CN106519941B - Hydrophobic anti-corrosion hydridization protective coating of one kind and preparation method thereof - Google Patents
Hydrophobic anti-corrosion hydridization protective coating of one kind and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/61—Polysiloxanes
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- 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
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- 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
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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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
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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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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Abstract
The present invention relates to coating and preparation method thereof, and in particular to a kind of to have hydrophobic, corrosion-resistance characteristics hydridization protective coating and preparation method thereof.Coating of the present invention includes following component in parts by mass：5~90 parts of hybrid collosol, 2~50 parts of isocyanates polymer, 0.1~5 part of auxiliary agent, 0~60 part of diluent.The present invention is using in-situ polymerization and collosol and gel technology of preparing, hydrophobic fluoroalkyl and the epoxy group with reactivity and hydroxyl are introduced in hybrid collosol, pass through organic inorganic hybridization method, isocyano in isocyanates polymer in hybrid collosol epoxy group and hydroxyl co-crosslinking occurs and reacts, form three-dimensional netted compact texture, so that prepared coating has excellent corrosion resistance in relatively thin thickness, while also with the excellent comprehensive performance such as hydrophobicity is good, hardness is high, flexibility is good, strong adhesive force, heat resistance are good.
Description
Technical field
The present invention relates to coating and preparation method thereof, and in particular to a kind of that there is the protection of hydrophobic, corrosion-resistance characteristics hydridization to apply
Material and preparation method thereof.
Background technology
Common metal erosion means of defence has phosphatization, chromaking, plating, an anodic oxidation, and coating organic coating, inorganic
Coating etc., but these methods have some disadvantages, as phosphatization, chromaking, plating, anodic oxidation these types technique will produce
Largely contain heavy metal or acid, alkali waste water, causes serious environmental pollution；Organic coating is generally with carbon-to-carbon fluoropolymer resin (such as ring
Oxygen resin, acrylic resin, phenolic resin etc.) it is film forming matter, there are inflammable, hardness is low, coating is thicker, corrosion resistance and resistance to height
The shortcomings of poor performance at low temperatures, inorganic coating solidification temperature is higher, and shock resistance is poor, and coating is crisp and easy to crack, although hardness is high,
But lacking toughness, limit its application.
The characteristic using hybrid inorganic-organic materials prepared by sol-gel technique with safety and environmental protection, due to organic phase
With inorganic phase in the compound of atom or molecular level, interfacial interaction greatly improved, have more compared with traditional defense material
Special performance, thus as the hot spot in coating new material research field.Patent CN 102925053A are disclosed with diphenyl two
Methoxy silane, methyltrimethoxysilane, γ-glycidyl ether oxygen propyl trimethoxy silicane, phenyltrimethoxysila,e,
Propylene glycol monomethyl ether, organic siliconresin organic-inorganic hybrid coatings as main component；Patent CN 104559351A disclose one
Preparation method of the kind for the Organic-inorganic composite colloidal sol of metal aluminum sheet surface anticorrosion, by using high rigidity aluminium hydroxide pair
Nano-silicon dioxide particle is coated, and coating hardness and corrosion resistance are improved；Patent CN 101481553A are with nano-silica
SiClx colloidal sol and nano titanic oxide sol are complex sol, after silane coupling agent is modified and hydroxy silicon oil are coordinated to be prepared for one
The nano anticorrosive coating of kind normal temperature cure.Rivers Jin Lu et al. exist《Coatings industry》【2014,44 (5), 18-24】In report with just
Silester and methyltrimethoxysilane are hydrolysis presoma, and γ-glycidoxypropyltrimethoxysilane alkane is coupling
Agent has synthesized hybrid inorganic-organic epoxy resin by sol-gel method, and the impedance value of the coating of preparation is than aluminium alloy bare board
High two orders of magnitude.Fourth newly more et al. exists《Materials Science and Engineering journal》【2010,28 (1), 22-25】In report with positive silicon
Acetoacetic ester and γ-glycidoxypropyltrimethoxysilane alkane are Organic-inorganic composite anti-corrosion film prepared by presoma,
Salt-fog resistant time on aluminium sheet and steel plate is respectively 240h and 8h.Chen Gang et al. exists《Corrosion science and guard technology》【2010,22
(5), 418-422】In report using ethyl orthosilicate, methyltriethoxysilane, dimethoxydiphenylsilane as presoma,
Organosilicon/the SiO prepared using sol-gel method2Hybrid coating, coating have certain heat resistance and corrosion resistance.
