CN115894928B - Preparation method of photo-curing epoxy fluorobenzene silicone resin and application of photo-curing epoxy fluorobenzene silicone resin in paint coating - Google Patents

Preparation method of photo-curing epoxy fluorobenzene silicone resin and application of photo-curing epoxy fluorobenzene silicone resin in paint coating Download PDF

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CN115894928B
CN115894928B CN202211454705.1A CN202211454705A CN115894928B CN 115894928 B CN115894928 B CN 115894928B CN 202211454705 A CN202211454705 A CN 202211454705A CN 115894928 B CN115894928 B CN 115894928B
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siloxane
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silane
phenyl
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CN115894928A (en
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黄灵智
张星
邓小文
安秋凤
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Dongguan Xiongchi Electronic Co ltd
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Abstract

A process for preparing photo-solidified epoxy fluorobenzene silicon resin includes such steps as hydrolytic copolycondensation of epoxy silane with fluorocarbon silane, phenyl silane or phenyl siloxane oligomer, and synthesizing epoxy/fluorocarbon/phenyl co-modified silicon resin EPFSi, which is the copolymer of epoxy siloxane-co-fluorocarbon siloxane-co-phenyl siloxane or epoxy siloxane-co-fluorocarbon siloxane-co- (phenyl siloxane-co-alkyl siloxane) oligomer. Then EPFSi is used as a water-repellent and oil-repellent component, and the resin is combined with siloxy modified epoxy resin SiER, an active epoxy diluent, a cationic photo-curing agent and the like to prepare the photo-curing coating (EPFSi/SiER), which shows that under the action of ultraviolet irradiation, the coating can be rapidly crosslinked and cured into a hard coating (film) and has good waterproof, flame-retardant, salt fog-resistant and aging-resistant effects and ideal adhesive force.

Description

Preparation method of photo-curing epoxy fluorobenzene silicone resin and application of photo-curing epoxy fluorobenzene silicone resin in paint coating
Technical Field
The invention belongs to the field of functional resin, paint and coating, and in particular relates to a preparation method of epoxy group-containing, fluorocarbon group-containing and phenyl co-modified silicone resin (epoxy group fluorobenzene silicone resin for short) in a photo-curable structure and application of the resin in photo-curable paint and coating.
Background
Photo-curable resins, i.e., a class of substances that rapidly initiate chemical reactions between monomers or resins under the influence of a photoinitiator and crosslink to cure into a solid or elastomer. The photo-curing resin has the advantages of high curing speed, cleanness, environmental protection, less solvent and low pollution, becomes the development direction of resin coating, and has wide application in the aspects of 3D printing, resin rapid curing molding, packaging, potting materials and the like. At present, domestic research on photocurable resins is mainly focused on the aspects of photocureable coatings and coatings (CN 105778103A, CN111607321A, CN 104177991A and the like) prepared by using the alkenyl or acrylate-based photocureable resins, and relatively few researches are conducted on cationic photocureable epoxy-based resins and coatings constructed by using the cationic photocureable epoxy-based resins.
In the literature, although many studies have been reported on water-repellent and oil-repellent fluorosilicones containing Si-OH and Si-OR (see CN101775144B, CN103408762B, CN 104558458B), there are few studies on epoxy fluorosilicones and photocurable coatings and coatings prepared based on the epoxy fluorosilicones.
Disclosure of Invention
The invention aims to disclose a preparation method of photo-curable epoxy fluorobenzene silicone resin and application of the resin in photo-curable paint and coating. Therefore, the epoxy silane containing D, T (namely containing 2-3 alkoxy groups) is hydrolyzed and copolycondensed with the fluorocarbon silane, the phenylsilane or the phenylsiloxane oligomer by utilizing molecular design, and firstly, the epoxy/fluorocarbon/phenyl co-modified silicone resin (called epoxy fluorobenzene silicone resin for short, EPFSi) which is not reported is synthesized; in order to overcome the defects that the water and oil repellency and the lower adhesive force of the fluorosilicone resin are higher, the invention also utilizes the characteristics of low surface energy and easy surface approaching of the fluorosilicone resin, and then composites the epoxy fluorobenzene silicone resin with the silicon alkoxy modified epoxy resin, the cationic photoinitiator and the like with high adhesive force, thereby not only obtaining the photo-curable epoxy fluorosilicone coating, but also effectively improving the defects of low adhesive force, poor intersolubility with other resins and the like of the existing fluorosilicone resin coating.
The organic silicon resin has good weather resistance, high and low temperature resistance and electrical insulation performance and a certain flame retardant function, and the phenyl group is introduced into the structure of the silicon resin, so that the refractive index of the resin can be improved, and the resin is endowed with high light transmittance and high temperature resistance; the fluorocarbon group is introduced, so that the target resin has excellent water and oil repellency, and the outdoor weather resistance and ageing resistance of the resin are further improved, because the bond energy of C-F (485 kJ/mol) is large, and the resin is not easy to break under the action of ultraviolet light; in addition, by introducing reactive functional groups into the structure of the silicone resin, the specific reactivity of the functional groups can be further endowed to the target resin on the basis of maintaining the original performance characteristics of the resin. Based on the above, the invention adopts the following technical scheme:
a photo-cured epoxy fluorobenzene silicone resin (EFPSi) is prepared from the epoxy resin containing D (difunctional, RR' SiO) 2/2 ) And/or T-form (trifunctional, RSiO) 3/2 ) The copolymer of the chain units of epoxy siloxane, fluorocarbon base siloxane, phenyl siloxane or phenyl siloxane oligomer, in other words, the copolymer of epoxy siloxane-co-fluorocarbon base siloxane-co-phenyl siloxane or epoxy siloxane-co-fluorocarbon base siloxane-co-phenyl siloxane oligomer is prepared by the multi-component hydrolytic polycondensation reaction of epoxy silane and fluorocarbon base silane, phenyl silane or phenyl siloxane oligomer.
