CN115558419A - Photocuring composite epoxy fluorosilicone resin coating and preparation method thereof and coating preparation method - Google Patents
Photocuring composite epoxy fluorosilicone resin coating and preparation method thereof and coating preparation method 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
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
- C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
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- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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Abstract
The invention provides a photocuring composite epoxy fluorine-silicon resin coating and a preparation method and a coating preparation method thereof.30-69 parts of epoxy phenyl fluorine-silicon resin, 20-45 parts of diisocyanate oligomer graft-g-triepoxy compound, 10-20 parts of active epoxy diluent and 1-5 parts of adhesion promoter, as well as modified nano silica sol with the mass x of 0wt% and x of 50w% and cationic photoinitiator with the mass y of 1wt% and y of 6wt% are stirred and dispersed to obtain the composite photocuring epoxy fluorine-silicon resin coating; uniformly coating the photocuring composite epoxy fluorosilicone resin coating on the surface of a base material, leveling at room temperature, pre-drying to remove a solvent, and then placing in an ultraviolet curing machine for UV photocuring to obtain the coating. The invention can increase the static contact angle, hardness, aging resistance and salt spray resistance of the water on the surface of the resin-containing coating on the premise of keeping the advantages of the organic silicon resin, thereby solving the problem of shortage of the cationic photo-curing fluorine-silicon resin coating.
Description
Technical Field
The invention belongs to the field of functional resin coatings and coatings, and relates to a preparation method and application of a photocuring composite coating and a coating prepared based on photocuring epoxy/fluorocarbon group/phenyl co-modified silicone resin (epoxy fluorobenzene silicone resin for short) and the like.
Background
The photocureable coating has the advantages of high curing speed, high production efficiency, cleanness and low pollution, and is widely applied to the fields of rapid forming, 3D printing and the like. At present, regarding the photo-curing resin coating produced and sold in China, the main component is mainly the coating prepared based on double bond-containing alkene compounds and oligomers thereof, such as 3-6 functional acrylate-based PU prepolymer, acrylic acid modified epoxy resin and the like (see patents CN105778103A, CN111607321A, CN 104177991A and the like), and the coating and coating agent developed based on photo-curing cationic epoxy resin (CN 106751877, CN 107602864A) are not only rarely researched, but also have few industrial products.
The fluorosilicone resin has excellent water and oil repellency, good weather resistance and ageing resistance, but low adhesive force; the phenyl functional group is introduced into the fluorine-silicon resin structure, so that the intersolubility of the fluorine-silicon resin and the organic coating can be improved, the refractive index of the fluorine-silicon coating is improved, and the fluorine-silicon resin coating is endowed with good light transmittance, high temperature resistance and other performances; and the introduction of the reactive epoxy group can endow the resin coating with the special reactivity of the epoxy group on the basis of keeping the original performance characteristics of the fluorosilicone resin, and the coating is expected to realize crosslinking curing under the action of a cationic photoinitiator. At present, although domestic research on fluorosilicone resins (mainly comprising Si-OH, si-OR and the like as active functional groups) and super-hydrophobic coatings constructed on the basis of the fluorosilicone resins is very intense and has been reported in many ways (see patents CN101775144B, CN103408762B, CN104558458B and the like), for example, CN101775144B "fluorosilicone resins, a preparation method thereof and antifouling paint", a fluorine-containing polymer containing molecular side chains containing isobornyl/acetoacetoxyethyl, fluoroalkyl/ester groups and siloxy groups is subjected to hydrolytic condensation with silicate/alkoxy silane and the like to obtain silicon dioxide hybridized fluorosilicone resin, and the antifouling paint constructed by using the silicon dioxide hybridized fluorosilicone resin has the pencil hardness of 4H-5H, the adhesion of 4B-5B, the salt spray resistance of 168H and the adhesion of 4B after 18 days of constant temperature and humidity; CN104558458B, a fluorosilicone resin, a process for preparation and use thereof, comprises the steps of first free radical copolymerizing vinyl alkoxy silane in a solution to obtain a prepolymer A, free radical copolymerizing 2- (perfluorobutyl) ethyl methacrylate in a solution to obtain a prepolymer B, then blending the prepolymer A, the prepolymer B and a small amount of coupling agent together and stirring at room temperature to obtain the siloxane modified fluorosilicone resin which is used for antifouling treatment of stone surfaces, has good antifouling effects of tea water resistance, coffee resistance and the like, and the WCA can reach 139 degrees. In summary, few studies and reports on photocuring functional coatings and coatings prepared from reactive functional silicone resins co-modified by epoxy/fluorocarbon groups/phenyl groups are reported in the literature.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a fluorine-containing functional resin material for water resistance and moisture resistance of electronic products, and aims to introduce a method for preparing a photocureable coating and a coating based on photocuring epoxy/fluorocarbon group/phenyl co-modified silicone resin (epoxy phenyl fluorosilicone resin for short) and diisocyanate oligomer graft (-g-) triepoxy compound on the premise of keeping the advantages of organic silicon resin, so as to increase the static contact angle, hardness, aging resistance and salt spray resistance of water on the surface of the resin-containing coating, thereby solving the problem of shortage of cationic photocuring fluorosilicone resin coating.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a photocuring composite epoxy fluorosilicone resin coating comprises, by mass, 30-69 parts of epoxy phenyl fluorosilicone resin, 20-45 parts of diisocyanate oligomer graft-g-triepoxy compound, 10-20 parts of active epoxy diluent and 1-5 parts of adhesion promoter, as well as modified nano silica sol with the mass x being more than 0wt% and the mass x being less than or equal to 50w% and cationic photoinitiator with the mass y being more than or equal to 1wt% and the mass y being less than or equal to 6 wt%.
The epoxy phenyl fluorosilicone resin is a copolymer of epoxy siloxane, fluorocarbon siloxane and phenyl siloxane containing D and T structures in the structure or a copolymer of epoxy siloxane, fluorocarbon siloxane and phenyl siloxane oligomer.
The phenyl siloxane oligomer is D, T type phenyl siloxane oligomer or (di) phenyl siloxane-co- (di) C 1-18 An oligomer formed by the copolymerization of an alkylsiloxane.
The epoxy phenyl fluorosilicone resin is a copolymer of D and T-type epoxy siloxane-co-fluorocarbon siloxane-co-phenyl siloxane or a copolymer of epoxy siloxane-co-fluorocarbon siloxane-co- [ (di) phenyl siloxane-co- (di) alkyl siloxane ] oligomer, the solid content is 50-80%, and the epoxy group content is 0.03-0.2 in terms of mole number of epoxy groups contained in 100 parts of resin.
The epoxy group is one of 2, 3-glycidoxypropyl, 3, 4-cyclohexylethyl or epoxy polyether group, and the epoxy polyether group is (2, 3-glycidoxy) polyoxyethylene polyoxypropylene ether group CH 2 (O)CHCH 2 O(C 2 H 4 O) x (C 3 H 6 O) y C 3 H 6 -, where x =0-6, y =3-6, x + y =3-6.
