CN116042091B - Preparation method of amino/phenyl fluorosilicone resin composite epoxy styrene-acrylic paint and coating - Google Patents

Preparation method of amino/phenyl fluorosilicone resin composite epoxy styrene-acrylic paint and coating Download PDF

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CN116042091B
CN116042091B CN202310056346.2A CN202310056346A CN116042091B CN 116042091 B CN116042091 B CN 116042091B CN 202310056346 A CN202310056346 A CN 202310056346A CN 116042091 B CN116042091 B CN 116042091B
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phenyl
epoxy
styrene
coating
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CN116042091A (en
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安秋凤
邱甲云
卢攀
焦岚姣
薛朝华
吴燕燕
黄良仙
赵霞
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Shaanxi University of Science and Technology
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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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
    • 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
    • C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
    • C09D125/02—Homopolymers or copolymers of hydrocarbons
    • C09D125/04—Homopolymers or copolymers of styrene
    • C09D125/08—Copolymers of styrene
    • C09D125/14—Copolymers of styrene with unsaturated esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation

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  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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Abstract

The invention discloses a preparation method of an amino/phenyl fluorosilicone resin composite epoxy styrene-acrylic coating and a coating. 100 parts of amino/phenyl fluorosilicone resin, 0.5 to 1.0 part of wetting dispersant, 25 to 50 parts of nano pigment filler, a proper amount of amino regulator and the like are prepared into a material A, and 100 parts of epoxy styrene-acrylic resin, 0.5 to 1.0 part of wetting dispersant, 25 to 50 parts of nano pigment filler, a proper amount of epoxy regulator and the like are prepared into a material B; when in use, A, B materials are mixed and regulated by an amino regulator or an epoxy regulator, so that the molar ratio of N-H bonds in the material A to epoxy groups in the material B of the system is controlled to be 1-1.05:1. The coating prepared by the amino/phenyl fluorosilicone resin composite epoxy styrene-acrylic coating disclosed by the invention has good adhesive force, water repellency, stain resistance and salt spray resistance.

Description

Preparation method of amino/phenyl fluorosilicone resin composite epoxy styrene-acrylic paint and coating
Technical Field
The invention belongs to the field of functional resins, coatings and coatings, and particularly relates to a coating and a coating prepared based on amino/phenyl fluorosilicone resin composite modified epoxy styrene-acrylate resin (epoxy styrene-acrylate resin for short).
Background
The fluorosilicone resin is polymer with water-repellent oil-repellent fluorocarbon radical and D, T siloxane chain units, and has excellent waterproof, oil-repellent, dustproof, salt fog-resistant and other functions, excellent weather resistance and ageing resistance, and may be used widely in anticorrosive coating, superhydrophobic interface construction and other fields. However, the traditional fluorosilicone resin has low surface energy, small adhesion to a substrate and poor intersolubility with other organic resins. Phenyl groups are introduced into the structure of the fluorosilicone resin, so that the intersolubility of the fluorosilicone resin and other organic resins is hopeful to be improved, and the refractive index, the light transmittance and the high temperature resistance of the fluorosilicone resin are improved; the amino group is introduced, so that the characteristic reactivity of the amino functional group of the fluorine-silicon resin can be endowed on the basis of keeping the original performance advantage of the fluorine-silicon resin.
The silicone resin or the fluorosilicone resin is physically combined or chemically bonded with other organic resins, so that the advantages of the two types of resins can be taken as the advantages of the two types of resins, which is always a strategy for constructing functional composite resin coatings conventionally used in the literature, for example, CN104293267 and CN106349460 are used for carrying out condensation reaction on the organic silicone resin or the organic silicone intermediate and the epoxy resin to prepare the organic silicone modified epoxy resin, and the resin can be said to effectively improve the performances of high temperature resistance, ultraviolet aging resistance and the like of the epoxy resin; and Dong Xihua and the like take amino cage type silsesquioxane as a curing agent to crosslink and cure the epoxy resin pouring sealant, so that the heat-resistant stability, high temperature resistance and other performances of the pouring sealant are improved [ Chinese adhesive, 2007, 16 (4): 29-32]. However, there is no report in the literature on crosslinking modified epoxy-based acrylic resin paints, coatings with fluorosilicone resins bearing amino functional groups.
Epoxy styrene-acrylate resins (ESA) are copolymers of styrene-acrylates containing epoxy groups in the structure. The ESA resin has the advantages of acrylic resin, such as light color, full luster, strong adhesive force, alkali resistance, heat resistance, corrosion resistance, good decorative effect and the like of a coating film, and also has the performances of reactivity of the resin endowed by epoxy groups, good weather resistance of the resin endowed by styrene and the like. It is well known that epoxy resins can be cured by crosslinking of organic amine curing agents to produce epoxy coatings; however, in contrast, there have been reports of crosslinking and curing an amino group-containing fluorosilicone resin with an ESA resin to form a water-repellent and oil-repellent functional coating.
Disclosure of Invention
The invention aims to provide a preparation method of an amino/phenyl fluorosilicone resin composite epoxy styrene-acrylic coating and a coating.
In order to achieve the above purpose, the invention adopts the following technical scheme:
An amino/phenyl fluorosilicone resin composite epoxy styrene-acrylic coating comprises a material A and a material B by mass; the material A consists of 100 parts of amino/phenyl fluorosilicone resin (AFPS), 0.5-1.0 part of wetting dispersant, 25-50 parts of nano pigment and filler (solid is the same as the description below if not shown), a proper amount of organic solvent S1 and a proper amount (more than or equal to 0 part) of amino regulator; the material B consists of 100 parts of epoxy styrene-acrylic resin (ESA), 0.5-1.0 part of wetting dispersant, 25-50 parts of nano pigment filler, a proper amount of organic solvent S2 and a proper amount (more than or equal to 0 part) of epoxy regulator; the ratio of the mole number of the N-H bond containing amino contained in the material A to the mole number of the epoxy group contained in the material B is 1-1.05:1; the amino/phenyl fluorosilicone resin comprises a siloxane copolymer (specifically an amino alkyl siloxane-co-fluorocarbon alkyl siloxane-co-phenyl siloxane copolymer or an amino alkyl siloxane-co-fluorocarbon alkyl siloxane-co-phenyl siloxane oligomer copolymer) of which the structure is simultaneously connected with D, T units such as amino alkyl siloxane, fluorocarbon alkyl siloxane, phenyl siloxane or phenyl siloxane oligomer; in the copolymer, the amino alkyl is one of gamma-aminopropyl, N-cyclohexyl-gamma-aminopropyl, N-dimethyl-gamma-aminopropyl (also called N, N-dimethyl aminopropyl), piperazinylpropyl and the like, the fluorocarbon alkyl is one of C 1～C8 perfluoroalkyl ethyl, perfluor aryl and perfluor polyether, the phenyl siloxane oligomer is D, T (di) phenyl siloxane (which means phenyl siloxane or diphenyl siloxane) or (di) phenyl siloxane-co- (di) alkyl siloxane copolymerized oligomer, and alkyl contained in the (di) phenyl siloxane-co- (di) alkyl siloxane copolymerized oligomer is-CH 3～-C18H37.
Preferably, the solid content of the amino/phenyl fluorosilicone resin is 60-80 wt%, the ammonia value (in terms of millimoles of amino contained in each gram of resin) is 0.8-2.4 mmol/g, and the amino/phenyl fluorosilicone resin is prepared by carrying out hydrolysis (2-3 functional amino hydrocarbyl silane autocatalysis) polycondensation reaction on 2-3 functional amino hydrocarbyl silane, fluorocarbon silane and phenylsilane or phenylsiloxane oligomer, and then diluting the mixture to the solid content of 60-80 wt% by using an organic solvent S4; the hydrolytic polycondensation reaction specifically comprises the following steps: weighing 10-35 parts by mass of 2-3 functional amino alkyl silane, 10-45 parts by mass of fluorocarbon alkyl silane and 20-80 parts by mass of phenyl silane or phenyl siloxane oligomer, and stirring and uniformly mixing to obtain a mixture A; then adding 50-200% of organic solvent S3 based on the mass of the mixture A, 0.5-2% of organic metal catalyst based on the mass of the mixture A, and water with the same molar quantity as alkoxy in silane contained in the mixture A, heating to 40-80 ℃ for hydrolysis polycondensation reaction for 4-8 hours, evaporating the solvent after the reaction is finished, removing low-boiling substances, and obtaining semitransparent-transparent viscous liquid, namely the copolymer of amino alkyl siloxane-co-fluorocarbon alkyl siloxane-co-phenyl siloxane or phenyl siloxane oligomer.