In spite of the report for preparing hybrid coating above by sol-gel method, but the coating prepared by it mainly passes through
Si-O-Si key crosslinking curings, internal stress is big in film forming procedure, easy embrittlement, between silanol key or between silanol key and siloxy
The small molecule by-product that will produce of condensation reaction, inevitably generate micropore in the coating during effusion, cause
Crosslink density and compactness decline；And coating surface hydrophobic effect is bad, is in hydrophilic state more, ground is penetrated by micropore,
Corrosion resistance is caused to be deteriorated.
Invention content
In view of the deficiencies of the prior art, it is an object of the present invention to provide it is a kind of it is hydrophobic, anti-corrosion, thickness is thin, hardness is high, flexible
The hydridization protective coating and preparation method thereof of the good, strong adhesive force of property, excellent heat resistance.
Technical solution of the invention：The coating includes following component in parts by mass：
5~90 parts of hybrid collosol,
2~50 parts of isocyanates polymer,
0.1~5 part of auxiliary agent,
0~60 part of diluent；
By silane mixture monomer, hydrolysis obtains the hybrid collosol under the action of catalyst, and synthetic method is：It presses
5~80 parts of nano silicon dioxide dispersions, 10~100 parts of deionized waters, 0.5~5 part of catalyst are added at room temperature for mass parts
Into reactor, it is 20~98 DEG C to stir and keep reaction temperature, 100~1000 parts of silane mixture monomers of dropwise addition, reaction 2~
72h is then cooled to room temperature, and is removed byproduct of reaction through rotary evaporation, is obtained transparent, sticky hybrid collosol；
The silane mixture monomer is SiX by least one general structure4, at least one general structure be
R1 aR2 bSiX4-a-b, at least one general structure be R3 cR4 dSiX4-c-d, at least one general structure be R5 eR6 fSiX4-e-fSilane
Composition, wherein X are selected from Cl, methoxyl group, ethyoxyl, positive propoxy, isopropoxy, n-butoxy, tert-butoxy, phenoxy group, second
Acyloxy or propionyloxy, R1The organic group for being 3~18 for the total carbon atom number containing epoxy group, R2It is 1~6 for carbon atom number
Alkyl, R3The organic group for being 3~25 for fluorine atom number, R4The alkyl for being 1~4 for H or carbon atom number, R5Selected from carbon
Alkyl that atomicity is 1~16, the organic group or phenyl that are 2~16 containing carbon-carbon double bond and entire carbon atom number, R6It is selected from
Alkyl, phenyl or the H that carbon atom number is 1~16；A, 1 c, e, b, d, f are 0 or 1；
The catalyst be formic acid, acetic acid, propionic acid, succinic acid, 2- hydroxysuccinic acids, benzoic acid, benzene sulfonic acid, citric acid,
One or more combination in tartaric acid, salicylic acid, acetylsalicylic acid, sulfuric acid, nitric acid, phosphoric acid, boric acid, silicic acid；
Nano silicon dioxide grain size in the nano silicon dioxide dispersion is 5~500nm, solid content is 0.1~
50wt%.
The isocyanates polymer is HDI trimer, HDI biurets, MDI tripolymers, IPDI tripolymers, TDI trimerizations
One or more combination in body；
The auxiliary agent is substrate wetting agents, levelling agent, antifoaming agent, anticrater agent, drier, anti-sagging agent, thickener, resists
Scratch combination one or more in agent；
The diluent is methanol, ethyl alcohol, isopropanol, n-butanol, neopentyl alcohol, methyl acetate, ethyl acetate, acetic acid positive third
Ester, n-butyl acetate, glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether, ethylene glycol monobutyl ether, diethylene glycol list
Methyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol methyl ether acetate, carbon
One or more combination in dimethyl phthalate；
Preparation method includes the following steps：Isocyanates polymer is added in hybrid collosol under stirring, so
After auxiliary agent is added, be eventually adding diluent and stir evenly to get to hydrophobic anti-corrosion hydridization protective coating.
The present invention has the advantage that and advantageous effect：The present invention is prepared using in-situ polymerization with sol-gel technique hydrophobic
Anti-corrosion hybridization coating, has the following advantages that：(1) when in-situ polymerization, the hydroxyl and nanometer titanium dioxide that are generated after silane monomer hydrolysis
Condensation reaction occurs for the hydroxyl of silicon face, makes to connect by chemical bond between nano-particle and polymer, has both realized and received
Effective stable dispersion of rice corpuscles, while the nano-particle disperseed plays " anchor point " effect, by polymer segment " nail anchor " one
Rise, reduce the internal stress during film-forming, inhibit coating cracking, play enhancing, toughening effect, so that coating is had both height
Hardness and toughness；(2) contain a large amount of epoxy groups and silicone hydroxyl in hybrid collosol, it can be with the isocyano in isocyanates polymer
Co-crosslinking occurs and reacts the 3 D stereo reticular structure film to form high crosslink density, and without small molecule by-product in reaction process
It generates, micropore will not be caused to film, there is excellent corrosion resistance under relatively thin thickness；(3) when film-forming, hydridization is molten
Fluoroalkyl in glue, which has, to be migrated to surface layer and in the characteristic of surface enrichment, reduces coating surface free energy, and it is excellent to assign coating
Different hydrophobic property, shipwreck further improve corrosion resistance to be sprawled in moistened surface.