Said fluorocarbon group is C 1-8 Perfluoroalkylethyl [ -C 2 H 4 (CF 2 ) m F]Pentafluorophenyl (-C) 6 F 5 ) Or one of a perfluoropolyether group, wherein m =1-8; the alkyl is-CH 3 ～-C 18 H 37 。
The epoxy group phenyl fluorosilicone resin is 2, 3-epoxypropoxy propyl (methyl) siloxane-co-C 1-8 Perfluoroalkylethylsiloxane-co- (di) phenylsiloxane, 2, 3-glycidoxypropyl (methyl) siloxane-co-pentafluorophenylsiloxane-co- (di) phenylsiloxane, 2, 3-glycidoxypropyl (methyl) siloxane-co-C 1-8 Perfluoroalkylethylsiloxane-co-phenylsiloxane-co-diphenylsiloxane, 2, 3-glycidoxypropyl (methyl) siloxane-co-C 1-8 Perfluoroalkylethylsiloxane-co- (di) phenylsiloxane, 2, 3-glycidoxypropyl (methyl) siloxane-co-pentafluorophenylsiloxane-co-diphenylsiloxane, 2, 3-glycidoxypropyl (methyl) siloxane-co-pentafluorophenylsiloxane-co-phenylsiloxane-co- (di) alkylsiloxane, 3, 4-epoxycyclohexylethylsiloxane-co-C 1-8 Perfluoroalkylethylsiloxane-co- (di) phenylsiloxane, 3, 4-epoxycyclohexylethylsiloxane-co-pentafluorophenylsiloxane-co- (di) phenylsiloxane, 3, 4-epoxycyclohexylethylsiloxane-co-C 1-8 Perfluoroalkylethylsiloxane-co-phenylsiloxane-co-diphenylsiloxane, 3, 4-epoxycyclohexylethylsiloxane-co-pentafluorophenyl-co-phenylsiloxane-co-diphenylsiloxane, 2, 3-glycidoxypropylpolyoxyethylenePolyoxypropylene Ether-based siloxane-co-C 1-8 Perfluoroalkylethyl siloxane-co-phenylsiloxane-C 1-18 Alkyl (methyl) siloxanes, 2, 3-glycidoxypropylpolyoxyethylenepolyoxypropylene Ether siloxanes-co-pentafluorophenyl-co-phenylsiloxanes-C 1-18 Alkyl (meth) siloxanes, 2, 3-glycidoxypropylpolyoxyethylenepolyoxypropylene ether-based (meth) siloxanes-co-C 1-8 Perfluoroalkylethyl siloxane-co- (di) phenylsiloxane, 2, 3-glycidoxypropylpolyoxyethylene polyoxypropylene ether (meth) siloxane-co-pentafluorophenyl siloxane-co- (di) phenylsiloxane, 2, 3-glycidoxypropylpolyoxyethylene polyoxypropylene ether (meth) siloxane-co-C 1-8 Perfluoroalkyl ethyl siloxane-co-phenyl siloxane-co-diphenyl siloxane, 2, 3-glycidoxypropyl polyoxyethylene polyoxypropylene Ether group (methyl) siloxane-co-C 1-8 One of perfluoroalkylethyl siloxane-co-phenyl siloxane- (di) alkyl siloxane, 2, 3-glycidoxy polyoxyethylene polyoxypropylene ether group (methyl) siloxane-co-pentafluorophenyl siloxane-co- (di) phenyl siloxane- (di) alkyl siloxane.
The epoxy phenyl fluorosilicone resin is prepared by hydrolysis and polycondensation reaction of epoxy silane and fluorocarbon silane, phenyl silane or phenyl siloxane oligomer and the like, and the preparation method comprises the following specific steps: weighing 7.5-20 parts of epoxy silane, 10-50 parts of fluorocarbon silane and 30-82.5 parts of phenyl silane or phenyl siloxane oligomer according to the mass ratio, and uniformly stirring to obtain a mixture A; then adding 100wt% -300wt% of organic solvent, 1wt% -2wt% of catalyst and theoretical amount of deionized water according to the mass of the A, and performing hydrolytic polycondensation reaction at 40-80 ℃ for 4-10h; after the reaction is finished, the catalyst is removed by water washing, the solvent is recovered, and low boiling point is removed by pressure reduction, so that transparent-semitransparent viscous liquid is obtained, namely the epoxy group/fluorocarbon group/phenyl group co-modified silicone resin, namely epoxy group phenyl fluorosilicone resin for short.
In the above synthesis step, the fluorocarbon silane is a compound having a C bonded to a molecule 1-8 Silane with perfluor alkyl ethyl group, perfluor aryl group or perfluor polyether group and 2-3 alkoxy groups, selected from heptadecafluorooctyl ethyl trimethoxy silane, heptadecafluorooctyl ethyl triethoxySilane, tridecafluorohexylethyltrimethoxysilane, tridecafluorohexylethyltriethoxysilane, nonafluorobutylethyltrimethoxysilane, nonafluorobutylethyltriethoxysilane, trifluoropropyltrimethoxysilane, trifluoropropylmethyldimethoxysilane, trifluoropropyltriethoxysilane, pentafluorophenyltrimethoxysilane, pentafluorophenyltriethoxysilane, perfluoropolyether-based trimethoxysilane having an average molecular weight of 1000 to 3000, and perfluoropolyether-based triethoxysilane having an average molecular weight of 1000 to 3000.
The epoxy silane is a silane containing one epoxy group and 2-3 alkoxy groups in a molecule, and one of (2, 3-glycidoxypropyl) trimethoxysilane, (2, 3-glycidoxypropyl) triethoxysilane, (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, (3, 4-epoxycyclohexyl) ethyltriethoxysilane, (2, 3-epoxypropoxypropyl) methyldimethoxysilane, (2, 3-epoxypropoxypropyl) methyldiethoxysilane, (2, 3-epoxypropoxypropyl) polyetheryltrimethoxysilane, (2, 3-epoxypropoxypropyl) polyetheryltriethoxysilane and (2, 3-epoxypropoxypropyl) polyetheryltriethoxysilane is selected; the polyether group is polyoxyethylene polyoxypropylene ether group- (C) 2 H 4 O) x (C 3 H 6 O) y C 3 H 6 -, where x =0-6, y =3-6, x + y =3-6.
The phenyl silane is silane which contains 1-2 phenyl groups and 2-3 alkoxy groups in the structure, one of phenyl trimethoxy silane, phenyl triethoxy silane, diphenyl dimethoxy silane and diphenyl diethoxy silane or a mixture of difunctional diphenyl dialkoxy silane and trifunctional phenyl trialkoxy silane in any proportion is selected, and the alkoxy groups are methoxy groups or ethoxy groups.