Preferably, the 2-3 functional amino hydrocarbyl silane is monoamine or diamine silane containing 1-2 primary and secondary amino groups and 2-3 alkoxy groups in the molecule, and the alkoxy groups are methoxy or ethoxy; the 2-3 functional aminoalkylsilane is specifically selected from the group consisting of gamma-aminopropyl trialkoxysilane (e.g., gamma-aminopropyl trimethoxysilane, gamma-aminopropyl triethoxysilane), gamma-aminopropyl methyl dialkoxysilane (e.g., gamma-aminopropyl methyldimethoxysilane, gamma-aminopropyl methyldiethoxysilane), N-butylaminopropyltrimethoxysilane, N-cyclohexyl-gamma-aminopropyl methyldialkoxysilane (e.g., N-cyclohexyl-gamma-aminopropyl methyldimethoxysilane), N-dimethyl-gamma-aminopropyl methyldialkoxysilane (e.g., N, N-dimethyl- γ -aminopropyl methyldimethoxy silane, N-dimethyl- γ -aminopropyl methyldiethoxy silane), N, N-dimethyl- γ -aminopropyl trialkoxysilane (e.g., N-dimethyl- γ -aminopropyl trimethoxysilane, N, N-dimethyl-gamma-aminopropyl triethoxysilane), piperazinylpropyl methyl dialkoxysilane (e.g., piperazinylpropyl methyl dimethoxy silane, piperazinylpropyl methyl diethoxy silane), piperazinylpropyl trialkoxysilane (e.g., piperazinylpropyl trimethoxysilane, piperazinyl propyl triethoxysilane), or the like.
Preferably, the fluorocarbon silane is silane with C 1～C8 perfluoroalkyl ethyl, perfluoroalkyl aryl (such as pentafluorophenyl) or perfluoro polyether group and 2-3 alkoxy groups in the molecule, and the alkoxy groups are methoxy or ethoxy; the fluorocarbon silane is specifically selected from heptadecafluorooctyl ethyl trialkoxysilane [ such as heptadecafluorooctyl ethyl trimethoxysilane (also known as 1H, 2H-perfluorodecyl trimethoxysilane), heptadecafluorooctyl ethyl triethoxysilane (also known as 1H, 2H-perfluorodecyl triethoxysilane) ] tridecyl fluorohexyl ethyl trialkoxysilane [ e.g., tridecyl fluorohexyl ethyl trimethoxysilane (also known as 1H, 2H-perfluorooctyl trimethoxysilane), tridecyl fluorohexyl ethyl triethoxysilane (also known as 1H, 2H-perfluorooctyl triethoxysilane) ] nine-fluoro-butyl ethyl trialkoxysilane [ e.g. nine-fluoro-butyl ethyl trimethoxysilane (also known as 1H, 2H-perfluoro-hexyl trimethoxysilane) nonafluorobutyl ethyl triethoxysilane (also known as 1H, 2H-perfluorohexyl triethoxysilane) ], 3-heptafluoroisopropoxypropyl trialkoxysilane (such as 3-heptafluoroisopropoxypropyl trimethoxysilane, 3-heptafluoroisopropoxypropyl triethoxysilane), trifluoropropyl methyl dialkoxysilane (such as trifluoropropyl methyl dimethoxy silane, trifluoropropyl methyl diethoxy silane), trifluoropropyl trialkoxysilane (such as trifluoropropyl trimethoxysilane, trifluoropropyl triethoxy silane), pentafluorophenyl trialkoxysilane (such as pentafluorophenyl trimethoxysilane, pentafluorophenyl triethoxy silane), perfluoropolyether-based trialkoxysilane having an average molecular weight Mn=1000 to 3000 (such as Mn=1000 to 3000 perfluoropolyether trimethoxysilane, mn=1000 to 3000 perfluoropolyether triethoxysilane), or the like, or a mixture of any 2 to 3 kinds.
Preferably, the phenylsilane is silane containing 1-2 phenyl groups and 2-3 alkoxy groups in the molecule, and the alkoxy groups are methoxy or ethoxy; the phenylsilane is specifically selected from one of phenyltrialkoxysilane (such as phenyltrimethoxysilane and phenyltriethoxysilane), diphenyldialkoxysilane (such as diphenyldimethoxy silane and diphenyldiethoxy silane) or a mixture of one of phenyltrialkoxysilane and one of diphenyldialkoxysilane in any proportion.
Preferably, the phenyl siloxane oligomer is a siloxane oligomer with the polymerization degree being less than 10, containing silicon hydroxyl groups or silicon alkoxy groups in the molecule, containing D, T phenyl siloxane units and having a linear, cyclic, dendritic or semi-closed cage-shaped structure; the phenyl siloxane oligomer is specifically selected from one or two of semi-closed cage phenyl heptapolysiloxane trisilyl, cyclic 1,3,5, 7-tetramethyl-1, 3,5, 7-tetraphenyl cyclotetrasiloxane, cyclic octaphenyl cyclotetrasiloxane, hydroxyl or alkoxy end-capped poly (di) phenyl siloxane (such as hydroxyl or alkoxy end-capped polydiphenyl siloxane), hydroxyl or alkoxy end-capped (di) phenyl siloxane-co- (di) alkyl siloxane (such as hydroxyl or alkoxy end-capped diphenyl siloxane-co-dialkyl siloxane, hydroxyl or alkoxy end-capped diphenyl siloxane-co-alkyl siloxane, hydroxyl or alkoxy end-capped phenyl siloxane-co-dialkyl siloxane), hydroxyl or alkoxy end-capped diphenyl siloxane-co-phenyl siloxane (also called phenyl siloxane-co-diphenyl siloxane), and the like oligomer, wherein the alkoxy is methoxy or ethoxy and the alkyl is-CH 3～-C18H37.
Preferably, the organic metal catalyst is an organotin catalyst, an organobismuth catalyst or an organozinc catalyst; the organic metal catalyst is specifically selected from one of dibutyl tin dilaurate, dibutyl tin diacetate, bismuth diisooctoate, zinc diisooctoate and the like.
Preferably, the organic solvents S1, S2, S4 may be the same or different, wherein S1, S2 are aromatic hydrocarbon, alcohol ether, ether ester, etc. solvents having good miscibility such as (fluoro) toluene (i.e. toluene or fluorotoluene), xylene, benzotrifluoride, propylene glycol methyl ether acetate (PMA), ethanol (i.e. ethanol or fluoroethanol), butanol, (fluoro) pentanol (i.e. pentanol or fluoropentanol), propylene glycol dimethyl ether (PDM), ethyl acetate (EAc), butyl Acetate (BA), etc. the solvents are selected from the group consisting of para-amino/phenyl fluorosilicone resin, epoxy styrene resin, amino modifier, epoxy modifier, etc.
Preferably, the organic solvent S3 and the organic solvents S1 and S2 may be the same or different, and S3 is selected from one or more solvents selected from alcohols, fluoroalcohols, alcohol ethers, alcohol ether esters, aromatic hydrocarbons and fluoroaromatics having good miscibility with an aminoalkylsilane, a fluorocarbon silane, a phenylsilane, a phenylsiloxane oligomer, etc., such as Ethanol (EA), trifluoroethanol, pentafluoropentanol, toluene (MB), fluorotoluene (FMB), benzotrifluoride, xylene, ethyl acetate (EAc), butyl Acetate (BA), ethylene glycol methyl ether, propylene glycol methyl ether, ethylene glycol methyl ether acetate, propylene glycol methyl ether acetate (PMA), etc.