Preferably, the epoxy group is one of 2, 3-glycidoxypropyl, 3, 4-cyclohexylethyl or 2, 3-glycidoxypolyether, and the polyether group is polyoxyethylene polyoxypropylene ether propyl- (C) 2 H 4 O) a (C 3 H 6 O) b C 3 H 6 -wherein a = 0-6, b = 3-6, a + b = 3-6; the fluorocarbon radical being C 1-8 One of a perfluoroalkyl ethyl group, a pentafluorophenyl group, or a perfluoropolyether group; the phenyl siloxane oligomer is D, T type (di) phenyl siloxane oligomer or (di) phenyl siloxane-co- (di) alkyl siloxane oligomer formed by copolymerization, and is selected from dihydroxy or siloxane-terminated polydiphenyl siloxane (also called phenyl siloxane oligomer), phenyl siloxane-co-diphenyl siliconOne of the oligomers of oxygen, phenyl siloxane-co-dialkyl siloxane, diphenyl siloxane-co-dialkyl siloxane and the like, wherein the alkyl is-CH 3 ～-C 18 H 37 。
The light-cured epoxy fluorobenzene silicone resin (EFPSi) has a solid content of about 50-80% and an epoxy group content (calculated by the mole number of epoxy groups contained in 100 parts of resin) of about 0.03-0.2, and is prepared by the following steps:
weighing 7.5-20 parts of Epoxy Silane (ESi), 10-50 parts of fluorocarbon silane FSi and 30-82.5 parts of Phenylsilane (PSi) or phenylsiloxane Oligomer (OSi) according to the mass ratio, and stirring and uniformly mixing to obtain a mixture A; then, according to the mass of A, adding about 100-300wt% of organic solvent, 1-2wt% of hydrolysis catalyst and theoretical amount of deionized water, wherein the theoretical amount of deionized water can be determined based on the hydrolysis condensation reaction of siloxane, and controlling the temperature to 40-80 ℃ to carry out hydrolysis polycondensation reaction for 4-10 hours; after the reaction is finished, the catalyst is removed by water, the solvent is recovered, and the reduced pressure and the low boiling point are carried out, thus obtaining transparent-semitransparent viscous liquid, namely epoxy group/fluorocarbon group/phenyl co-modified silicone resin, which is called as EFPSi for short, and the transparent-semitransparent viscous liquid is stored after being diluted by the solvent until the solid content is about 50 to 80 weight percent.
The epoxysilane is silane containing one epoxy group and 2-3 alkoxy groups in the molecule, and one of (2, 3-glycidoxypropyl) trimethoxysilane, (2, 3-glycidoxypropyl) triethoxysilane, (2, 3-glycidoxypropyl) methyldimethoxy silane, (2, 3-glycidoxypropyl) methyldiethoxy silane, (3, 4-epoxycyclohexyl) ethyltrimethoxy silane, (3, 4-epoxycyclohexyl) ethyltriethoxy silane, (2, 3-epoxypropoxy) polyether trimethoxy silane, (2, 3-epoxypropoxy) polyether methyldimethoxy silane, (2, 3-epoxypropoxy) polyether triethoxy silane and (2, 3-epoxypropoxy) polyether methyldiethoxy silane is selected; the polyether is polyoxyethylene polyoxypropylene propyl- (C) 2 H 4 O) a (C 3 H 6 O) b C 3 H 6 In the formula, a and b have the same values as the values.
The fluorocarbon silane is C connected with the molecule 1-8 A perfluoroalkyl ethyl group, a perfluoroalkyl aryl group or a perfluoro polyether group, and a silane with 2-3 alkoxy groups, selecting heptadecafluorooctyl ethyl trimethoxysilane (also known as 1H, 2H-perfluoro decyl trimethoxysilane), heptadecafluorooctyl ethyl triethoxysilane (also known as 1H, 2H-perfluoro decyl triethoxysilane), tridecanyl ethyl trimethoxysilane (also known as 1H, 2H-perfluoro octyl trimethoxysilane) tridecyl fluorohexyl ethyl triethoxysilane (also known as 1H, 2H-perfluorooctyl triethoxysilane), nonafluorobutyl ethyl trimethoxysilane (also known as 1H, 2H-perfluorohexyl trimethoxysilane), nonafluorobutyl ethyl triethoxysilane (also known as 1H, 2H-perfluorohexyl triethoxysilane) 3-heptafluoroisopropoxypropyl trimethoxysilane, 3-heptafluoroisopropoxypropyl triethoxysilane, trifluoropropyl trimethoxysilane, trifluoropropyl methyl dimethoxy silane, trifluoropropyl triethoxysilane, trifluoropropyl methyl diethoxy silane, pentafluorophenyl trimethoxysilane, pentafluorophenyl triethoxysilane, perfluoropolyether trimethoxysilane having an average molecular weight of mn=1000-3000, perfluoropolyether triethoxysilane having an average molecular weight of mn=1000-3000, and the like; the perfluoro polyether group is CF 3 Or C 3 F 7 Copolymers of end-capped polyhexafluoropropane oxide or hexafluoropropane oxide-co-tetrafluoroethane oxide.