The phenyl siloxane oligomer is a siloxane oligomer which contains Si-hydroxyl and siloxy in the molecule and contains D and T phenyl siloxane chain links and has a linear, cyclic, dendritic or semi-closed cage structure, and is prepared from semi-closed cage phenyl heptapolysiloxane trisilanol, cyclic 1,3,5, 7-tetramethyl-1, 3,5, 7-tetraphenyl cyclotetrasiloxane and cyclic octaphenylcyclotetrasiloxaneSiloxane, hydroxy terminated polydiphenylsiloxane [ HO (ph) 2 SiO) n H]Or diphenylsiloxane-co-phenylsiloxane [ HO (ph) 2 SiO) n (phSiO 3/2 ) n1 H]Or diphenylsiloxane-co-dialkylsiloxane HO (ph) 2 SiO) n (R 2 SiO) m1 H. Or diphenylsiloxane-co-alkylsiloxane [ HO (ph) 2 SiO) n (RSiO 3/2 ) m2 H]Or phenylsiloxane-co-alkylsiloxane [ HO (phSiO) 3/2 ) n1 (RSiO 3/2 ) m2 H]Or phenylsiloxane-co-dialkylsiloxane [ HO (phSiO) 3/2 ) n1 (R 2 SiO) m1 H]Wherein the alkyl is-CH 3 ～-C 18 H 37 ，n、n 1 ＝1-20，m 1 、m 2 ＝0-19，n+m 1 、n+m 2 、n 1 +m 1 、n 1 +m 2 ＝2-20。
The organic solvent is one or a mixture of more of toluene, trifluorotoluene, xylene, acetone, butanone, cyclohexanone, methyl isobutyl ketone, ethyl acetate, butyl acetate, trifluoroethanol, penta-fluoropentanol, ethylene glycol methyl ether, propylene glycol methyl ether and propylene glycol methyl ether acetate in any proportion, and the dosage of the solvent is 100-300 wt% of the mass of the monomer mixture A.
The catalyst is one of concentrated hydrochloric acid, citric acid and acetic acid.
The diisocyanate oligomer-g-triepoxy compound has a structure shown as a formula (1) or (2), is a compound which contains three epoxy carbamate groups in the structure and is bonded with a polyurea ring body in the middle,
wherein A =0 or- (C) 2 H 4 O) a (C 3 H 6 O) b -，a,b＝0-6，a+b＝0-6。
The diisocyanate oligomer-g-triepoxy compound is prepared by the reaction of diisocyanate trimer and hydroxy epoxy compound; the diisocyanate trimer is hexamethylene diisocyanate trimer or isophorone diisocyanate trimer.
The hydroxyl epoxy compound is glycidyl ether or hydroxyl-terminated polyoxyethylene polyoxypropylene ether epoxy ether (HOACH) 2 CH(O)CH 2 ]Wherein A =0 or- (C) 2 H 4 O) a (C 3 H 6 O) b -, a, b =0-6, a + b =0-6; the reaction of diisocyanate trimer and hydroxyl epoxy compound at 60-80 deg.c for 1-3 hr, and the molar ratio of diisocyanate trimer to hydroxyl epoxy compound in the reaction is controlled to 1 (3-3.1).
The reactive epoxy diluent is selected from butyl glycidyl ether and C 12-14 Aliphatic alkyl glycidyl ether, phenyl glycidyl ether, benzyl glycidyl ether, o-tolyl glycidyl ether, diglycidyl ether [ di (2, 3-epoxypropyl) ether ]]1, 6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, and polypropylene glycol diglycidyl ether.
The adhesion promoter is one of (2, 3-glycidoxypropyl) trimethoxysilane, (2, 3-glycidoxypropyl) methyldimethoxysilane, (2, 3-glycidoxypropyl) triethoxysilane, (2, 3-glycidoxypropyl) methyldiethoxysilane, (2, 3-glycidoxypropyl) polyoxyethylene polyoxypropylene ether trimethoxysilane, (2, 3-glycidoxypropyl) polyoxyethylene polyoxypropylene ether methyldimethoxysilane and (2, 3-glycidoxypropyl) polyoxyethylene polyoxypropylene ether triethoxysilane; the average molecular weight of the polyoxyethylene polyoxypropylene ether is 100-500.
The modified nano silica sol RSiO 2 The nano-silica sol is phenyl or fluorocarbon modified nano-silica sol, the solid content is 20-35%, the dispersion medium is alcohol ether or ether ester, the average particle size is 20-30nm, and the pH is =6-7.
The cationic photoinitiator is selected from one of cationic diphenyl- (4-phenyl sulfur) phenyl sulfonium hexafluoroantimonate, (4-phenyl sulfur) phenyl diphenyl sulfonium hexafluorophosphate, bis (4-tert-butyl benzene) iodonium hexafluorophosphate, 4-isobutyl phenyl-4' -methyl phenyl iodonium hexafluorophosphate, triaryl sulfonium hexafluorophosphate salt and eta 6-isopropylbenzene cyclopentadienyl iron (II) hexafluorophosphate.
The preparation method of the photocuring composite epoxy fluorosilicone resin coating comprises the following steps: weighing epoxy group fluorobenzene silicone resin, diisocyanate oligomer-g-triepoxy compound, reactive epoxy diluent and adhesion promoter in sequence according to the mass ratio, uniformly stirring, adding modified nano silicon sol and cationic photoinitiator, and stirring and dispersing for 20-30min to obtain a uniform mixture, namely the composite type photocuring epoxy fluorosilicone coating.
The preparation method of the photocuring composite epoxy fluorosilicone resin coating comprises the following steps: uniformly coating the photo-curing composite epoxy fluorosilicone resin coating on the surface of a base material, leveling at room temperature for 20-30min, pre-drying at 100-120 ℃ for 3-10min to remove a solvent, and then placing in an ultraviolet curing machine for UV photo-curing.
The base material is one of roughened clean tinplate, aluminum alloy, steel plate, copper-clad plate, glass, ceramic or PC circuit board and the like.
The coating mode comprises one of spraying, brushing, rolling, bar coating, spin coating, dipping, pulling and film forming and the like.
The beneficial effects of the invention are: in order to improve the current situation of shortage of cationic photo-curing fluorine silicone resin coating, epoxy silane and fluoro-silicone silane, phenyl silane or phenyl siloxane oligomer are subjected to hydrolysis copolycondensation, firstly, a copolymer of epoxy siloxane-co-fluoro-silicone-co-phenyl siloxane or epoxy siloxane-co-fluoro-silicone-co- (phenyl siloxane-co-alkoxy siloxane) oligomer containing D and T chain links in a synthetic structure, namely epoxy phenyl fluoro-silicone resin EFPSi, and the mutual solubility of the resin and the non-fluoro-silicone component can be effectively improved by utilizing the characteristic that phenyl and an organic mutual solvent in the EFPSi structure are soluble; secondly, the epoxy phenyl fluorosilicone resin is used as a water-repellent and oil-repellent component, and then the epoxy phenyl fluorosilicone resin, a self-made diisocyanate oligomer with strong adhesiveness, a g-triepoxy compound (TE), a phenyl modified nano silica sol, a cationic photocuring initiator and the like are organically combined to prepare the photocuring coating, so that the quick curing of the coating and the coating can be effectively realized under the action of ultraviolet light, and the photocuring coating has good adhesive force and can also show excellent waterproof, oil-proof, dustproof and aging-resistant effects by the way that water-repellent and oil-repellent fluorosilicone chain segments tend to the surface and are directionally arranged towards an air interface and the adhesiveness TE is enriched towards a base material and a fluorosilicone intermediate layer.