Specific implementation mode
Below by specific embodiment, the present invention will be further described, but protection scope of the present invention is not limited to
This variation that can readily occur in or is replaced it should be understood by a person of ordinary skill in the art that in range disclosed by the invention
It changes, should all cover within the pending claims of the present patent application.
Embodiment 1
Hydrophobic anti-corrosion hydridization protective coating provided in this embodiment, in parts by mass, including following raw material：
The preparation process of hydrophobic anti-corrosion hydridization protective coating includes the following steps：
Step (1)：20g nano silicon dioxide dispersions, 80g deionized waters, 1g acetic acid are added to reactor at room temperature
In, it is 80 DEG C to stir and keep temperature；
Step (2)：By 145g tetraethoxysilanes, 260g 3- glycidoxypropyltrimethoxysilanes alkane, 18g ten
After difluoro heptyl propyl trimethoxy silicane, 65g vinyltriethoxysilane are sufficiently mixed, it is added drop-wise to the reaction of step (1)
In device, reaction for 24 hours, then cools to room temperature, and removes byproduct of reaction through rotary evaporation, obtains transparent, sticky hybrid collosol；
Step (3)：By 3 parts of isocyanates polymers (by 2 parts of HDI trimers and 1 part of IPDI tripolymer under stirring
Composition) it is added in 9 parts of hybrid collosols, 0.2 part of auxiliary agent (being made of 0.1 part of levelling agent, 0.1 part of scratching resistant) is then added,
It is eventually adding 5 parts of diluents (being made of 1 part of ethyl alcohol, 4 parts of glycol monoethyl ethers) and stirs evenly to get to hydrophobic anti-corrosion hydridization
Protective coating.
Embodiment 2
Hydrophobic anti-corrosion hydridization protective coating provided in this embodiment, in parts by mass, including following raw material：
The preparation process of hydrophobic anti-corrosion hydridization protective coating includes the following steps：
Step (1)：36g nano silicon dioxide dispersions, 50g deionized waters, 1g phosphoric acid, 1g succinic acid are added at room temperature
Into reactor, it is 60 DEG C to stir and keep temperature；
Step (2)：By 245g tetramethoxy-silicanes, 126g2- (3,4- 7-oxa-bicyclo[4.1.0s base) ethyl triethoxysilane,
After 52g trifluoro propyls trimethoxy silane, 32g dimethoxydiphenylsilanes are sufficiently mixed, it is added drop-wise to the reactor of step (1)
In, 48h is reacted, is then cooled to room temperature, byproduct of reaction is removed through rotary evaporation, obtains transparent, sticky hybrid collosol；
Step (3)：20 parts of IPDI tripolymers are added in 80 parts of hybrid collosols under stirring, are then added 2 parts
Auxiliary agent (is made of) 1 part of antifoaming agent, 1 part of anticrater agent, be eventually adding 10 parts of propylene glycol methyl ether acetates and stir evenly to get
To hydrophobic anti-corrosion hydridization protective coating.
Embodiment 3
Hydrophobic anti-corrosion hydridization protective coating provided in this embodiment, in parts by mass, including following raw material：
The preparation process of hydrophobic anti-corrosion hydridization protective coating includes the following steps：
Step (1)：60g nano silicon dioxide dispersions, 30g deionized waters, 1g 2- hydroxysuccinic acids are added at room temperature
Into reactor, it is 95 DEG C to stir and keep temperature；
Step (2)：By 30g tetrachloro silicanes, 210 4 n-butoxy silanes, 400g 3- glycydoxy methyl
Diethoxy silane after 17 fluorine ruthenium triethoxysilanes of 26g, 280g dimethyl diethoxysilanes are sufficiently mixed, is added dropwise
Into the reactor of step (1), react 3h, then cool to room temperature, through rotary evaporation remove byproduct of reaction, obtain it is transparent,
Sticky hybrid collosol；
Step (3)：10 parts of TDI tripolymers are added in 36 parts of hybrid collosols under stirring, are then added 0.5 part
Antifoaming agent simultaneously stirs evenly to get to hydrophobic anti-corrosion hydridization protective coating.