The phenylsilane is silane containing 1-2 phenyl groups and 2-3 alkoxy groups in the structure, and one of phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane and diphenyldiethoxysilane or a mixture of phenyltrialkoxysilane and diphenyldialkoxysilane in any proportion is selected.
The phenyl siloxane oligomer is a siloxane oligomer which contains silicon hydroxyl or silicon alkoxy in the molecule and D, T phenyl siloxane chain segments and has a linear, annular, dendritic or semi-closed cage-shaped structure, and is selected from semi-closed cage-shaped phenyl heptapolysiloxane trisilanol, annular 1,3,5, 7-tetramethyl-1, 3,5, 7-tetraphenyl cyclotetrasiloxane, annular octaphenyl cyclotetrasiloxane and hydroxyl-terminated polydiphenyl siloxane [ 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 isooligomers, wherein the alkyl is-CH 3 ～-C 18 H 37 ，n，n 1 ＝2-20，m 1 ，m 2 ＝0-18，n+m 1 、n+m 2 、n 1 +m 1 、n 1 +m 2 ＝2-20。
The organic solvent is a solvent such as fluorine alcohol, alcohol ether, ketone, alcohol ether ester, aromatic hydrocarbon or fluorinated aromatic hydrocarbon which has good intersolubility to fluorocarbon silane, phenyl silane, epoxy silane and the like, can be used singly or in a mixed mode, and is selected from one or a mixture of multiple of toluene (MB), benzotrifluoride, dimethylbenzene, (hexafluoro) acetone, butanone, cyclohexanone, methyl isobutyl ketone (MIBK), ethyl acetate, butyl Acetate (BA), ethylene glycol methyl ether, propylene glycol methyl ether acetate (PMA) and the like. Preferably, mixed solvents composed of (fluorine-containing) arene-alcohol, (fluorine-containing) arene-ester, (fluorine-containing) arene-ether ester, ester-ketone and the like are selected, such as (trifluoro) toluene-ethanol, benzotrifluoride-ethanol-butyl acetate, butyl acetate-pentafluoropentanol, PMA-propylene glycol methyl ether and the like.
The hydrolysis catalyst is inorganic acid or organic acid, and one of concentrated hydrochloric acid, citric acid, acetic acid and the like is selected.
The application of the photo-cured epoxy fluorobenzene silicone resin in paint and coating comprises two steps of paint preparation and coating curing:
(1) Preparing a coating: according to the mass portion, 35-74 portions of epoxy fluorobenzene silicone resin EFPSi, 20-50 portions of siloxy modified epoxy resin SiER, 5-10 portions of active epoxy diluent ED, 1-5 portions of epoxy adhesion promoter AP, 0-50wt% of modified nano silica sol based on the total mass of the substances (EFPSi+SiER+ED+AP) and 1-6wt% of cationic photoinitiator are weighed, stirred and dispersed for 20-30min to obtain a uniform mixture, namely the coating prepared based on the photo-cured epoxy fluorobenzene silicone resin, and the coating is marked as EFPSi/SiER.
(2) And (3) curing the coating: and (3) diluting the EFPSi/SiER coating with a solvent until the solid content is about 30-40wt%, uniformly coating the coating on the surface of a substrate by using a spray gun, leveling at room temperature for 20-30min, pre-drying at 100-120 ℃ for 3-10min, and then placing in an ultraviolet curing machine for photo-curing for 2-4min to obtain the coating, namely the EFPSi/SiER sample.
The structure of the siloxy modified epoxy resin SiER is shown as a formula (1), and the siloxy modified epoxy resin SiER is a product generated by substituting part of hydroxyl groups in the epoxy resin structure with trialkoxy silicon propyl carbamate groups, wherein m=0, 1; r=ch 3 Or C 2 H 5 。
The siloxy modified epoxy resin SiER has an epoxy value (the mole number of epoxy groups contained in 100g of resin) of about 0.2-0.55 and a viscosity of about 1000-25000mPa.s, and is prepared by reacting epoxy resin containing C-hydroxyl in the structure with 3-isocyanatosilane at 70-80 ℃ for 1-3 hours; preferably, the Epoxy Resin (ER) containing C-hydroxyl in the structure is one of bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin and the like; the 3-isocyanatosilane (SiNCO) is one of 3-isocyanatopropyl trimethoxysilane, 3-isocyanatopropyl triethoxysilane, (3-isocyanatopropyl) methyldimethoxy silane and (3-isocyanatopropyl) methyldiethoxy silane; the ratio (molar ratio) of the epoxy resin containing the C-hydroxyl group to the 3-isocyanatosilane in the structure is controlled to be n (C-OH): n (SiNCO) =1:1-0.25; if the viscosity of the system is too high during the reaction, a proper amount of solvent can be added for proper dilution and then the reaction is carried out.