The application shows that the adhesive force of the coating prepared by the composite epoxy phenyl fluorosilicone resin coating can reach 1 level, and the contact angle theta of the surface of the coating H2O 99.2-120.4 degrees, the aging resistance is more than or equal to 1000 hours, and the coating integrally shows good comprehensive application effect.
Detailed Description
The present invention is further illustrated by the following examples, which include, but are not limited to, the following examples.
Aiming at the current situation of research and production of cationic light-cured epoxy group fluorosilicone resin coatings which are rare in China, the invention discloses a method for preparing a light-cured coating and a coating based on grafting (-g-) triepoxy compound and the like on light-cured epoxy group/fluorocarbon group/phenyl group co-modified silicone resin (epoxy group phenyl fluorosilicone resin for short) and diisocyanate oligomer.
The structure and performance of the photocuring fluorine-silicon resin and isocyanate oligomer-g-triepoxy compound are innovation points of the invention, and reports about the reaction of epoxy silane and phenyl silane for synthesizing epoxy group organic silicon resin are reported in China, but the synthesis of fluorine-containing epoxy group fluorine-silicon resin is not reported.
Therefore, the invention adopts the following technical scheme:
a photocuring composite epoxy fluorosilicone resin coating comprises, by mass, 30-69 parts of epoxy phenyl fluorosilicone resin (EFPSi), 20-45 parts of diisocyanate oligomer graft-g-triepoxy compound (TE), 10-20 parts of active Epoxy Diluent (ED), 1-5 parts of Adhesion Promoter (AP), 0-50w% of modified nano silica sol calculated by the total mass of the EFPSi + TE + ED + AP, and 1-6wt% of cationic photoinitiator.
The epoxy phenyl fluorosilicone resin (EFPSi) is a copolymer of epoxy siloxane, fluorine-containing siloxane and phenyl siloxane containing D and T structures in the structure or a copolymer of epoxy siloxane, fluorine-containing siloxane and phenyl siloxane oligomer.
The phenyl siloxane oligomer is D, T type phenyl siloxane oligomer or (di) phenyl siloxane-co- (di) C 1-18 An oligomer formed by the copolymerization of an alkylsiloxane.
The diisocyanate oligomer-g-triepoxy compound (TE) has the structures shown in formulas (1) and (2), and is a compound which contains three epoxy carbamate groups in the structure and is bonded with a polyurea ring body in the middle, wherein A =0 or- (C) 2 H 4 O) a (C 3 H 6 O) b -，a,b＝0-6，a+b＝0-6。
The epoxy phenyl fluorosilicone resin (EFPSi) is D, T type epoxy siloxane-co-fluorocarbon siloxane-co-phenyl siloxane copolymer, or epoxy siloxane-co-fluorocarbon siloxane-co- [ (di) phenyl siloxane-co- (di) alkyl siloxane]An oligomer copolymer having a solid content of about 50 to 80% and an epoxy group content of about 0.03 to 0.2 in terms of the number of moles of epoxy groups contained in 100 parts of the resin; preferably, the epoxy group is one of 2, 3-glycidoxypropyl, 3, 4-cyclohexylethyl or epoxy polyether group, and the epoxy polyether group is (2, 3-glycidoxy) polyoxyethylene polyoxypropylene ether group CH 2 (O)CHCH 2 O(C 2 H 4 O) x (C 3 H 6 O) y C 3 H 6 -, where x =0-6, y =3-6, x + y =3-6; said fluorocarbon group is C 1-8 Perfluoroalkylethyl [ -C 2 H 4 (CF 2 ) m F]Penta-fluorinePhenyl (-C) 6 F 5 ) Or one of a perfluoropolyether group, wherein m =1-8; the alkyl is-CH 3 ～-C 18 H 37 。
The epoxy phenyl fluorosilicone resin (EFPSi) is 2, 3-glycidoxypropyl (methyl) siloxane-co-C 1-8 Perfluoroalkylethylsiloxane-co- (di) phenylsiloxane, 2, 3-glycidoxypropyl (methyl) siloxane-co-pentafluorophenylsiloxane-co- (di) phenylsiloxane, 2, 3-glycidoxypropyl (methyl) siloxane-co-C 1-8 Perfluoroalkylethylsiloxane-co-phenylsiloxane-co-diphenylsiloxane, 2, 3-glycidoxypropyl (methyl) siloxane-co-C 1-8 Perfluoroalkylethylsiloxane-co- (di) phenylsiloxane, 2, 3-glycidoxypropyl (methyl) siloxane-co-pentafluorophenylsiloxane-co-diphenylsiloxane, 2, 3-glycidoxypropyl (methyl) siloxane-co-pentafluorophenylsiloxane-co-phenylsiloxane-co- (di) alkylsiloxane, 3, 4-epoxycyclohexylethylsiloxane-co-C 1-8 Perfluoroalkylethylsiloxane-co- (di) phenylsiloxane, 3, 4-epoxycyclohexylethylsiloxane-co-pentafluorophenylsiloxane-co- (di) phenylsiloxane, 3, 4-epoxycyclohexylethylsiloxane-co-C 1-8 Perfluoroalkylethylsiloxane-co-phenylsiloxane-co-diphenylsiloxane, 3, 4-epoxycyclohexylethylsiloxane-co-pentafluorophenyl-co-phenylsiloxane-co-diphenylsiloxane, 2, 3-glycidoxypropylpolyoxypropylenepolyoxane-co-C 1-8 Perfluoroalkylethyl siloxane-co-phenylsiloxane-C 1-18 Alkyl (methyl) siloxanes, 2, 3-glycidoxypropylpolyoxyethylenepolyoxypropylene Ether siloxanes-co-pentafluorophenyl-co-phenylsiloxanes-C 1-18 Alkyl (meth) siloxanes, 2, 3-glycidoxypropylpolyoxyethylenepolyoxypropylene ether (meth) siloxanes-co-C 1-8 Perfluoroalkylethylsiloxane-co- (di) phenylsiloxane, 2, 3-glycidoxypropylpolyoxyethylenepolyoxypropylene ether (meth) siloxane-co-pentafluorophenylsiloxane-co- (di) phenylsiloxane, 2, 3-glycidoxypropylpolyoxyethylenepolyoxypropylene ether (Methylpropyl)Radical) siloxane-co-C 1-8 Perfluoroalkyl ethyl siloxane-co-phenyl siloxane-co-diphenyl siloxane, 2, 3-glycidoxypropyl polyoxyethylene polyoxypropylene Ether group (methyl) siloxane-co-C 1-8 One of perfluoroalkylethyl siloxane-co-phenyl siloxane- (di) alkyl siloxane, 2, 3-glycidoxy polyoxyethylene polyoxypropylene ether group (methyl) siloxane-co-pentafluorophenyl siloxane-co- (di) phenyl siloxane- (di) alkyl siloxane and the like, wherein the polyoxyethylene ether polyoxypropylene ether group- (C) is a compound of formula (I) 2 H 4 O) x (C 3 H 6 O) y C 3 H 6 -and alkyl are as before.