Preferably, the organic solvent S3 is selected from one of mixed solvents such as fluoroarene-alcohol, fluoroarene-ester, fluoroarene-alcohol ether ester, and the like.
Preferably, the amino regulator is a small molecular compound or a large molecular compound (such as an oligomer) containing more than or equal to 2 amino groups in the molecule, and mainly comprises aliphatic diamine, alicyclic diamine, polyamine, polyether diamine, polyimide and the like; the amino regulator is specifically selected from one of ethylenediamine, diethylenetriamine, isophoronediamine, 4' -diamino dicyclohexylmethane, polyetheramine D230, polyetheramine D400, polyimide 650 (the amino content is equivalent to about 220 mgKOH/g) and the like.
Preferably, the epoxy group regulator is a substance containing 2-3 epoxy groups in the molecule; the epoxy group regulator is specifically selected from one of bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol A epoxy resin, 1, 6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, polypropylene glycol diglycidyl ether and the like.
Preferably, the epoxy styrene-acrylic resin (ESA) comprises a copolymer of an aliphatic C 1～C18 (meth) acrylate-co-styrene-co-allylepoxy-co-alkenyl functional monomer (i.e., a copolymer of an aliphatic C 1～C18 acrylate-co-styrene-co-allylepoxy-co-alkenyl functional monomer, or a copolymer of an aliphatic C 1～C18 methacrylate-co-styrene-co-allylepoxy-co-alkenyl functional monomer) or a copolymer of an alicyclic C 1～C18 (meth) acrylate-co-styrene-co-allylepoxy-co-alkenyl functional monomer, in the copolymer, the aliphatic or alicyclic C 1～C18 (meth) acrylate is methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isooctyl (meth) acrylate, dodecyl (meth) acrylate, myristyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, and, isobornyl (meth) acrylate and the like, the allyl epoxy compound is one or any 2 to 3 of Allyl Glycidyl Ether (AGE), 1, 2-epoxy-4-vinylcyclohexane, allyl polyether epoxy compound CH2＝CHCH2O(C2H4O)a(C3H6O)bCH2CH(O)CH2(, wherein a=0 to 3, b=2 to 6 and a+b=3 to 6), or one of glycidyl (meth) acrylate, and the alkenyl functional monomer is a polymerizable monomer compound containing a functional group such as hydroxyl group, C-Cl bond or siloxy group in the molecule and further containing a double bond, such as one or two of hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, 4-chloromethylstyrene, allyl hydroxyethyl ether (also known as hydroxyethyl allyl ether), allyl hydroxybutyl ether (also known as hydroxybutyl allyl ether), vinyl trialkoxysilane and the like.
Preferably, the copolymer in the epoxystyrene-acrylic resin (ESA) is cyclohexyl (meth) acrylate (CHMA) -co-Styrene (ST) -co-Allyl Glycidyl Ether (AGE) -co-hydroxyethyl acrylate (HEA), isobornyl (meth) acrylate (IBOMA) -co-Styrene (ST) -co-Allyl Glycidyl Ether (AGE) -co-hydroxyethyl acrylate (HEA), cyclohexyl (meth) acrylate (CHMA) -co-Styrene (ST) -co-Allyl Glycidyl Ether (AGE) -co-hydroxypropyl acrylate (HPA), isobornyl (OMA) -co-Styrene (ST) -co-Allyl Glycidyl Ether (AGE) -co-hydroxypropyl acrylate (HPA), C 1～C18 (meth) acrylate-co- (meth) cyclohexyl acrylate (CHMA) -co-styrene (CO-allyl glycidyl ether (ST) -co-hydroxypropyl Acrylate (AGE), C 1～C18 (meth) acrylate-co- (meth) acrylate Isobornyl (IBOMA) -co-Styrene (ST) -co-Allyl Glycidyl Ether (AGE) -co-hydroxypropyl acrylate (HPA), C 1～C18 (meth) acrylate-co- (meth) cyclohexyl acrylate (CHMA) -co-Styrene (ST) -co-Allyl Glycidyl Ether (AGE) -co-hydroxyethyl acrylate (HEA), C 1～C18 (meth) acrylate-co- (meth) acrylate Isobornyl (IBOMA) -co-Styrene (ST) -co-Allyl Glycidyl Ether (AGE) -co-hydroxyethyl acrylate (HEA), cyclohexyl (CHMA) -co-Styrene (ST) -co-Allyl Glycidyl Ether (AGE) -co-Vinyl Trialkoxysilane (VTS), isobornyl (IBMA) -co-styrene (IBE) -co-allyl glycidyl ether (VTS) -co-Vinyl Trialkoxysilane (VTS), cyclohexyl (meth) acrylate (CHMA) -co-Styrene (ST) -co-Allyl Glycidyl Ether (AGE) -co-3-chloro-2-hydroxypropyl (meth) acrylate (CHPA), C 1～C18 (meth) acrylate-co- (meth) Cyclohexyl (CHMA) -co-Styrene (ST) -co-Allyl Glycidyl Ether (AGE) -co-3-chloro-2-hydroxypropyl (meth) acrylate (CHPA), isobornyl (meth) acrylate (IBOMA) -co-Styrene (ST) -co-Allyl Glycidyl Ether (AGE) -co-3-chloro-2-hydroxypropyl (meth) acrylate (CHPA), C 1～C18 (meth) acrylate-co- (meth) isobornyl acrylate (IBOMA) -co-Styrene (ST) -co-Allyl Glycidyl Ether (AGE) -co-3-chloro-2-hydroxypropyl (meth) acrylate (CHPA), cyclohexyl (meth) acrylate (CHMA) -co-Styrene (ST) -co-1, 2-epoxy-2-hydroxy-cyclohexane (HEA) acrylate, isobornyl (meth) acrylate (IBOMA) -co-Styrene (ST) -co-1, 2-epoxy-4-vinylcyclohexane-co- (meth) acrylate hydroxyethyl, cyclohexyl (meth) acrylate (CHMA) -co-Styrene (ST) -co-1, 2-epoxy-4-vinylcyclohexane-co- (meth) acrylate Hydroxypropyl (HPA), isobornyl (IBOMA) -co-Styrene (ST) -co-1, 2-epoxy-4-vinylcyclohexane-co-Hydroxypropyl (HPA), cyclohexyl (meth) acrylate (CHMA) -co-Styrene (ST) -co-1, 2-epoxy-4-vinylcyclohexane-co-hydroxyethyl allyl ether (HEA), isobornyl (IBOMA) -co-Styrene (ST) -co-1, 2-epoxy-4-vinylcyclohexane-co-hydroxyethyl allyl ether, aliphatic C 1～C18 (meth) acrylate-co-methylcyclohexane-co-allyl glycidyl ether, aliphatic C 1～C18 (meth) acrylate-co-isobornyl methacrylate-co-styrene-co-allyl glycidyl ether-co-hydroxybutyl allyl ether, aliphatic or cycloaliphatic C 1～C18 (meth) acrylate-co-styrene-co-allyl glycidyl ether-co-hydroxyethyl allyl ether, aliphatic or cycloaliphatic C 1～C18 (meth) acrylate-co-styrene-co-allyl glycidyl ether-co-3-chloro-2-hydroxypropyl (meth) acrylate, aliphatic or cycloaliphatic C 1～C18 (meth) acrylate-co-Styrene (ST) -co-allyl polyether epoxy (a=0, b=3) -co-Vinyl Trialkoxysilane (VTS), aliphatic or cycloaliphatic C 1～C18 (meth) acrylate-co-styrene-co-allyl polyether epoxy (a=0, b=3) -co-3-chloro-2-hydroxypropyl (meth) acrylate, and the like, the alkoxy group being methoxy or ethoxy.