The active epoxy diluent is a compound containing1-2 epoxy groups, and compound or oligomer capable of participating in the special chemical reaction of epoxy groups and having similar solvent dilution effect, butyl glycidyl ether and C 12-14 Aliphatic alkyl glycidyl ether, phenyl glycidyl ether, benzyl glycidyl ether, o-tolyl glycidyl ether, 1, 6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and the like.
The epoxy adhesion promoter is a substance which contains epoxy groups and siloxy groups, can participate in the photo-curing reaction of resin or paint and can increase the cohesiveness between a substrate and an organic coating, and one of (2, 3-glycidoxypropyl) methyldimethoxy silane, (2, 3-glycidoxypropyl) methyldiethoxy silane, (2, 3-glycidoxypropyl) trimethoxy silane (KH-560), (2, 3-glycidoxypropyl) triethoxy silane, (2, 3-glycidoxypropyl) polyether trimethoxy silane, (2, 3-glycidoxypropyl) polyether methyldimethoxy silane and the like is selected; the polyether group is polyoxyethylene polyoxypropylene ether group- (C) 2 H 4 O) a1 (C 3 H 6 O) b1 -, which may be the same as or different from, in the formula a 1 ＝0-6,b 1 ＝3-6，a 1 +b 1 ＝3-6。
The modified nano silica sol is phenyl or fluorocarbon group modified nano silica sol, the solid content is about 20-35% (the dispersion medium is alcohol ether or alcohol ether ester solvent), the average particle diameter is about 20-30nm, the pH is about 6-7, and the modified nano silica sol is ordered from Qingdao Yida silica gel reagent Co.
The cationic photoinitiator is a substance capable of initiating epoxy radical cationic ring-opening reaction under ultraviolet irradiation, and one of cationic diphenyl- (4-phenylthio) phenylsulfonium hexafluoroantimonate (cationic photoinitiator 6976), 4-phenylthio) phenyldiphenylsulfonium hexafluorophosphate (cationic photoinitiator 6992), bis (4-tert-butylphenyl) iodonium hexafluorophosphate (cationic photoinitiator PI 9388), 4-isobutylphenyl-4' -methylphenyl iodohexafluorophosphate (cationic photoinitiator 250), triaryl hexafluorosulfonium phosphate (cationic photoinitiator 1176), eta 6-isopropylbenzene ferrocene (II) hexafluorophosphate (cationic photoinitiator 261) and the like is selected.
The substrate of the photo-curing coating is one of clean tinplate, aluminum alloy, steel plate, copper-clad circuit board, glass, ceramic, PC circuit board and the like after roughening treatment; the coating modes comprise spraying, brushing, rolling, silk rod coating (rod coating), spin coating, dipping and pulling method film forming and the like.
The application performance of the photo-cured epoxy fluorobenzene silicone resin coating is evaluated according to the following method:
light transmittance (T), measured with a Cary 5000 uv-vis spectrophotometer using glass as the coating substrate; ageing resistance (1000 h×85 ℃ C. ×RH 85%): the test is carried out by referring to GB/T2423.24-1995 standard and using a KK-SN-150 xenon lamp aging resistance test box; the water repellency of the coating surface is measured by the static contact angle (θ H2O ) The water drop size was about 5. Mu.L using a JC-2000C1 static contact angle measuring instrument; salt spray resistance: taking 5wt% NaCl aqueous solution as a test solution, and referring to GB/T10125-1997 standard; adhesion force: with reference to HGT3792-2014 standard, the test is carried out by an electric adhesion tester; impact resistance: reference GB/T1732-1993, measured with an impact resistor; flexibility: measured by a paint film elasticity tester according to the method of GB/T1731-1993; hardness: evaluation with pencil hardness was carried out by the method of GB/T6739-1996; antifouling properties: the fly ash is classified into five classes of 0,1,2,3 and 4, and the class 0 is the best, as measured by the fly ash method specified in GB/T9780-1988.
The invention has the beneficial effects that: based on the molecular design and similar compatibility principle, the epoxy silane and fluorocarbon silane, phenyl silane or phenyl silane oligomer are hydrolyzed and copolycondensed, and the reactive epoxy fluorosilicone resin with epoxy, fluorocarbon and phenyl functional groups bonded simultaneously in a structure is designed and synthesized, so that the defects of poor compatibility and the like of the existing (fluorocarbon/methyl group-containing group) fluorosilicone resin and the modified epoxy resin can be obviously improved; secondly, the new epoxy fluorobenzene silicone resin is used as a low-surface-energy water-repellent and oil-repellent component, and then the resin is compounded with a strong-adhesion siloxy modified epoxy resin, an adhesion promoter, a nano hardening component (such as phenyl modified nano silica sol), a cationic photoinitiator and the like to prepare the cationic photo-curing coating, so that the rapid curing of the fluorosilicon coating can be realized under the action of ultraviolet light, the obvious difference of the surface energy of the fluorosilicon resin and the surface energy of the components such as the modified epoxy resin is utilized, the fluorosilicon chain segments are driven to migrate to the surface of the coating by means of predrying, solvent volatilizing and the like, and meanwhile, the strong-adhesion siloxy modified epoxy resin is concentrated in a distributed manner between a base material and the fluorosilicon coating, so that the photo-cured coating can play the roles of water-repellent, oil-repellent, dust-proof and ageing resistance to the greatest extent, and the adhesion of the coating and the base material is not influenced, and a reference is provided for solving the adhesion of the water-repellent oil-repellent fluorosilicon coating.