The epoxy phenyl fluorosilicone resin can be prepared by hydrolysis and polycondensation reaction of epoxy silane and fluorocarbon silane, phenyl silane or phenyl siloxane oligomer and the like. The preparation method comprises the following specific steps:
weighing 7.5-20 parts of Epoxy Silane (ESi), 10-50 parts of Fluorocarbon Silane (FSi), 30-82.5 parts of Phenyl Silane (PSi) or phenyl siloxane Oligomer (OSi) according to the mass ratio, and uniformly stirring to obtain a mixture A; then adding 100wt% -300wt% of organic solvent, 1-2wt% of catalyst and theoretical amount of deionized water according to the mass of the A, and carrying out hydrolytic polycondensation reaction for 4-10h at 40-80 ℃. After the reaction is finished, the catalyst is removed by water washing, the solvent is recovered, and the low boiling point is removed by pressure reduction, so as to obtain transparent-semitransparent viscous liquid, namely epoxy/fluorocarbon group/phenyl group co-modified silicon resin, which is called as epoxy phenyl fluorosilicone resin for short, and the EFPSi is diluted by the solvent until the solid content is about 50-80% for standby.
In the above synthesis step, the fluorocarbon silane is a compound having a C bonded to a molecule 1-8 A silane of perfluoroalkylethyl group, perfluoroaryl group or perfluoropolyether group to which 2 to 3 alkoxy groups are bonded, selecting heptadecafluorooctylethyltrimethoxysilane (also known as 1H, 2H-perfluorodecyltrimethoxysilane), heptadecafluorooctylethyltriethoxysilane (also known as 1H, 2H-perfluorodecyltriethoxysilane), and optionally adding water tridecafluorohexylethyltrimethoxysilane (also known as 1H, 2H-perfluorooctyltrimethoxysilane), tridecafluorohexylethyltriethoxysilane (also known as 1H, 2H-perfluorooctyltriethoxysilane), nonadecafluorohexylethyltriethoxysilaneOne of fluorobutylethyltrimethoxysilane (also known as 1H, 2H-perfluorohexyltrimethoxysilane), nonafluorobutylethyltriethoxysilane (also known as 1H, 2H-perfluorohexyltriethoxysilane), trifluoropropyltrimethoxysilane, trifluoropropylmethyldimethoxysilane, trifluoropropyltriethoxysilane, pentafluorophenyltrimethoxysilane, pentafluorophenyltriethoxysilane, average molecular weight (Mn) =1000-3000 perfluoropolyether-based trimethoxysilane, mn =1000-3000 perfluoropolyether-based triethoxysilane, and the like.
The epoxy silane is a silane containing one epoxy group and 2-3 alkoxy groups in the molecule, and one of (2, 3-glycidoxypropyl) trimethoxysilane, (2, 3-glycidoxypropyl) triethoxysilane, (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, (3, 4-epoxycyclohexyl) ethyltriethoxysilane, (2, 3-glycidoxypropyl) methyldimethoxysilane, (2, 3-glycidoxypropyl) methyldiethoxysilane, (2, 3-glycidoxypropyl) polyetheryltrimethoxysilane, (2, 3-glycidoxypropyl) polyetheryltriethoxysilane, and (2, 3-glycidoxypropyl) polyetheryltriethoxysilane is selected; the polyether group is polyoxyethylene polyoxypropylene ether group- (C) 2 H 4 O) x (C 3 H 6 O) y C 3 H 6 In the formula, the values of x, y and x + y are the same as before.
The phenylsilicone is silane containing 1-2 phenyl groups and 2-3 alkoxy groups in the structure, one of phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane and diphenyldiethoxysilane or a mixture of difunctional diphenyldialkoxysilane and trifunctional phenyltrialkoxysilane in any proportion is selected, and the alkoxy groups are methoxy groups or ethoxy groups.
The phenyl siloxane oligomer is a siloxane oligomer which contains Si-hydroxyl and siloxy in the molecule and contains D and T phenyl siloxane chain links and has a linear, cyclic, dendritic or semi-closed cage structure, and is selected from semi-closed cage phenyl heptapolysiloxane trisilicol, cyclic 1,3,5, 7-tetramethyl-1, 3,5, 7-tetraphenyl cyclotetrasiloxane and cyclic octaphenylcyclotetrasiloxaneHydroxy-terminated polydiphenylsiloxane HO (ph) 2 SiO) n H]Or diphenylsiloxane-co-phenylsiloxane [ HO (ph) 2 SiO) n (phSiO 3/2 ) n1 H]Or diphenylsiloxane-co-dialkylsiloxane HO (ph) 2 SiO) n (R 2 SiO) m1 H. Or diphenylsiloxane-co-alkylsiloxane [ HO (ph) 2 SiO) n (RSiO 3/2 ) m2 H]Or phenylsiloxane-co-alkylsiloxane [ HO (phSiO) 3/2 ) n1 (RSiO 3/2 ) m2 H]Or phenylsiloxane-co-dialkylsiloxane [ HO (phSiO) 3/2 ) n1 (R 2 SiO) m1 H]One of the iso-copolymerization oligomers, the alkyl is-CH 3 ～-C 18 H 37 ，n，n 1 ＝1-20，m 1 ，m 2 ＝0-19，n+m 1 、n+m 2 、n 1 +m 1 、n 1 +m 2 ＝2-20。
The organic solvent is fluorine alcohol, alcohol ether, ketone, alcohol ether ester, fluoro aromatic hydrocarbon and the like which have good intersolubility with fluorocarbon silane, phenyl silane, epoxy silane and the like, can be used by mixing single components or a plurality of solvents in any proportion, and is one or a mixture of a plurality of components in any proportion, such as toluene (MB), benzotrifluoride (TFT), xylene, acetone, butanone, cyclohexanone, methyl isobutyl ketone (MIBK), ethyl Acetate (EA), butyl Acetate (BA), trifluoroethanol, penta-amyl alcohol, ethylene glycol methyl ether, propylene glycol methyl ether acetate (PMA) and the like, wherein the dosage of the solvent is generally 100-300 wt% of the mass of the monomer mixture A. Preferably (fluorine-containing) arene-alcohol, arene-ester, ether ester-ether, ether ester- (fluorine) alcohol and other mixtures in any proportion, such as (trifluoro) toluene-ethanol, trifluoro toluene-ethanol-butyl acetate or butyl acetate-ethanol, PMA-propylene glycol methyl ether and the like.
The catalyst is one of inorganic acid such as concentrated hydrochloric acid or organic acid such as citric acid and acetic acid.
The diisocyanate oligomer-g-triepoxy compound is prepared by the reaction of diisocyanate trimer (DICT) and hydroxy epoxy compound (HE); the DICT is hexamethylene diisocyanate trimer (N3390) or isophorone diisocyanate trimer (Z4470).
The hydroxyl epoxy compound (HE) is glycidyl ether or hydroxyl-terminated polyoxyethylene polyoxypropylene ether epoxy ether [ HOACH 2 CH(O)CH 2 ]Wherein A =0 or- (C) 2 H 4 O) a (C 3 H 6 O) b -, a, b =0-6, a + b =0-6; the DICT and HE react at the temperature of about 60-80 ℃ for 1-3h, and the reaction time is DICT: the molar ratio of HE is controlled to be 1.