Preferably, the epoxy styrene-acrylic resin (ESA) has a solid content of 60 to 80wt% and an epoxy content (mole% based on the number of epoxy groups contained in each 100g of resin) of 0.1 to 0.3%, and can be synthesized by radical copolymerization of aliphatic/alicyclic C 1～C18 (meth) acrylate with styrene, allyl epoxy, alkenyl functional monomers, and the like, by a method ordered from manufacturers of the acrylic resins or referred to the literature (Wu. Synthesis of solvent-based fluoroacrylate resins and application study in fluorocarbon coatings [ M. University of shanxi science and technology, 2013).
Preferably, in the materials A and B, the wetting dispersant is BYK-161 or BYK-ATU.
Preferably, in the material a and the material B, the nano pigment filler is one selected from hydrophobically modified nano titanium dioxide (i.e. hydrophobic nano TiO 2), hydrophobically modified nano Al 2O3, hydrophobically modified nano F 3O4, hydrophobically modified silicon carbide, hydrophobically modified boron nitride, hydrophobically modified glass frit, phenyl modified nano silica sol, fluorocarbon-based modified nano silica sol, and the like.
The preparation method of the amino/phenyl fluorosilicone resin composite epoxy styrene-acrylic coating comprises the following steps:
Weighing components (namely amino/phenyl fluorosilicone resin, wetting dispersant, nano pigment filler and organic solvent S1) except the amino regulator in the material A and components (namely epoxy styrene-acrylic resin, wetting dispersant, nano pigment filler and organic solvent S2) except the epoxy regulator in the material B according to mass, respectively stirring and dispersing for 20-60 min by using high-speed dispersing equipment (the rotating speed is 1000-1500 r/min) to obtain a material A premix (without the amino regulator, the solid content is controlled to be 45-60 wt% by using the organic solvent S1) and a material B premix (without the epoxy regulator, the solid content is controlled to be 45-60 wt% by using the organic solvent S2), then the amino regulator in the material A or the epoxy regulator in the material B is used for regulating so that the molar ratio of the corresponding amino N-H bond (the material A) to the epoxy group (the material B) in the two premix materials of the material A and the material B is controlled to be 1-1.05:1 after regulation (or not regulation), the material A and the material B are uniformly mixed and then stirred and dispersed for 30-60 min (the rotating speed is 1000-1500 r/min), and finally air bubbles are removed, so that a uniform mixture (a compound system of the material A and the material B is obtained, wherein the mass ratio of the premix material A to the premix material B is 1:9-3:2), and the amino/phenyl fluorosilicone compound styrene-acrylic paint is recorded as APFS/ESA.
A preparation method of an amino/phenyl fluorosilicone resin composite epoxy styrene-acrylic coating comprises the following steps:
Taking APFS/ESA coating, and diluting with an organic solvent S5 (which can be the same as or different from S1 and S2) until the solid content is 40-45 wt% to obtain APFS/ESA working solution; and then placing the clean substrate on a sample table, uniformly coating APFS/ESA working solution on the surface of the substrate, leveling at 20-35 ℃ for 25-35 min after coating, pre-baking at 120-130 ℃ for 20-30 min, and curing at 150-180 ℃ for 15-30 min to obtain the APFS/ESA coating on the surface of the substrate.
Preferably, the substrate is selected from one of clean tin plate, aluminum alloy, steel plate, copper-clad circuit board, glass, ceramic, PC circuit board and the like; the coating mode is selected from one of spraying (for example, using a spray gun), brushing, rolling coating, wire rod coating (rod coating), spin coating, dipping and pulling method film forming and the like.
The beneficial effects of the invention are as follows:
According to the invention, an amino/phenyl fluorosilicone resin (APFS) and an epoxy styrene-acrylic resin (ESA) and other components are utilized to form a composite system, namely APFS/ESA coating, APFS/ESA coating is heated and cured, and in the coating curing process, the APFS resin in the material A contains low-surface-energy fluorocarbon radicals, and the ESA resin is concentrated in the surface, so that the cured composite fluorosilicone coating has good adhesive force, the surface of the coating is flat, and the coating shows excellent water resistance (the contact angle of water on the surface of the coating can reach 122.4 degrees), antifouling (the antifouling grade of the coating reaches 0-1 grade), weather resistance, salt fog resistance (the salt fog resistance of the coating reaches 1000-1200 h) and impact resistance, and the coating has good comprehensive application effect.
The invention combines APFS resin and nano pigment filler to prepare A material premix containing APFS resin, and combines styrene-acrylic resin (ESA in particular) containing epoxy groups in the structure and nano pigment filler to prepare B material premix containing epoxy groups; and then an amino regulator or an epoxy regulator is used for regulating, so that the mass ratio of N-H bonds contained in the material A to substances containing epoxy groups in the material B in the composite coating (which is compounded according to a certain proportion of the material A premix to the material B premix during use) is controlled to be 1-1.05:1, and APFS/ESA coating is obtained. The preparation method of the coating is based on the similarity compatibility of APFS resin structures and ESA resin structures (all contain phenyl groups) and the multipoint reactivity between the A material (containing amino groups) and the B material (containing epoxy groups) high molecular components, provides a new way for preparing compatible composite fluorosilicone coatings through thermal curing, and solves the problems that the coatings cannot be cured or have poor curing effect due to phase separation and layering of the traditional physically blended fluorosilicone resin coatings and aliphatic resin coatings.
Furthermore, the invention utilizes the hydrolytic polycondensation reaction of 2-3 functional amino alkyl silane and fluorocarbon alkyl silane, phenyl silane or phenyl siloxane oligomer to synthesize the siloxane copolymer with D, T amino alkyl siloxane, fluorocarbon alkyl siloxane, phenyl siloxane or phenyl siloxane oligomer and other chain links in the structure, and through the regulation and control of the phenyl and fluorocarbon alkyl carried in the structure, the APFS resin can realize the mutual solubility with ESA resin due to a large amount of phenyl groups, improve the problem that the traditional fluorine silicon resin cannot be mutually dissolved and compatible with aliphatic organic resin due to strong water and oil repellency, realize high light transmittance and easy curing in performance of the composite coating, and combine the network structure generated after the crosslinking of long-chain water and oil repellency and low surface energy fluorocarbon alkyl in APFS macromolecules through the accumulation of Van der Waals force and pi bond in the benzene ring in APFS macromolecules and the film formation, thereby effectively limiting the movement of the chain segment, further being beneficial to the roughening of the APFS coating after curing (being beneficial to the generation of super-hydrophobic, excellent in the performance of the water and the pollution and fog resistance of the traditional fluorine, the comprehensive resistance, the resistance of the silicone resin, and the like.
Detailed Description
The invention is further illustrated below with reference to examples, which are only intended to illustrate the invention and are not intended to limit the scope of the invention.
In view of the poor intersolubility of the traditional fluorosilicone resin and the aliphatic epoxy acrylic resin, the phase separation easily occurs in the blending process, the invention firstly designs and synthesizes the fluorosilicone resin with amino and phenyl bonded in a structure by utilizing a molecular design principle, and then composites the resin as an amino provider with styrene-acrylic resin (epoxy provider) containing epoxy groups in the structure, nano pigment and filler and the like to prepare the coating. Experimental tests show that the coating prepared by the composite coating not only realizes the effective curing (in view of the ring-opening reaction characteristics of amino groups and epoxy groups) of the amino/phenyl fluorosilicone resin modified epoxy styrene-acrylic coating and prepares the coating with good adhesive force, but also utilizes the advantages of large Si-F bond (bond energy 485 KJ/mol), si-O bond (422.5 KJ/mol) and Si-C bond (347 KJ/mol) bond energy and good ultraviolet resistance in the fluorosilicone resin structure contained in the composite coating, and can improve the performances of the coating such as impact resistance, ageing resistance, salt spray resistance and the like, so that the coating is used for functional coating or potting system and is hopeful to achieve the purpose of prolonging the service life of the coating.