Detailed Description
The present invention will be further described with reference to examples, but the present invention is not limited to the following examples.
Example 1
20.0g of 2, 3-glycidoxypropyl methyl dimethoxy silane KH781, 10.0g of heptadecafluorooctyl ethyl trimethoxy silane and 70.0g of phenylsilane mixture consisting of 35.0g of phenyltrimethoxy silane and 35.0g of diphenyl dimethoxy silane are sequentially added into a three-necked flask provided with a thermometer, a reflux condenser and a stirrer, and the mixture is stirred and uniformly mixed to obtain a total of about 100.0g of mixture A; then, 100wt% toluene-ethanol (1:1, wt/wt) solvent, 1wt% concentrated hydrochloric acid hydrolysis catalyst and theoretical amount of deionized water were added in terms of mass of A to carry out hydrolytic polycondensation reaction at 40℃for 10 hours. After the reaction, heating to 85 ℃, firstly steaming to remove the alcohol solvent, then washing with the deionized water with the same volume for 2 times to remove the catalyst, and then adding the catalyst into P Watch (watch) Reduced pressure, reduced boiling at about 0.8MPa, resulted in about 75.83g of a clear viscous liquid, namely, an epoxyfluorobenzene silicone resin, 2, 3-glycidoxypropyl methyl silicone-co-heptadecafluorooctyl ethyl silicone-co-phenyl silicone-co-diphenyl silicone, designated EFPSi-1, having an epoxy content (expressed as moles of epoxy groups contained in 100g of the resin, mol%, the same applies hereinafter) of about 0.1197, diluted with a benzotrifluoride-ethyl acetate solvent (1:1, wt/wt, the same applies hereinafter) to a solids content of about 60% for use.
Example 2
20.0g of 3, 4-cyclohexyl ethyl trimethoxy silane KH560, 50.0g of pentafluorophenyl triethoxy silane and 30.0g of diphenyl dimethoxy silane are sequentially added into a three-necked flask equipped with a thermometer, a reflux condenser and a stirrer, and the mixture is stirred and mixed uniformly to obtain a total of about 100.0g of mixture A; then, about 300wt% of benzotrifluoride-ethanol (mass ratio 1:1) solvent, 1% concentrated hydrochloric acid catalyst and theoretical amount of deionized water were added in terms of mass of A to carry out hydrolytic polycondensation reaction at 80℃for 4 hours. After the reaction, heating to 85 ℃, firstly steaming to remove the alcohol solvent, then washing with the deionized water with the same volume for 2 times to remove the catalyst, and then adding the catalyst into P Watch (watch) Reduced pressure and reduced boiling under about 0.9MPa to obtain about 72.91g of transparent-semitransparent viscous liquid, namely epoxy fluorobenzene silicone resin-3, 4-cyclohexyl ethyl siloxane-co-pentafluorophenyl siloxane-co-diphenyl siloxane, which is marked as EFPSi-2, wherein the epoxy content is about 0.1114, and the liquid is diluted to the solid content of about 80 percent by benzotrifluoride-ethyl acetate (1:1, wt/wt) for later use.
Example 3
10.0g of 2, 3-glycidoxypropyl trimethoxysilane KH560, 20.0g (0.0427 mol) of tridecyl ethyl trimethoxysilane, 20.0g of trifluoropropyl methyl dimethoxy silane and 50.0g of phenyl siloxane-co-dimethyl siloxane oligomer (chain link ratio 1:1, mol/mol) are sequentially added into a three-necked flask equipped with a thermometer, a reflux condenser and a stirrer, and the mixture is stirred and mixed uniformly to obtain a total of about 100.0g of mixture A; then, about 200wt% of benzotrifluoride-ethanol (1:1, wt/wt) solvent, 1wt% of concentrated hydrochloric acid catalyst and a theoretical amount of deionized water were added in terms of the mass of A to carry out hydrolytic polycondensation reaction at 60℃for 6 hours. After the reaction, heating to 85 ℃, firstly steaming to remove the alcohol solvent, then washing with the deionized water with the same volume for 2 times to remove the catalyst, and then adding the catalyst into P Watch (watch) Reduced pressure, reduced boiling at about 0.85MPa to give about 89.58g of a transparent-translucent viscous liquid, namely an epoxyfluorobenzene silicone resin-2, 3-epoxypropoxypropyl siloxane-co-tridefluorohexyl ethyl siloxane-co-trifluoropropyl methyl siloxane-co- (phenyl siloxane-co-dimethyl siloxane) oligomer, designated EFPSi-3, having an epoxy content of about 0.0473, diluted with benzotrifluoride-propylene glycol methyl ether (1:1, wt/wt) to a solids contentAbout 70wt% for use.