The active Epoxy Diluent (ED) is a compound which contains 1-2 epoxy groups in a molecule, can participate in the specific chemical reaction of the epoxy groups and can play a role of diluting similar solvents, and butyl glycidyl ether and C are selected 12-14 Aliphatic alkyl glycidyl ether, phenyl glycidyl ether, benzyl glycidyl ether, o-tolyl glycidyl ether, diglycidyl ether [ di (2, 3-epoxypropyl) ether ]]1, 6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and the like.
The Adhesion Promoter (AP) is a substance which contains an epoxy group, can participate in the photocuring reaction of resin or paint and can increase the adhesive property between a base material and an organic coating, and is selected from one of (2, 3-glycidoxypropyl) trimethoxysilane, (2, 3-glycidoxypropyl) methyldimethoxysilane, (2, 3-glycidoxypropyl) triethoxysilane, (2, 3-glycidoxypropyl) methyldiethoxysilane, (2, 3-glycidoxypropyl) polyoxyethylene polyoxypropylene ether trimethoxysilane, (2, 3-glycidoxypropyl) polyoxyethylene polyoxypropylene ether methyldimethoxysilane, (2, 3-glycidoxypropyl) polyoxyethylene polyoxypropylene ether triethoxysilane and the like; the polyoxyethylene polyoxypropylene ether group has an average molecular weight of about 100-500.
The modified nano silica sol RSiO 2 The nano silica sol is phenyl or fluorocarbon modified nano silica sol, has the solid content of about 20-35% (the dispersion medium is alcohol ether or ether ester and the like), the average particle size of 20-30nm, the pH value of 6-7, and the limited silica gel reagent from Qingdao YidaA company, etc.
The cationic photoinitiator is a substance capable of initiating an epoxy group cation ring-opening reaction under ultraviolet irradiation, and is selected from one of cationic diphenyl- (4-phenylsulfide) phenyl sulfonium hexafluoroantimonate (cationic photoinitiator 6976), (4-phenylsulfide) phenyl diphenyl sulfonium hexafluorophosphate (cationic photoinitiator 6992), bis (4-tert-butyl benzene) iodonium hexafluorophosphate (cationic photoinitiator PI 9388), 4-isobutylphenyl-4' -methylphenyl iodonium hexafluorophosphate (cationic photoinitiator 250), triaryl sulfonium hexafluorophosphate (cationic photoinitiator 1176), eta.6-isopropylbenzene cyclopentadienyl iron (II) hexafluorophosphate (cationic photoinitiator 261) and the like.
The preparation method of the photocuring composite epoxy fluorosilicone resin coating comprises the following steps: weighing epoxy fluorobenzene silicone resin (EFPSi), diisocyanate oligomer-g-triepoxy compound, reactive epoxy diluent (ME) and Adhesion Promoter (AP) in sequence according to the mass ratio, stirring and mixing uniformly, adding modified nano silica sol and cationic photoinitiator, stirring and dispersing for 20-30min to obtain a uniform mixture, namely the composite photocuring epoxy fluorosilicone coating, which is marked as FPTE.
The preparation method of the photocuring composite epoxy fluorosilicone resin coating comprises the following steps: and (2) uniformly coating the FPTE coating on the surface of a substrate, leveling at room temperature for 20-30min, pre-drying at 100-120 ℃ for 3-10min to remove the solvent, and then placing in an ultraviolet curing machine for UV (ultraviolet) light curing to obtain a coating, namely an FPTE coating sample.
The base material is one of roughened clean tinplate, aluminum alloy, steel plate, copper-clad plate, glass, ceramic or PC circuit board and the like.
The coating mode comprises one of spraying, brushing, rolling, bar coating, spin coating, dip-draw film forming and the like.
The application performance of the photocuring composite epoxy fluorosilicone resin coating is evaluated according to the method shown in the table 1:
TABLE 1 application Performance and test method
The preparation method of the epoxy phenyl fluorosilicone resin comprises the following steps:
20.0g of 2, 3-glycidoxypropylmethyldimethoxysilane KH781, 30.0g of tridecafluorohexylethyltrimethoxysilane and 50.0g of a phenylsilane mixture consisting of 25.0g of phenyltrimethoxysilane and 25.0g of diphenyldimethoxysilane are sequentially added into a three-necked flask provided with a thermometer, a reflux condenser and a stirrer, and are uniformly stirred to obtain about 100.0g of a mixture A; then, 200wt% of a benzotrifluoride-ethanol (1,wt/wt) solvent, about 200.0g of a concentrated hydrochloric acid catalyst, and a theoretical amount of deionized water were added in an amount of 200 parts by mass of a to perform a hydrolytic polycondensation reaction at 60 ℃ for 6 hours. After the reaction is finished, heating to 85 ℃, distilling off the alcohol solvent, washing with deionized water with the same volume for 2 times to remove the catalyst, and then performing reaction on the mixture in P Watch (A) Reducing the pressure and removing low boiling point under the condition of about 0.9MPa to obtain transparent-semitransparent viscous liquid, namely, the epoxy phenyl fluorosilicone resin-2, 3-glycidoxypropyl methyl siloxane-co-tridecafluorohexyl ethyl siloxane-co-phenyl siloxane-co-diphenyl siloxane copolymer, which is marked as EFPSi-1, the epoxy group content is about 0.1164, and the epoxy phenyl fluorosilicone copolymer is diluted by benzotrifluoride-ethyl acetate (1, wt/wt) until the solid content is about 60% for later use.
The epoxy phenyl fluorosilicone resins in the other examples were synthesized by the above method, but the raw materials and the amounts thereof are listed in Table 2.
TABLE 2 summary of raw materials and products for synthesis of epoxy phenyl fluorosilicone resin
| EFPSi-1 | EFPSi-2 | EFPSi-3 | EFPSi-4 | |
| 2, 3-glycidoxypropylmethyldimethoxysilane/g | 20.0 | |||
| 3, 4-Cyclohexylethyltrimethoxysilane/g | 20.0 | |||
| 2, 3-glycidoxypropyltrimethoxysilane/g | 10 | 15 | ||
| Tridecafluorohexylethyltrimethoxysilane/g | 30.0 | |||
| Heptadecafluorooctylethyltrimethoxysilane/g | 35 | |||
| Pentafluorophenyltriethoxysilane/g | 20.0 | |||
| Trifluoropropyltrimethoxysilane/g | 50 | |||
| Phenyltrimethoxysilane/g | 25.0 | |||
| Diphenyldimethoxysilane/g | 25.0 | 50 | ||
| Hydroxy-terminated phenylsiloxane-co-diethylsiloxane oligomer/g | 40 | |||
| Diphenylsiloxane-co-hexadecylsiloxane oligomer/g | 60 | |||
| Product mass/g | 77.99 | 88.06 | 81.27 | 81.96 |
| Epoxy group content/mol/100 g resin | 0.1164 | 0.0922 | 0.0522 | 0.0774 |
| Target EFPSi solid content | 60％ | 70％ | 80％ | 50％ |
* EFPSi-1:2, 3-glycidoxypropylmethylsiloxane-co-tridecafluorohexylethylsiloxane-co-phenylsiloxane-co-diphenylsiloxane; EFPSi-2, 3,4-cyclohexylethylsiloxane-co-pentafluorophenylsiloxane-co-diphenylsiloxane-co-hexadecylsiloxane oligomer; EFPSi-3:2, 3-glycidoxypropylsiloxane-co-trifluoropropylsiloxane-co-phenylsiloxane-co-diethylsiloxane oligomer; EFPSi-4:2, 3-glycidoxypropylsiloxane-co-heptadecafluorooctylethylsiloxane-co-diphenylsiloxane.