In the examples, unless otherwise specified, the amount of the alkenyl functional monomer in the segment of the epoxy styrene-acrylic resin (ESA) is generally controlled to 1/10 to 2/10 of the molar amount of the epoxy alkenyl monomer, and the amount of styrene is generally 40% to 50% of the total mass of the monomers.
Example 1
(1) Synthesis of amino/phenyl fluorosilicone AFPS-1
10.0G of gamma-aminopropyl methyl dimethoxy silane (KBM 904, japanese Kogyo), 10.0g of heptadecafluoro octyl ethyl trimethoxy silane, 80.0g of phenylsilane mixture composed of phenyltrimethoxy silane (40.0 g) and diphenyldimethoxy silane (40.0 g) are added in sequence into a three-necked flask equipped with a thermometer, reflux condenser and stirrer, and stirred and mixed uniformly to obtain a total of 100.0g of mixture A; then 50% (50.0 g) of mixed solvent of fluorotoluene/ethanol (FMB: EA=1:1, w/w) based on the mass of the mixture A and 1% (1.0 g) of dibutyl tin dilaurate as an organic metal catalyst were added, deionized water in an amount equal to the molar amount of alkoxy groups in silane was added dropwise under stirring, and then the mixture was heated to 40 ℃ for hydrolysis polycondensation reaction for 8 hours. After the reaction, heating to about 85 ℃ and removing part of the solvent under normal pressure, and then decompressing and removing low boiling under the condition of P Watch (watch) about 0.85MPa to obtain about 73.11g of total transparent viscous liquid, namely the amino/phenyl fluorosilicone resin-gamma-aminopropyl methyl siloxane-co-heptadecafluorooctyl ethyl siloxane-co-phenyl siloxane-co-diphenyl siloxane, wherein the ammonia value (expressed by millimoles of amino contained in each gram of resin, the same applies hereinafter) is about 0.8371mmol/g, and the mixed solvent of fluorotoluene/butyl acetate (FMB: BA=1:1, w/w) is used for dilution until the solid content is about 60wt%, and is marked as AFPS-1 for standby.
(2) Preparation of amino/phenyl fluorosilicone resin composite epoxy styrene-acrylic coating APFS/ESA-1
A1, preparing a paint (paint, the following are prepared): 100.0g of amino/phenyl fluorosilicone resin APFS-1 with an ammonia value of about 0.8371mmol/g and a solid content of about 60wt%, 1.0g of wetting dispersant BYK-161, 50.0g of hydrophobic nano TiO 2 and 25.0gFMB/BA (1:1, w/w) mixed solvent are taken, stirred and dispersed for 30min by a dispersing machine with a rotating speed of 1500r/min, and then the solid content of the mixture is regulated by 46.0g of FMB/BA to be about 50wt%, so as to obtain a total 222.0g of mixture, namely A1 material, wherein the N-H content (calculated by the mole number of N-H bonds contained in 100g of paint, the same applies hereinafter) is about 0.0452%.
B1 (paint, the following are prepared) material: 100.0g of a mixed solvent of about 60% by weight of epoxy resin ESA-1-cyclohexyl methacrylate-co-styrene-co-allyl glycidyl ether-co-hydroxyethyl acrylate with a solid content of about 0.2513% by mole of epoxy groups contained in each 100g of the resin, 1.0g of a wetting dispersant BYK-161, 50.0g of hydrophobic nano TiO 2 and 25.0g of FMB/BA (1:1, w/w) was stirred and mixed uniformly, the mixture was stirred and dispersed for 30 minutes by using a dispersing machine with a rotational speed of 1500r/min, and then the solid content of the system was adjusted to about 50% by using 46.0g of the mixed solvent of FMB/BA (1:1, w/w) to obtain a total of 222.0g of a mixture, namely a B1 material, with an epoxy group content (the same applies below) of about 0.0679% by mole of epoxy groups contained in each 100g of the paint.
Preparing a composite coating: 60.0g of A1 material and 40.0g of B1 material (A1 material: B1 material mass ratio=3:2, N-H bond in A1 material: molar ratio of epoxy group in B1=1:1) are taken, stirred and mixed uniformly, stirred and dispersed for 30min by a high-speed dispersing machine with the rotating speed of 1000r/min, and defoamed under reduced pressure to obtain a uniform mixture, namely the amino/phenyl fluorosilicone resin composite epoxy styrene-acrylic coating, which is recorded as APFS/ESA-1.
(3) Coating preparation
Taking APFS/ESA-1 coating, and diluting with FMB/BA (1:1, w/w) mixed solvent until the solid content is about 40wt%, thus obtaining APFS/ESA-1 working solution; then, clean tinplate or glass is placed on a sample table, APFS/ESA-1 working solution is uniformly sprayed on the surface of a substrate by a spray gun, the substrate is leveled at room temperature for 30min, then baked at 120 ℃ for 30min and cured at 150 ℃ for 30min, and a APFS/ESA-1 coating sample is obtained.
Example 2
(1) Synthesis of amino/phenyl fluorosilicone AFPS-2
In a three-necked flask equipped with a thermometer, reflux condenser and stirrer, 35.0g of gamma-aminopropyl triethoxysilane (KH 550), 45.0g of a fluorocarbon-based silane mixture composed of pentafluorophenyl triethoxysilane (15.0 g) and trifluoropropyl methyldimethoxysilane (30.0 g), 20.0g of a methoxy-terminated diphenyl siloxane-co-methyl siloxane trimer having a degree of polymerization of about 3 (ph 2SiO:CH3SiO3/2 mer ratio=2:1, mol/mol) were successively added, and stirred and mixed to give a total of about 100.0g of a mixture A; then 200% (about 200.0 g) of FMB/EA (1:1, w/w) mixed solvent and 2.0% (about 2.0 g) of organic metal catalyst zinc diisooctoate are added in the mass of the mixture A, deionized water with the same molar quantity as alkoxy in silane is added dropwise under stirring, and then the mixture is heated to 80 ℃ for hydrolysis polycondensation reaction for 4 hours. After the reaction is finished, heating to about 85 ℃, firstly evaporating part of the solvent under normal pressure, then decompressing and removing low boiling under the condition of P Watch (watch) about 0.87MPa to obtain about 70.88g of total transparent viscous liquid, namely the amino/phenyl fluorosilicone resin-gamma-aminopropyl siloxane-co-pentafluorophenyl siloxane-co-trifluoropropyl methyl siloxane-co- (diphenyl siloxane-co-methyl siloxane) trimer, wherein the ammonia value is about 2.2305mmol/g, and diluting the mixed solvent of FMB/BA (1:1, w/w) to the solid content of about 80wt percent, and recording the mixture as AFPS-2 for later use.
(2) Preparation of amino/phenyl fluorosilicone resin composite epoxy styrene-acrylic coating APFS/ESA-2
And A2, preparing: 100.0g of amino/phenyl fluorosilicone resin APFS-2 with an ammonia value of about 2.2305mmol/g and a solid content of about 80wt%, 0.5g of wetting dispersant BYK-ATU, 25.0g of hydrophobic nano TiO 2 and 25.0g of FMB/BA (1:1, w/w) mixed solvent are taken, stirred and dispersed for 20min by a dispersing machine with a rotating speed of 1500r/min, and then the mixed solvent of 25.3g of FMB/BA (1:1, w/w) is used for regulating the solid content of the system to about 60wt%, so that a total of about 175.8g of mixture is obtained, namely the A2 material with an N-H bond content of about 0.20%.
And B2, preparing: 100.0g of epoxy styrene-acrylic resin ESA-2-butyl acrylate-co-cyclohexyl methacrylate-co-styrene-co-1, 2-epoxy-4-vinylcyclohexane-co-3-chloro-2-hydroxypropyl methacrylate with a solid content of about 80wt percent and an epoxy content of about 0.24 percent, 0.5g of wetting dispersant BYK-ATU, 25.0g of hydrophobic nano TiO 2 and 25.0g of mixed solvent of FMB/BA (1:1, w/w) are taken, stirred and mixed uniformly, the mixture is stirred and dispersed for 20min by a dispersing machine with a rotating speed of 1500r/min, the solid content of the mixed solvent of FMB/BA (1:1, w/w) is regulated to about 60wt percent, and the obtained total mixture is about 175.8g, namely the material B2, and the epoxy content is about 0.1092 percent.