Example 4
7.50g of 2, 3-glycidoxypropyl trimethoxy silane KH560, 10.0g of tridecyl fluorohexyl ethyl trimethoxy silane and 82.5g of diphenylsiloxane-co-hexadecyl siloxane oligomer (chain link ratio 2:1, mol/mol) are sequentially added into a three-necked flask equipped with a thermometer, a reflux condenser and a stirrer, and the mixture is stirred and mixed uniformly to obtain a total of about 100.0g of mixture A; then, about 150% by weight of benzotrifluoride-ethanol (1:1, wt/wt) solvent, 1% concentrated hydrochloric acid catalyst and a theoretical amount of deionized water were added in terms of the mass of A to carry out hydrolytic polycondensation reaction at 70℃for 5 hours. After the reaction, heating to 80 ℃, firstly steaming to remove the alcohol solvent, then washing with the deionized water with the same volume for 2 times to remove the catalyst, and then adding the catalyst into P Watch (watch) Reduced pressure and low boiling under the condition of =0.87 MPa to obtain about 96.34g of transparent viscous liquid, namely epoxy fluorobenzene silicone resin-2, 3-glycidoxypropyl siloxane-co-tridecyfluorohexyl ethyl siloxane-co- (diphenyl siloxane-co-hexadecyl siloxane) oligomer, which is marked as EFPSi-4, wherein the epoxy group content is about 0.0330, and the epoxy fluorobenzene silicone ether (1:1, wt/wt) is diluted to the solid content of about 50 percent for standby.
Example 5
Into a three-necked flask equipped with a thermometer, reflux condenser and stirrer, 19.5g, a=0, b=3 of 2, 3-glycidoxypropyl polyoxypropylene ether methyl dimethoxy silane, 15.0g of perfluoro polyether trimethoxy silane with Mn=1000, 20.0g of nine fluorohexyl trimethoxy silane (also called nine fluorobutyl ethyl trimethoxy silane) and 47.0g of hydroxy-terminated phenyl siloxane-co-diethyl siloxane oligomer (chain link ratio 1:2, mol/mol) were added in this order, and stirred and mixed to obtain a total of about 100.0g of mixture A; then, about 230wt% of benzotrifluoride-ethanol (1:1, wt/wt) solvent, 1% concentrated hydrochloric acid catalyst and theoretical amount of deionized water were added in terms of mass of A to carry out hydrolytic polycondensation reaction at 60℃for 6 hours. After the reaction, heating to 80 ℃, firstly steaming to remove the alcohol solvent, then washing with the deionized water with the same volume for 2 times to remove the catalyst, and then adding the catalyst into P Watch (watch) Reduced pressure and low boiling under the condition of about 0.89MPa to obtain about 94.45g of semitransparent-transparent viscous liquid, namely the epoxy fluorobenzene silicone resin-2, 3-glycidoxypropyl polyoxypropylene ether methyl siloxane-co-perfluoropolyether siloxane-co-nonafluorohexyl siloxane-co- (phenylsiloxane-co-diethylsiloxane) oligomer, designated EFPSi-5, having an epoxy content of about 0.0523, diluted with benzotrifluoride-propylene glycol methyl ether (1:1, wt/wt) to a solids content of about 70% for use.
Example 6
15.0g of 3, 4-cyclohexyl ethyl trimethoxy silane A186, 36.0g of tridecyl fluorohexyl ethyl trimethoxy silane, 5.0g of phenyl hepta polysiloxane trisilanol and 44.0g of hydroxyl-terminated diphenyl siloxane-co-dimethyl siloxane oligomer (chain link ratio 1:1, mol/mol) are sequentially added into a three-necked flask provided with a thermometer, a reflux condenser and a stirrer, and the mixture is stirred and mixed uniformly to obtain a total of about 100.0g of mixture A; then, about 180wt% of benzotrifluoride-ethanol (1:1, wt/wt) solvent, 1% concentrated hydrochloric acid catalyst and theoretical amount of deionized water were added in terms of mass of A to carry out hydrolytic polycondensation reaction at 55℃for 7 hours. After the reaction, heating to 85 ℃, firstly steaming to remove the alcohol solvent, then washing with the deionized water with the same volume for 2 times to remove the catalyst, and then adding the catalyst into P Watch (watch) Reduced pressure, reduced boiling at about 0.83MPa, yielded about 90.49g of a translucent-transparent viscous liquid, 3, 4-cyclohexylethyl siloxane-co-tridecylfluorohexyl ethyl siloxane-co-phenylheptapolysiloxane trisilanol-co- (diphenylsiloxane-co-dimethylsiloxane) oligomer, designated EFPSi-6, having an epoxy content of about 0.0673, diluted with benzotrifluoride-ethyl acetate (1:1, wt/wt) to a solids content of about 60% for use.
The photocurable epoxy fluorosilicone resins EFPSi-1 to 6 prepared in examples 1 to 6 were adjusted to a solid content of about 50% by weight with a solvent, and a photocurable coating was prepared as follows:
the siloxy modified epoxy resin SiER used for the coating takes 3-isocyanatopropyl trimethoxy silane modified bisphenol A epoxy resin E44 as an example, and is prepared by the following method:
(1) Preparation of raw material siloxy modified epoxy resin-trimethoxy silicon propyl carbamate-g-E44
In a dry three-necked flask equipped with a thermometer, a reflux condenser and a stirrer, bisphenol A epoxy resin E44 containing C-hydroxy groups in the structure (the epoxy group content is about 0.44, the viscosity is about 18000mPa.s, the hydroxyl value is about 0.0887 based on the mol number of hydroxy groups contained in 100g of resin) is sequentially added into the three-necked flask, then the molar ratio of C-OH to SiNCO contained in the E44 is about 1:0.3, then 0.0266mol and about 5.46g of 3-isocyanatopropyl trimethoxysilane (SiNCO-1) are added, and the temperature is controlled to be 80 ℃ for stirring reaction for 3 hours to obtain transparent liquid, namely E44-trimethoxy silicon propyl carbamate-g-E44 after the modification of the 3-isocyanatopropyl trimethoxy silane, which is abbreviated as SiER-44.