The synthesis of the diisocyanate oligomer-g-triepoxy compound (TE) comprises the following steps:
0.1mol of diisocyanate trimer N3390 or Z4470 is added into a dry three-neck flask provided with a reflux condenser, a thermometer and a stirrer according to the metering ratio, stirred, then 0.3 to 0.31mol of hydroxy epoxy compound (HE) is added, and then the mixture is heated to 60 to 80 ℃ to react for 1 to 3 hours, thus obtaining the product, namely diisocyanate oligomer-g-triepoxy compound (TE). The starting materials and the amounts used for the synthesis of TE in the examples are shown in Table 3.
TABLE 3 raw material amounts of diisocyanate oligomer-g-triepoxy compound (TE)
Example 1
(1) Preparation of FPTE-1 for composite photocuring epoxy fluorosilicone resin coating
According to the mass ratio, 65.0g of epoxy phenyl fluorosilicone resin EFPSi-1-2, 3-glycidoxypropyl methyl siloxane-co-tridecafluorohexylethyl siloxane-co-phenyl siloxane-co-diphenyl siloxane with the epoxy content of about 0.1164 and the solid content of about 60 percent, 20.0g of hexamethylene diisocyanate trimer (N3390) -g-triglycidyl ether (TE-1) with the structure shown in formula (1) and A =0, 10.0g of benzyl glycidyl ether active epoxy diluent, 5.0g of 2, 3-glycidoxypropyl methyl dimethoxysilane adhesion promoter, 6wt% of the total mass of the components and about 6.0g of cationic photoinitiator 6976 are weighed in sequence and stirred and dispersed for 30min to obtain a uniform mixture, namely the light-cured epoxy fluorosilicone resin coating (FPTE-1).
(2) Preparation of composite photocuring FPTE-1 coating
Diluting an FPTE-1 coating by using a benzotrifluoride-ethyl acetate (1, wt/wt) mixed solvent to a solid content of about 30wt%, uniformly spraying the coating on the surface of clean tinplate or glass by using a spray gun with the caliber of about 0.8mm, controlling the spraying amount to control the thickness of the dried coating to be about 20 mu m, leveling at room temperature for 30min, drying at 100 ℃ for 3min, and curing for 2min by using an ultraviolet curing machine with the power of 1000W to obtain the FPTE-1 coating sample.
Example 2
(1) Preparation of FPTE-2 composite photo-curing epoxy fluorosilicone resin coating
According to the mass ratio, 69.0g of epoxy phenyl fluorosilicone resin EFPSi-2-3, 4-cyclohexyl ethyl siloxane-co-pentafluorophenyl siloxane-co-diphenyl siloxane-co-hexadecyl siloxane oligomer with the epoxy group content of about 0.0922 and the solid content of about 70 percent and 20.0g of epoxy phenyl fluorosilicone oligomer with the structure shown as the formula (2) and A = (C =) 3 H 6 O) 3 The coating comprises isophorone diisocyanate trimer-g-trimeric oxypropylene epoxy ether TE-2 with a =0 and b =3, 10.0g of neopentyl glycol diglycidyl ether reactive epoxy diluent, 1.0g of 2, 3-glycidoxypropyl trimethoxysilane (KH-560) adhesion promoter, 25wt% of phenyl modified nano silica sol with the solid content of about 25g and 1wt% of cationic photoinitiator 6976, and the uniform mixture is the composite type photocuring epoxy fluorosilicone resin coating (FPTE-2) after stirring and dispersing for 20 min.
(2) Preparation of composite photocuring FPTE-2 coating
Diluting an FPTE-2 coating by using a benzotrifluoride-ethyl acetate (1, wt/wt) mixed solvent until the solid content is about 40wt%, uniformly spraying the coating on the surface of clean tinplate by using a spray gun with the caliber of about 0.8mm, controlling the spraying amount to control the thickness of the dried coating to be about 25 mu m, leveling at room temperature for 20min, drying at 100 ℃ for 10min, and curing for 4min by using an ultraviolet curing machine with the power of 1000W to obtain the coating, namely an FPTE-2 sample.
Example 3
(1) Preparation of composite photocuring epoxy fluorosilicone coating FPTE-3
According to the mass ratio, 30.0g of epoxy phenyl fluorosilicone resin EFPSi-3-2, 3-glycidoxypropylsiloxane-co-trifluoropropylsiloxane-co- (phenylsiloxane-co-diethylsiloxane) oligomer with the epoxy group content of about 0.0522 and the solid content of about 80 percent are weighed in sequence, 45.0g of the oligomer with the structure shown in formula (1), a =3, b =3 and A = (C =) 2 H 4 O) 3 (C 3 H 6 O) 3 Hexamethylene diisocyanate trimer (N3390) -g-polyoxypropylene epoxy ether (TE-3), 20.0g of 1, 6-hexanediol diglycidyl ether reactive epoxy diluent, 5.0g of (2, 3-glycidoxypropyl) polyoxypropylene ether-based trimethoxysilane adhesion promoter having a polyether group average molecular weight of about 102, and 50% by weight, about 50g of solids content, about 35% by weight, and an average particle diameter based on the total mass of the above
About 30nm of phenyl modified nano silica sol and 5.0g of cationic photoinitiator PI9388 are stirred and dispersed for 25min to obtain a uniform mixture, namely the composite photocuring epoxy fluorosilicone resin coating (FPTE-3).
(2) Preparation of composite photocuring FPTE-3 coating
Diluting an FPTE-3 coating with a trifluorotoluene-ethyl acetate (1, wt/wt) solvent until the solid content is about 30wt%, uniformly spraying the coating on the surface of clean tinplate or glass by using a spray gun with the caliber of about 0.8mm, controlling the spraying amount to control the thickness of the dried coating to be about 22 mu m, leveling at room temperature for 30min, then drying at 100 ℃ for 5min, and curing for 2min by using an ultraviolet curing machine with the power of 1000W to obtain a coating sample, namely the FPTE-3 coating.
Example 4
(1) Preparation of composite photocuring epoxy fluorosilicone coating FPTE-4
According to the mass ratio, 40.0g of epoxy phenyl fluorosilicone resin EFPSi-4 with the epoxy content of about 0.0774 and the solid content of about 50 percent, 2, 3-glycidoxypropyl siloxane-co-heptadecafluorooctylethyl siloxane-co-diphenylsiloxane, 42.0g of isophorone diisocyanate trimer-g-triglycidyl ether TE-4 with the structure shown in formula (2) and A =0, 15.0g of neopentyl glycol diglycidyl ether active epoxy diluent, 3.0g of 2, 3-glycidoxypropyl triethoxysilane adhesion promoter, 20wt% of the total mass of the materials, about 20g of tridecafluorooctyl modified nano-silica sol with the solid content of about 20 percent and the average particle size of about 25nm, 3.5wt% of cationic photoinitiator 6976 are weighed in sequence, stirred and dispersed for 30min, and the obtained uniform mixture is the composite type photocuring epoxy phenyl fluorosilicone coating FPTE-4.