Preparing a composite coating: taking 10.0g N-H bond content about 0.20% (containing N-H bond 0.02 mol) of A2 material, 90.0g of epoxy group content about 0.1092% (containing epoxy group 0.098 mol) of B2 material (A2 material: B2 material mass ratio=1:9), adding 4.77g of amino regulator polyether amine D230 into the A2 material to regulate so that the molar ratio of the N-H bond to epoxy group in the B2 material in the obtained system A2 is about 1.05:1, stirring and mixing the three materials uniformly, stirring and dispersing the mixture for 60min by using a high-speed dispersing machine with the rotating speed of 1000r/min, and carrying out vacuum defoaming to obtain a uniform mixture, namely the amino/phenyl fluorosilicone resin composite epoxy styrene-acrylic paint which is recorded as APFS/ESA-2.
(3) Coating preparation
Taking APFS/ESA-2 coating, and diluting with FMB/BA (1:1, w/w) mixed solvent until the solid content is about 45wt%, namely APFS/ESA-2 working solution; then, clean tinplate or glass is placed on a sample table, APFS/ESA-2 working solution is uniformly sprayed on the surface of a substrate by a spray gun, the substrate is leveled for 30min at room temperature, then baked for 20min at 130 ℃ and cured for 15min at 180 ℃ to obtain a APFS/ESA-2 coating sample.
Example 3
(1) Synthesis of amino/phenyl fluorosilicone AFPS-3
24.50G N-cyclohexyl-gamma-aminopropyl methyldimethoxysilane (KH-106), 35.0g pentafluorophenyl triethoxysilane, 40.5 g methoxy-terminated phenyl siloxane-co-diethyl siloxane tetramer having a degree of polymerization of about 4 (phSiO 3/2:(C2H5)2 SiO mer ratio=2:2, mol/mol) were added in sequence to a three-necked flask equipped with thermometer, reflux condenser, stirrer, and stirred to mix well to give a total of about 100.0g of mixture A; then 150% (about 150.0 g) of FMB/EA (1:1, w/w) mixed solvent and 2% (about 2.0 g) of organic metal catalyst bismuth diisooctoate are added in the mass of the mixture A, deionized water with the same molar quantity as alkoxy in silane is added dropwise under stirring, and then the mixture A is heated to 70 ℃ for hydrolysis polycondensation reaction for 6 hours. After the reaction, heating to about 85 ℃ and removing part of the solvent under normal pressure, decompressing and removing low boiling under the condition of P Watch (watch) about 0.90MPa to obtain about 83.82g of transparent viscous liquid, namely amino/phenyl fluorosilicone resin-N-cyclohexyl-gamma-aminopropyl methyl siloxane-co-pentafluorophenyl siloxane-co- (phenyl siloxane-co-diethyl siloxane) tetramer, wherein the ammonia value is about 1.1930mmol/g, and diluting with FMB/PMA (3:1, w/w) mixed solvent to the solid content of about 70wt percent, and recording as AFPS-3 for later use.
(2) Preparation of amino/phenyl fluorosilicone resin composite epoxy acrylate resin paint APFS/ESA-3
And A3, preparing: 100.0g of amino/phenyl fluorosilicone resin AFPS-3 with an ammonia value of about 1.1930mmol/g and a solid content of about 70wt%, 0.6g of wetting dispersant BYK-ATU, 30.0g of hydrophobic nano Al 2O3 and 25.0g of mixed solvent of FMB/PMA (3:1, w/w) are taken, stirred and dispersed for 30min by a dispersing machine with a rotating speed of 1500r/min, and then the mixed solvent of FMB/PMA (3:1, w/w) is used for regulating the solid content of the system to about 60wt%, so as to obtain about 167.67g of mixture in total, namely the A3 material with the N-H bond content of about 0.0498%.
And B3, preparing a material: 100.0g of epoxy styrene-acrylic resin ESA-3-isobornyl methacrylate-co-styrene-co-allyl glycidyl ether-co-vinyl trimethoxysilane with the solid content of about 70wt percent and the epoxy content of about 0.2196 percent, 0.6g of wetting dispersant BYK-ATU, 30.0g of hydrophobic nano Al 2O3 and 25.0g of mixed solvent of FMB/PMA (3:1, w/w) are taken, stirred and dispersed for 30min by a dispersing machine with the rotating speed of 1500r/min, and then the mixed solvent with the solid content of about 60wt percent is regulated by about 12.07g of mixed solvent of FMB/BA (3:1, w/w) to obtain about 167.67g of mixture in total, namely the B3 material with the epoxy content of about 0.0917 percent.
Preparing a composite coating: weighing an A3 material with the bond content of 50.0g N-H of about 0.0498 percent and a B3 material with the epoxy group content of about 0.0917 percent (A3 material: B3 material mass ratio=1:1), adding 2.1g of amino regulator polyether amine D400 into the A3 material to regulate the molar ratio of N-H bonds in the A3 material to epoxy groups in the B3 material to be about 1:1, stirring and mixing uniformly, stirring and dispersing for 30min by using a high-speed dispersing machine with the rotating speed of 1000r/min, and carrying out vacuum defoaming to obtain a uniform mixture, namely the amino/phenyl fluorosilicone resin composite epoxy styrene-acrylate coating which is APFS/ESA-3.
(3) Coating preparation
Taking APFS/ESA-3 coating, diluting with FMB/PMA (3:1, w/w) mixed solvent until the solid content is about 40wt%, namely APFS/ESA-3 spraying working solution; then, clean tinplate or glass is placed on a sample table, APFS/ESA-3 working solution is uniformly sprayed on the surface of a substrate by a spray gun, the substrate is leveled for 30min at room temperature, then baked for 30min at 125 ℃ and then cured for 20min at 160 ℃ to obtain a APFS/ESA-3 coating sample.
Example 4
(1) Synthesis of amino/phenyl fluorosilicone AFPS-4
15.0G of an aminoalkylsilane mixture of gamma-aminopropyl triethoxysilane (KH-550, 10.0 g) and N, N-dimethyl-gamma-aminopropyl methyldimethoxysilane (5.0 g), 35.0g of tridecyl fluorohexylethyltrimethoxysilane, 50.0g of a hydroxy-terminated diphenylsiloxane-co-hexadecylsiloxane oligomer having a degree of polymerization of about 3 (ph 2SiO:C16H33SiO3/2 mer ratio = 2:1, mol/mol) were successively added to a three-necked flask equipped with thermometer, reflux condenser, stirrer, and stirred to give a total of about 100.0g of mixture A; then 120% (about 120.0 g) of FMB/EA (1:1, w/w) mixed solvent and 1.5% (about 1.5 g) of organic metal catalyst zinc diisooctoate are added in the mass of the mixture A, deionized water with the same molar quantity as alkoxy in silane is added dropwise under stirring, and then the mixture A is heated to 70 ℃ for hydrolysis polycondensation reaction for 5 hours. After the reaction, heating to about 85 ℃ and removing part of the solvent under normal pressure, decompressing and removing low boiling under the condition of P Watch (watch) about 0.88MPa to obtain about 88.89g of transparent viscous liquid, namely the amino/phenyl fluorosilicon resin-gamma-aminopropyl siloxane-co-N, N-dimethyl aminopropyl ammopropyl methyl siloxane-co-tridecyl fluorohexyl ethyl siloxane-co- (diphenyl siloxane-co-hexadecyl siloxane) oligomer, wherein the ammonia value is about 0.9613mmol/g, and diluting the mixture with FMB/BA (1:1, w/w) mixed solvent to the solid content of about 70wt percent, and marking the mixture as AFPS-4 for later use.