(2) Preparing a photo-curing coating: according to the mass portion, 60.0g of epoxy fluorobenzene silicone resin EFPSi-1-6 with the solid content of about 50%, 30.0g of trimethoxy silicon-based modified epoxy resin SiER-44, 8.0g of active epoxy diluent neopentyl glycol diglycidyl ether, 2.0g of epoxy adhesion promoter KH-560, 25wt% (about 25.0 g) of phenyl modified nano silica sol with the solid content of 30% and the average particle size of 20-30nm and 3.5wt% (about 3.50 g) of cationic photoinitiator 6976 are weighed, stirred and dispersed for 30min, and a uniform mixture is obtained, namely the photo-curing coating prepared based on the epoxy fluorobenzene silicone resin EFPSi-1-6 and SiER-44 and the like, and is marked as EFPSi/SiER-1-6.
(3) Preparing a photo-curing coating: and (3) thinning the EFPSi/SiER-1-6 coating to 30% by using benzotrifluoride-ethyl acetate (1:1, wt/wt), then uniformly spraying the coating on the surfaces of clean tinplate and glass by using a spray gun with the caliber of about 0.8mm, leveling at room temperature for 30min, drying at 100 ℃ for 5min, and then placing in an ultraviolet curing machine with the power of 1000W for photo-curing for 2min to obtain a coating sample, namely the EFPSi/SiER-1-6 coating sample.
(4) Performance test: the photocurable coatings EFPSi/SiER-1 to 6 prepared in examples 1 to 6 were taken and left at room temperature for 24 hours, and then subjected to performance test as follows. The light transmittance is measured by using a Cary 5000 ultraviolet-visible spectrophotometer by taking a coating prepared from a glass substrate as a test sample and taking blank glass as a reference; the water-proof property of the coating surface is expressed by the static contact angle (theta H2O ) The expression, with JC-2000C1 static contact angle measuring instrument,the water droplet size was 5. Mu.L. Ageing resistance (1000 h. Times.85 ℃ C. X/RH 85%): the test is carried out by referring to GB/T2423.24-1995 standard and using a KK-SN-150 xenon lamp aging resistance test box; salt spray resistance: taking 5wt% NaCl aqueous solution as a test solution, and referring to GB/T10125-1997 standard; adhesion force: with reference to HGT3792-2014 standard, the test is carried out by an electric adhesion tester; impact resistance: reference GB/T1732-1993, measured with an impact resistor; flexibility: reference is made to the GB/T1731-1993 method, measured with a paint film elasticity tester; hardness: evaluation was carried out by pencil hardness according to the method of GB/T6739-1996. Antifouling properties of the coating surface: the fly ash is measured by a fly ash test method specified in GB/T9780-1988 and is divided into five grades of 0,1,2,3 and 4, and the grade 0 is the best; cold and hot cycle resistance: taking a coating sample, placing the coating sample in a freezing environment at the temperature of minus 40 ℃ for 30min, taking the coating sample out, placing the coating sample in a baking oven at the temperature of 70 ℃ for 30min, alternately operating the coating sample until the testing time is about 7 days (168 h), and observing the changes of the surface of the coating after the cold and hot cycles or the occurrence of cracking, rhagadia and other phenomena; after flame combustion time: referring to GB 11020-2005, a vertical burning test was performed using a vertical burner to prepare a 130mm by 13mm by 2mm specimen, the air flow and air intake were adjusted to produce a flame with a height of 20mm, the specimen was placed in the flame to make the tip of the torch 10mm below the end point of the specimen, the torch was evacuated after 3 seconds and the after flame burning time was started to be measured.
In addition, the EFPSi-1 to 6 and the trimethoxy silicon-based modified epoxy SiER-44 in the preparation of the photo-curing coating in the step (2) are replaced by the epoxy resin E51 and the epoxy resin E44 with equal mass respectively, and the photo-curing coating is prepared by the same method and used as a reference of the invention. The results of the performance measurements for all coatings are shown in Table 1.