(2) Preparation of composite photocuring FPTE-4 coating
Diluting an FPTE-4 coating by using a benzotrifluoride-ethyl acetate (1,wt/wt) mixed solvent to a solid content of about 35wt%, uniformly spraying the coating on the surface of clean tinplate by using a spray gun with the caliber of about 0.8mm, controlling the spraying amount to control the thickness of the dried coating to be about 21.5 mu m, leveling at room temperature for 25min, drying at 100 ℃ for 5min, and curing for 2min by using an ultraviolet curing machine with the power of 1000W to obtain the FPTE-4 sample.
The composite type photocuring epoxy fluorosilicone resin coating samples FPTE-1-4 prepared in the embodiments 1-4 are taken, placed at room temperature for 24 hours, and then subjected to application performance test according to the method shown in the table 4:
TABLE 4 application Performance and test methods
In addition, the experiment was performed in the same manner as in example 4 using epoxy resin E51 in place of the epoxy phenyl fluorosilicone resin, and the resultant coating samples were used as references in the present invention, and all the results of the measurement are shown in Table 5.
TABLE 5 Properties of FPTE-1-4 of composite photocuring epoxy fluorosilicone resin coating
Reference-a coating made on the basis of epoxy resin; it means that the coating surface is unchanged.
As can be seen from Table 5, the composite photocuring epoxy fluorosilicone resin coating FPTE-1-4 of the invention has obviously increased static contact angle (theta) of water on the surface of the coating compared with the reference H2O 99.2-120.4 degree, increased hardness, aging resistance (more than or equal to 1000 h) and enhanced salt spray resistance (more than or equal to 1000-1200 h), antifouling grade generally reaches 0-1 level, and the adhesive force and flexibility are similar to those of a reference epoxy resin coating; the light-cured composite fluorosilicone resin coating and the coating prepared on the basis of the epoxy phenyl fluorosilicone resin, the diisocyanate trimer-g-triepoxy compound and the like can realize light curing of the coating, the coating prepared from the light-cured composite fluorosilicone resin coating has excellent water resistance, antifouling property, salt mist resistance and aging resistance, and the influence of a fluorosilicone component in the resin on the adhesive force and flexibility of a target coating is small. In addition, under the influence of the lack of intersolubility of the fluorocarbon-based modified nanoparticles and the fat component in the system, the light transmittance of the reference epoxy resin coating is lower, but the reference FPTE-4 coating does not have the phenomenon, which indicates that the intersolubility of the components in the FPTE-4 coating is good, and the overall performance of the coating is better.
Claims (9)
1. A photocuring composite epoxy fluorosilicone resin coating is characterized by comprising, by mass, 30-69 parts of epoxy phenyl fluorosilicone resin, 20-45 parts of diisocyanate oligomer graft-g-triepoxy compound, 10-20 parts of reactive epoxy diluent and 1-5 parts of adhesion promoter, as well as modified nano silica sol with the mass x being 0wt% and x being less than or equal to 50w% and cationic photoinitiator with the mass y being 1wt% and y being less than or equal to 6 wt%.
2. The photo-curable composite epoxy fluorosilicone resin coating as claimed in claim 1, wherein the epoxy phenyl fluorosilicone resin is a copolymer of epoxy siloxane, fluorocarbon siloxane and phenyl siloxane containing D and T structures in the structure, or a copolymer of epoxy siloxane, fluorocarbon siloxane and phenyl siloxane oligomer.
3. The photo-curable composite epoxy fluorosilicone resin coating of claim 1, wherein the diisocyanate oligomer-g-triepoxy compound has a structure as shown in formula (1) or (2), which is a compound having three epoxy urethane groups in the structure and polyurea ring bodies bonded in the middle,
wherein A =0 or- (C) 2 H 4 O) a (C 3 H 6 O) b -，a,b＝0-6，a+b＝0-6。
4. The photo-curing composite epoxy fluorosilicone resin coating as claimed in claim 1, wherein said reactive epoxy diluent is selected from butyl glycidyl ether and C 12-14 Aliphatic alkyl glycidyl ether, phenyl glycidyl ether, benzyl glycidyl ether, o-tolyl glycidyl ether, diglycidyl ether [ di (2, 3-epoxypropyl) ether ]]1, 6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, and polypropylene glycol diglycidyl ether.
5. The photo-curable composite epoxy fluorosilicone resin coating of claim 1, wherein the adhesion promoter is one selected from (2, 3-glycidoxypropyl) trimethoxysilane, (2, 3-glycidoxypropyl) methyldimethoxysilane, (2, 3-glycidoxypropyl) triethoxysilane, (2, 3-glycidoxypropyl) methyldiethoxysilane, (2, 3-glycidoxypropyl) polyoxypropylene ether trimethoxysilane, (2, 3-glycidoxypropyl) polyoxyethylene polyoxypropylene ether methyldimethoxysilane, and (2, 3-glycidoxypropyl) polyoxyethylene polyoxypropylene ether triethoxysilane; the average molecular weight of the polyoxyethylene polyoxypropylene ether is 100-500.
6. The photo-curing composite epoxy fluorosilicone resin coating as claimed in claim 1, wherein the modified nano silica sol is a phenyl or fluorocarbon group modified nano silica sol, the solid content is 20-35%, the dispersion medium is alcohol ether or ether ester, the average particle size is 20-30nm, and the pH is not less than 6-7.
7. The photo-curing composite epoxy fluorosilicone resin coating as claimed in claim 1, wherein the cationic photoinitiator is one selected from cationic diphenyl- (4-phenylsulfide) phenyl sulfonium hexafluoroantimonate, (4-phenylsulfide) phenyl diphenyl sulfonium hexafluoro phosphate, bis (4-tert-butyl phenyl) iodonium hexafluorophosphate, 4-isobutylphenyl-4' -methylphenyl iodonium hexafluorophosphate, triarylsulfonium hexafluorophosphate salt, and η 6-cumeneiron (II) hexafluorophosphate.
8. A preparation method of the photocuring composite epoxy fluorosilicone resin coating as claimed in claim 1, which is characterized in that epoxy group fluorosilicone resin, diisocyanate oligomer-g-triepoxy compound, active epoxy diluent and adhesion promoter are weighed in sequence according to mass ratio, stirred and mixed uniformly, then modified nano silica sol and cationic photoinitiator are added, and stirred and dispersed for 20-30min to obtain a uniform mixture, namely the composite photocuring epoxy fluorosilicone coating.
9. A preparation method of a photocuring composite epoxy fluorosilicone resin coating by using the coating of claim 1 is characterized in that the photocuring composite epoxy fluorosilicone resin coating is uniformly coated on the surface of a base material, and is leveled for 20-30min at room temperature, then a solvent is pre-dried for 3-10min at 100-120 ℃, and then the coating is placed in an ultraviolet curing machine for UV photocuring.
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