(2) Preparation of amino/phenyl fluorosilicone resin composite epoxy styrene-acrylic coating APFS/ESA-4
And A4, preparing: 100.0g of amino/phenyl fluorosilicone resin AFPS-4 with an ammonia value of about 0.9613mmol/g and a solid content of about 70wt%, 1.0g of wetting dispersant BYK-161 with a solid content of about 25% and tridecanylethyl modified solvent nano silica sol (containing 25.0g of solid and serving as FMB/EA (1:1, w/w) as solvent) are taken, and stirred and dispersed for 30min by a dispersing machine with a rotating speed of 1500r/min to obtain a total of 201.0g of mixture, namely A4 material, wherein the N-H bond content is about 0.0256% and the solid content of the system is about 47.76wt%.
And B4, preparing: 100.0g of epoxy styrene-acrylic resin ESA-4-butyl methacrylate-co-stearyl acrylate-co-styrene-co-glycidyl methacrylate-co-hydroxyethyl allyl ether with a solid content of about 70wt percent and an epoxy content of about 0.1383 percent, 1.0g of wetting dispersant BYK-161 and 100.0g of solvent-type phenyl modified nano silica sol with a solid content of about 25 percent (25.0 g of solid content, wherein the solvent is FMB/EA (1:1, w/w)) are taken, and stirred and dispersed for 30 minutes by a dispersing machine with a rotating speed of 1500r/min to obtain a total of 201.0g of mixture, namely a B4 material, with the epoxy content of about 0.0482 percent and the solid content of about 47.76wt percent.
Preparing a composite coating: 45.0g of A4 material and 55.0g of B4 material (A4 material: B4 material mass ratio=9:11) are taken, 0.31g of amino regulator diethylenetriamine is added into the A4 material so that the molar ratio of N-H bond to epoxy group in the B4 material in the obtained system A4 is about 1:1, the mixture is stirred and uniformly mixed, the mixture is stirred and dispersed for 30min by a high-speed dispersing machine with the rotating speed of 1000r/min, and the mixture is defoamed under reduced pressure to obtain a uniform mixture, namely the amino/phenyl fluorosilicone resin composite styrene-acrylic coating, which is recorded as APFS/ESA-4.
(3) Coating preparation
Taking APFS/ESA-4 paint, and diluting with FMB/BA (1:1, w/w) mixed solvent until the solid content is about 40wt%, namely APFS/ESA-4 working solution; then, clean tinplate or glass is placed on a sample table, APFS/ESA-4 working solution is uniformly sprayed on the surface of a substrate by a spray gun, the substrate is leveled for 30min at room temperature, then baked for 30min at 120 ℃ and then cured for 30min at 150 ℃ to obtain a APFS/ESA-4 coating sample.
Example 5
(1) Synthesis of amino/phenyl fluorosilicone AFPS-5
The monomer mixture of example 3 (KH-106 and pentafluorophenyl triethoxysilane and methoxy-terminated phenyl siloxane-co-diethylsiloxane tetramer of about 4 in terms of polymerization) was replaced with a fluorocarbon-based silane of 25.0g of gamma-aminopropyl methyldimethoxysilane, 15.0g of tridecyl ethyltrimethoxysilane and 20.0g of 3-heptafluoro-isopropyl propyltrimethoxysilane, and a hydroxy-terminated oligomeric diphenylsiloxane trimer of about 3 in terms of polymerization of 10.0g of semi-closed cage phenyl heptapolysiloxane trisilanol and 30.0g of a hydroxy-terminated oligomeric diphenylsiloxane trimer of about 3, the synthesis of AFPS-3 in example 3 was carried out by hydrolytic polycondensation, solvent evaporation and reduced pressure to give a total of about 86.79g of amino/phenyl fluorosilicon-gamma-aminopropyl methylsiloxane-co-tridecyl-ethyl siloxane-co-phenyl heptapolysiloxane trisilanol-co-polydiphenylsiloxane trimer having an ammonia value of about 1.7640mmol/g (N-H3.5281 mol/g), and the mixed solvent of AFPS-1, 1:w/w was used as a solid solvent for dilution to about 70% by weight.
(2) Preparation of amino/phenyl fluorosilicone resin composite epoxy styrene-acrylic coating APFS/ESA-5
And A5, preparing: the corresponding paint was prepared by substituting 100g of AFPS-3 of example 3 with an ammonia value of 1.7640mmol/g and a solid content of about 70wt% of AFPS-5 (containing N-H0.247 mol) and the like, and the total amount was about 167.67g of the mixture, namely, A5, with a solid content of about 60wt% and an N-H bond content of about 0.1473%.
And B5, preparing: the ESA-3 resin of example 3 was replaced with 100.0g of an epoxystyrene-acrylic resin ESA-5-cyclohexyl methacrylate-co-styrene-co-allyl polyether epoxy compound CH2＝CHCH2O(C2H4O)a(C3H6O)bCH2CH(O)CH2(a＝0、b＝3)-co- -vinyltrimethoxysilane having a solids content of about 70% by weight and an epoxy content of about 0.20% by weight, and the corresponding paint was prepared in the same manner to give a total of about 167.67g of a mixture, namely, a B5 material having a solids content of about 60% by weight and an epoxy content of about 0.0835%.
Preparation of composite coating and preparation of coating: an amino/phenyl fluorosilicone composite styrene-acrylic coating (designated APFS/ESA-5) was prepared and APFS/ESA-5 coating samples were prepared by taking 50.0g N-H bond content of about 0.1473% (N-H0.0737 mol) in A5 material, 50.0g epoxy group content of about 0.0835% (epoxy group-containing 0.0418 mol) in A5 material (A5 material: B5 mass ratio=1:1), and adding 6.25g epoxy group regulator bisphenol A epoxy resin E51 to the B5 material to adjust the molar ratio of N-H bond in the A5 material to epoxy group in the resulting system B5 to 1:1, otherwise as in example 3.
The APFS/ESA-1-5 coating samples prepared in examples 1-5 were equilibrated at room temperature (25.+ -. 2 ℃ C.) at a relative humidity RH of 42% for 24 hours, and the following coating property measurements were performed:
Waterproof property of the coating surface: the water drop size is about 5 mu L, which is expressed by the static contact angle (theta H2O) of the water drop on the surface of the coating and measured by a JC-2000C1 static contact angle measuring instrument;
salt spray resistance of the coating: taking 5wt% NaCl aqueous solution as a test solution, and referring to GB/T10125-1997 standard, measuring by using YWX/Q-150 salt spray resistance tester;
Coating hardness: evaluation was performed with pencil hardness by reference to GB/T6739-1996 method;
impact resistance of the coating: with reference to GB/T1732-1993 standard, with an impact resistor;
coating adhesion: with reference to HGT3792-2014 standard, the level 0 is the best, as measured by an electric adhesion tester;
Ageing resistance of the coating (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;
antifouling properties of the coating: the fly ash is measured by the method specified in GB/T9780-1988 and is classified into five grades of 0, 1, 2, 3 and 4, and the grade 0 is the best.
In addition, the material A3 in example 3 was crosslinked and cured with neopentyl glycol diglycidyl ether (not compounded with the material B3) to give a coating sample reference-1 (amino fluorosilicone coating); in contrast, the material B3 of example 3 was crosslinked and cured (without compounding with the material A3) with polyetheramine D400 to give a coating sample reference-2 (epoxystyrene coating). The coating performance test results are shown in Table 1.
TABLE 1 amino/phenyl fluorosilicone resin composite epoxy styrene-acrylic coating Performance test and comparison results
* -No significant change in the surface of the coating; # yellowing or local chalking of the coating surface
As can be seen from Table 1, for the APFS/ESA-1-5 coating samples prepared in examples 1-5 of the present invention, the contact angle θ H2O of water on the surface of the coating reached 106.3-122.4 °, the salt spray resistance of the coating reached 1000-1200H, the hardness reached 2H-4H, the impact resistance reached 50-70 cm, the aging resistance reached 2500H (no change of the coating), and the antifouling grade generally reached 0-1 grade; compared with reference 2 (D400 crosslinked and cured epoxy styrene-acrylic coating), the APFS/ESA-1-5 coating has enhanced water resistance, soil resistance, impact resistance, salt spray resistance, aging resistance and other properties, and the adhesive force of the coating can still reach 0-1 level; and compared with reference 1 (neopentyl glycol diglycidyl ether crosslinked cured amino fluorosilicone coating), APFS/ESA-1-5 coating has better adhesive force. The result shows that the composite coating prepared based on APFS/ESA coating has the advantages of water resistance, stain resistance, salt spray resistance, aging resistance, excellent impact resistance, good adhesive force and good comprehensive application effect of the whole coating.