TABLE 1 Properties of Photocurable coatings EFPSi/SiER-1-6 and comparison with reference
Test item Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Reference(s)
Transmittance T/% 98 98 95 92 88 96 95
Hardness of 4H 4H 2H 1H 2H 3H 2H
Adhesion/grade 0 1 1 0 1 1 1
Flexibility/cm 1.5 2 1 1 0.5 1 2
θ H2O /° 112.3 127.8 106.1 110.7 118.4 121.5 73.6
Dirt resistance grade 1 0 0 1 0 0 3
Salt spray resistance/h ≥1000 ≥1300 ≥1200 ≥1000 ≥1200 ≥1200 ≥1000
Ageing resistance ★ ★ ★ ★ ★ ★ Yellow surface color
Resistant to cold and hot cycles No abnormality No abnormality No abnormality No abnormality No abnormality No abnormality Local shedding
After flame burn time/s 19 16 18 22 18 15 >30
?. Reference-photo-cured epoxy coating
As can be seen from Table 1, the coatings EFPSi/ER-1 to 6 prepared with the photo-curable epoxy phenyl fluorosilicone resins of the present invention have a coating surface θ compared to the reference cationic photo-curable epoxy resin coating H2O Obviously increase the surface of the aging-resistant 1000h coating without changeThe salt fog resistance reaches 1000-1300h, the antifouling grade generally reaches 0-1 grade, the minimum flexibility reaches 0.5mm, the adhesive force is 0-1 grade, the coating is resistant to cold and hot circulation at minus 40 ℃ and 70 ℃ for 7 days without abnormality, and the after flame combustion time (flame retardance) is generally 15-22s, which shows that the waterproof, antifouling, ultraviolet aging resistance and salt fog resistance of the surface of the EFPSi/ER coating are enhanced, and the coating has good adhesive force, cold and hot temperature resistance and a certain flame retardance. Obviously, the photo-curing fluorosilicone coating composition and the coating prepared by combining photo-curing epoxy phenyl fluorosilicone resin and siloxy modified epoxy resin with strong adhesive force not only can realize quick photo-curing, but also can achieve the effects of water resistance, pollution resistance, salt fog resistance, aging resistance, cold and heat resistance and flame retardance on the performance of the coating prepared by the invention without affecting the adhesive force and flexibility of the coating due to the adhesion of siloxy in the coating and the curing promotion effect of moisture.

Claims (5)

1. The application of the photo-curing epoxy fluorobenzene silicone resin for preparing a photo-curing paint or coating is characterized in that the photo-curing epoxy fluorobenzene silicone resin is obtained by a method comprising the following steps:
performing hydrolysis polycondensation reaction on epoxy silane ESi, fluorocarbon silane FSi and phenyl siloxane oligomer OSi to obtain photo-cured epoxy fluorobenzene silicone resin;
the epoxy silane ESi is silane containing 1 epoxy group and 2-3 alkoxy groups in the molecule;
the fluorocarbon silane FSi is a compound containing 2-3 alkoxy groups and C in the molecule 1-8 Perfluoroalkyl, pentafluorophenyl or perfluoropolyether-based silanes;
the phenyl siloxane oligomer OSi is a silicon hydroxyl or silicon alkoxy end-capped polydiphenyl siloxane, silicon hydroxyl or silicon alkoxy end-capped phenyl siloxane-co-diphenyl siloxane, silicon hydroxyl or silicon alkoxy end-capped phenyl siloxane-co-dialkyl siloxane, silicon hydroxyl or silicon alkoxy end-capped diphenyl siloxane-co-dialkyl siloxane or semi-closed cage-shaped phenyl heptapolysiloxane trisilanol; the phenyl siloxane oligomer OSi contains silicon hydroxyl or silicon alkoxy in structure and containsHaving D-type siloxane units and/or T-type siloxane units; the alkyl is-CH 3 ～-C 18 H 37 ；
The alkoxy is methoxy or ethoxy;
the application comprises siloxane modified epoxy resin and photo-curing epoxy fluorobenzene silicone resin, wherein the structure of the siloxane modified epoxy resin is shown as a formula (1):
in formula (1), m=0, 1; r=ch 3 Or C 2 H 5 。
2. The use according to claim 1, wherein the epoxy group is 2, 3-glycidoxypropyl, 3, 4-cyclohexylethyl or 2, 3-glycidoxypolyether group, and the polyether group is polyoxyethylene polyoxypropylene ether propyl (C 2 H 4 O) a (C 3 H 6 O) b C 3 H 6 Wherein a=0 to 6, b=3 to 6, and a+b=3 to 6.
3. Use according to claim 1 or 2, characterized by comprising the following preparation steps:
weighing 7.5-20 parts by mass of epoxy silane ESi, 10-50 parts by mass of fluorocarbon silane FSi and 30-82.5 parts by mass of phenyl siloxane oligomer OSi, and uniformly stirring and mixing to obtain a mixture A; then adding 100-300wt% of organic solvent, 1-2wt% of hydrolysis catalyst and deionized water into the total mass of A, and performing hydrolytic polycondensation reaction on the mixture A at 40-80 ℃ for 4-10h; and then washing with water, recovering the solvent and removing low boiling point to obtain transparent viscous liquid, namely the photo-curing epoxy fluorobenzene silicone resin, which is marked as EFPSi.
4. Use according to claim 1, wherein the fluorocarbon base silane FSi is heptadecafluorooctyl ethyl trialkoxysilane, tridecanyl ethyl trialkoxysilane, nonafluorobutyl ethyl trialkoxysilane, 3-heptafluoroisopropyl propyl trialkoxysilane, pentafluorophenyl trialkoxysilane or a perfluoropolyether-based trialkoxysilane having a number average molecular weight Mn = 1000-3000.
5. The use according to claim 1, wherein the epoxysilane ESi is 2, 3-glycidoxypropyl trialkoxysilane, 2, 3-glycidoxypropyl methyl dialkoxysilane, 3, 4-epoxycyclohexyl ethyl trialkoxysilane, 2, 3-glycidoxypolyether methyl dialkoxysilane or 2, 3-glycidoxypolyether trialkoxysilane.
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