tail end with epoxy resin under the action of a catalyst B to obtain modified epoxy resin containing hydrophilic polyether; the solvent N is an organic solvent, and the catalyst B is a catalyst capable of catalyzing a reaction;
the organic dicarboxylic acid anhydride in the step (S1) is one or more of maleic anhydride, phthalic anhydride, and succinic anhydride; the modified polyether with the hydroxyl at the tail end is at least one of polyoxyethylene monobutyl ether, polyoxyethylene monomethyl ether or polyoxyethylene polyoxypropylene monobutyl ether.
3. The aqueous organosilicon fluorine modified graphene oxide/epoxy resin coating according to claim 2, wherein:
the reaction condition in the step (S1) is that the reaction is carried out for 6-9 h at the temperature of 90-130 ℃; the reaction condition in the step (S2) is that the reaction is carried out for 8-12 h at 80-120 ℃;
in the step (S1), the mass ratio of the organic dicarboxylic anhydride, the modified polyether with the hydroxyl at the tail end, the solvent M and the catalyst A is (2-10): (30-75): (40-100): (1-4);
in the step (S2), the mass ratio of the organic dibasic acid anhydride, the epoxy resin, the solvent N and the catalyst B in the hydrophilic polyether with the carboxyl at the tail end is (2-10): (20-100): (40-150): (1-4);
the relative molecular mass of the polyoxyethylene monobutyl ether is 400-600; the relative molecular mass of the polyoxyethylene monomethyl ether is 2000-5000; the relative molecular mass of the polyoxyethylene polyoxypropylene monobutyl ether is 2000-5000;
the solvent N in the solvents M and (S2) in the step (S1) is at least one of toluene, dioxane, butanone, ethyl acetate, ethylene glycol dimethyl ether and N, N' -dimethylformamide; the solvent M is the same as or different from the solvent N;
in the step (S1), the catalyst a is any one of p-toluenesulfonic acid, organotin, and triethylamine;
in the step (S2), the catalyst B is any one of triethylamine, quaternary ammonium salt and triphenylphosphine;
in the step (S2), the epoxy resin is one or more of an F-type novolac epoxy resin or a bisphenol a-type epoxy resin.
4. The aqueous organosilicon fluorine modified graphene oxide/epoxy resin coating according to claim 1, wherein: the organic silicon fluorine modified graphene oxide has a structure shown in a formula II:
wherein R is the same or different and at least R is a fluorine-containing group.
5. The aqueous organosilicon fluorine modified graphene oxide/epoxy resin coating according to claim 4, wherein: r is-OH, - (CH)2)3NH2And a fluorine-containing group.
6. The aqueous organosilicon fluorine modified graphene oxide/epoxy resin coating according to claim 1, wherein: the preparation method of the organic silicon fluorine modified graphene oxide comprises the following steps:
hydrolyzing organosilane to obtain a hydrolysate; and reacting the hydrolysate with graphene oxide to obtain the organic silicon fluorine modified graphene oxide.
7. The aqueous organosilicon fluorine modified graphene oxide/epoxy resin coating according to claim 6, wherein: the mass ratio of the organosilane to the graphene oxide is (5-20): 5; the hydrolysis condition is that the reaction is carried out for 2-5 h at 40-70 ℃; the reaction condition of the reaction of the hydrolysate and the graphene oxide is that the reaction is carried out for 1-3 h at the temperature of 40-70 ℃;
the hydrolysis refers to the hydrolysis of organosilane in ethanol and water; the hydrolysis requires the addition of a catalyst.
8. The aqueous organosilicon fluorine modified graphene oxide/epoxy resin coating according to claim 6, wherein:
the organosilane is a mixture of organosilane containing a fluorine group or a mixture of organosilane containing a fluorine group and at least one of methyl orthosilicate, ethyl orthosilicate and gamma-aminopropyltriethoxysilane;
the organosilane containing the fluorine group is one or more of trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, hexafluorobutylpropyltrimethoxysilane, dodecafluoroheptylpropyltrimethoxysilane, tridecafluorooctyltrimethoxysilane, tridecafluorooctyltriethoxysilane, heptadecafluorodecyltrimethoxysilane and heptadecafluorodecyltriethoxysilane.
9. The aqueous organosilicon fluorine modified graphene oxide/epoxy resin coating according to claim 1, wherein: the epoxy resin is bisphenol A type epoxy resin, F type novolac epoxy resin or a mixture of the bisphenol A type epoxy resin and the F type novolac epoxy resin;
the waterborne epoxy curing agent is one or more of a polyamide curing agent, a fatty amine curing agent and a phenolic amine curing agent;
the defoaming agent is a mineral oil defoaming agent or a polysiloxane defoaming agent;
the dispersing agent is polyacrylate, acrylate, sodium polycarboxylate or sodium carboxylate;
the leveling agent is a cellulose and/or siloxane dispersant.
10. The preparation method of the aqueous organosilicon fluorine modified graphene oxide/epoxy resin coating according to any one of claims 1 to 9, characterized in that: the method comprises the following steps:
(1) preparation of component A: uniformly mixing epoxy resin, modified epoxy resin containing hydrophilic polyether and water to obtain a component A;
(2) preparation of the component B: uniformly mixing the water-based epoxy curing agent, water, a dispersing agent, a defoaming agent, a wetting agent and a flatting agent, adding the organic silicon fluorine modified graphene oxide, montmorillonite and zinc phosphate, and uniformly stirring to obtain a component B;
(3) and mixing the component A with the component B to obtain the water-based organic silicon fluorine modified graphene oxide/epoxy resin coating.
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