Claims (10)

1. An amino/phenyl fluorosilicone resin composite epoxy styrene-acrylic coating is characterized in that: the coating comprises a material A and a material B by mass; the material A comprises 100 parts of amino/phenyl fluorosilicone resin, 0.5-1.0 part of wetting dispersant, 25-50 parts of nano pigment and filler and more than or equal to 0 part of amino regulator; the material B comprises 100 parts of epoxy styrene-acrylic resin, 0.5-1.0 part of wetting dispersant, 25-50 parts of nano pigment filler and more than or equal to 0 part of epoxy regulator; the mass ratio of the N-H bond contained in the material A to the epoxy group contained in the material B is 1-1.05:1; the amino/phenyl fluorosilicone resin comprises a copolymer of amino alkyl siloxane-co-fluorocarbon alkyl siloxane-co-phenyl siloxane or a copolymer of amino alkyl siloxane-co-fluorocarbon alkyl siloxane-co-phenyl siloxane oligomer; in the copolymer, the amino alkyl is one of gamma-amino propyl, N-cyclohexyl-gamma-amino propyl, N-dimethyl-gamma-amino propyl and piperazinyl propyl, the fluorocarbon alkyl is one of C 1~C8 perfluoroalkyl ethyl, perfluor aryl and perfluor polyether, and the phenyl siloxane oligomer is a siloxane oligomer with the polymerization degree of <10, containing silicon hydroxyl or silicon alkoxy in the molecule and containing phenyl siloxane chain units and having a linear, annular, dendritic or semi-closed cage structure;
The amino/phenyl fluorosilicone resin is prepared by carrying out hydrolytic polycondensation on 2-3 functional amino alkyl silane, fluorocarbon alkyl silane and phenyl silane or phenyl siloxane oligomer in the presence of an organic metal catalyst and then diluting;
The epoxy styrene-acrylic resin comprises a copolymer of aliphatic or alicyclic C 1~C18 (methyl) acrylic ester-co-styrene-co-allyl epoxy compound-co-alkenyl functional monomer, wherein the aliphatic or alicyclic C 1~C18 (methyl) acrylic ester is single (methyl) acrylic ester or a plurality of (methyl) acrylic esters, the allyl epoxy compound is one of allyl glycidyl ether, 1, 2-epoxy-4-vinyl cyclohexane, allyl polyether epoxy compound CH2=CHCH2O(C2H4O)a(C3H6O)bCH2CH(O)CH2 or glycidyl (methyl) acrylate, a=0-3, b=2-6 and a+b=3-6 in the allyl polyether epoxy compound, and the alkenyl functional monomer is one or two of the following polymerizable monomers containing hydroxyl, C-Cl bond or siloxy and double bonds in the molecule: hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, 4-chloromethylstyrene, allyl hydroxyethyl ether, allyl hydroxybutyl ether, vinyl trialkoxysilane.
2. The amino/phenyl fluorosilicone resin composite epoxy styrene-acrylic coating according to claim 1, wherein: the solid content of the amino/phenyl fluorosilicone resin is 60% -80%, and the ammonia value is 0.8-2.4 mmol/g.
3. The amino/phenyl fluorosilicone resin composite epoxy styrene-acrylic coating according to claim 2, wherein: the 2-3 functional amino hydrocarbyl silane is silane containing primary amino and/or secondary amino and containing 2-3 alkoxy in the molecule, and the alkoxy is methoxy or ethoxy; the fluorocarbon silane is silane containing C 1~C8 perfluoroalkyl ethyl, perfluoroalkyl aryl or perfluoropolyether group in the molecule and containing 2-3 alkoxy, and the alkoxy is methoxy or ethoxy.
4. The amino/phenyl fluorosilicone resin composite epoxy styrene-acrylic coating according to claim 2, wherein: the phenylsilane is silane containing 1-2 phenyl groups and 2-3 alkoxy groups in the molecule, and the alkoxy groups are methoxy or ethoxy.
5. The amino/phenyl fluorosilicone resin composite epoxy styrene-acrylic coating according to claim 2, wherein: the organic metal catalyst is an organic tin catalyst, an organic bismuth catalyst or an organic zinc catalyst.
6. The amino/phenyl fluorosilicone resin composite epoxy styrene-acrylic coating according to claim 1, wherein: the amino regulator is one of the following compounds containing more than or equal to 2 amino groups in the molecule: aliphatic diamine, alicyclic diamine, diethylenetriamine, polyether diamine, polyimide.
7. The amino/phenyl fluorosilicone resin composite epoxy styrene-acrylic coating according to claim 1, wherein: the epoxy group regulator is selected from one of the following substances containing 2-3 epoxy groups: bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol A epoxy resin, 1, 6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, and polypropylene glycol diglycidyl ether.
8. The amino/phenyl fluorosilicone resin composite epoxy styrene-acrylic coating according to claim 1, wherein: the solid content of the epoxy styrene-acrylic resin is 60% -80%, and the epoxy content is 0.1% -0.3%.
9. A method for preparing the amino/phenyl fluorosilicone resin composite epoxy styrene-acrylic coating according to any one of claims 1-8, which is characterized in that: the method comprises the following steps:
adding an amino regulator into the premix of the material A or adding an epoxy regulator into the premix of the material B, so that the mass ratio of N-H bonds contained in the material A to epoxy groups contained in the material B in a compound system of the material A and the material B obtained after regulation and mixing is 1-1.05:1, wherein the premix of the material A is a mixture containing amino/phenyl fluorosilicone resin, a wetting dispersant and a nano pigment filler, and the premix of the material B is a mixture containing epoxy styrene-acrylic resin, a wetting dispersant and a nano pigment filler; or the A material premix and the B material premix are respectively used as the A material and the B material and are directly mixed, so that the mass ratio of N-H bonds contained in the A material to epoxy groups contained in the B material in the obtained A material and B material composite system is 1-1.05:1.
10. A preparation method of an amino/phenyl fluorosilicone resin composite epoxy styrene-acrylic coating is characterized by comprising the following steps of: the method comprises the following steps:
The amino/phenyl fluorosilicone resin composite epoxy styrene-acrylic coating is prepared by diluting the amino/phenyl fluorosilicone resin composite epoxy styrene-acrylic coating according to any one of claims 1-8 with a solvent, coating the coating on the surface of a substrate, leveling, heating and curing.
CN202310056346.2A 2023-01-16 2023-01-16 Preparation method of amino/phenyl fluorosilicone resin composite epoxy styrene-acrylic paint and coating Active CN116042091B (en)

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CN109897503A (en) * 2019-03-08 2019-06-18 胡志忠 A kind of normal temperature cure modifying epoxy resin by organosilicon coating and the preparation method and application thereof
CN111925525A (en) * 2020-08-28 2020-11-13 东莞市溢美材料科技有限公司 Preparation method and application of amino fluorosilicone resin and composition thereof
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CN114276732A (en) * 2022-01-18 2022-04-05 陕西科技大学 Antibacterial and anticorrosive paint and coating based on silver-doped quaternary ammonium-based nano silica sol and epoxy fluorine-containing acrylate resin
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CN103937357A (en) * 2014-03-28 2014-07-23 陕西科技大学 Preparation method of water-repellent hybrid fluorine-containing resin coating
CN109897503A (en) * 2019-03-08 2019-06-18 胡志忠 A kind of normal temperature cure modifying epoxy resin by organosilicon coating and the preparation method and application thereof
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