Embodiment 4
Hydrophobic anti-corrosion hydridization protective coating provided in this embodiment, in parts by mass, including following raw material：
The preparation process of hydrophobic anti-corrosion hydridization protective coating includes the following steps：
Step (1)：10g nano silicon dioxide dispersions, 90g deionized waters, 3g citric acids are added to reaction at room temperature
In device, it is 45 DEG C to stir and keep temperature；
Step (2)：By 420 tetraethoxysilanes, 260g 3- glycidyl ether oxypropyltriethoxysilanes, 40g ten
After trifluoro octyl trimethoxy silane, 20g methyltrimethoxysilane are sufficiently mixed, it is added drop-wise in the reactor of step (1), instead
72h is answered, is then cooled to room temperature, byproduct of reaction is removed through rotary evaporation, obtains transparent, sticky hybrid collosol；
Step (3)：By 36 parts of isocyanates polymers (by 30 parts of HDI trimers and 6 parts of HDI contractings two under stirring
Urea forms) it is added in 48 parts of hybrid collosols, 1 part of auxiliary agent (being made of 0.5 part of antifoaming agent, 0.5 part of anti-sagging agent) is then added,
It is eventually adding 52 parts of diluents (being made of 4 parts of isopropanols, 18 parts of ethylene glycol monobutyl ethers and 30 parts of n-butyl acetates) and stirs equal
It is even to get to hydrophobic anti-corrosion hydridization protective coating
By the coating of above-described embodiment 1~4 be sprayed on as defined on base material, after film-forming, to be formed by film into
The following performance test of row：It is appearance, thickness, hardness, adhesive force, flexibility, corrosion resistance, heat resistance, artificial ageing resistance, resistance to molten
Agent wiping, water contact angle.Properties test result see the table below：
Claims (5)
1. a kind of hydrophobic anti-corrosion hydridization protective coating, which is characterized in that the coating includes following component in parts by mass：
5~90 parts of hybrid collosol,
2~50 parts of isocyanates polymer,
0.1~5 part of auxiliary agent,
0~60 part of diluent；
By silane mixture monomer, hydrolysis obtains the hybrid collosol under the action of catalyst, and synthetic method is：By quality
Part, 5~80 parts of nano silicon dioxide dispersions, 10~100 parts of deionized waters, 0.5~5 part of catalyst are added to instead at room temperature
It answers in device, it is 20~98 DEG C to stir and keep reaction temperature, and 100~1000 parts of silane mixture monomers are added dropwise, react 2~72h, so
Postcooling removes byproduct of reaction to room temperature, through rotary evaporation, obtains transparent, sticky hybrid collosol；
The silane mixture monomer is SiX by least one general structure4, at least one general structure be R1 aR2 bSiX4-a-b, extremely
A kind of few general structure is R3 cR4 dSiX4-c-d, at least one general structure be R5 eR6 fSiX4-e-fSilane composition, wherein X is selected from
Cl, methoxyl group, ethyoxyl, positive propoxy, isopropoxy, n-butoxy, tert-butoxy, phenoxy group, acetoxyl group or propionyl oxygen
Base, R1The organic group for being 3~18 for the total carbon atom number containing epoxy group, R2The alkyl for being 1~6 for carbon atom number, R3For fluorine original
The organic group that sub- number is 3~25, R4The alkyl for being 1~4 for H or carbon atom number, R5It is 1~16 selected from carbon atom number
Alkyl, the organic group or phenyl that are 2~16 containing carbon-carbon double bond and entire carbon atom number, R6It is 1~16 selected from carbon atom number
Alkyl, phenyl or H；A, 1 c, e, b, d, f are 0 or 1；
The catalyst is formic acid, acetic acid, propionic acid, succinic acid, 2- hydroxysuccinic acids, benzoic acid, benzene sulfonic acid, citric acid, winestone
One or more combination in acid, salicylic acid, acetylsalicylic acid, sulfuric acid, nitric acid, phosphoric acid, boric acid, silicic acid；
Nano silicon dioxide grain size in the nano silicon dioxide dispersion is 5~500nm, and solid content is 0.1~50wt%.
2. hydrophobic anti-corrosion hydridization protective coating according to claim 1, it is characterised in that：The isocyanates polymer is
One or more combination in HDI trimer, HDI biurets, MDI tripolymers, IPDI tripolymers, TDI tripolymers.
3. hydrophobic anti-corrosion hydridization protective coating according to claim 1, it is characterised in that：The auxiliary agent soaks for base material
One or more combination in agent, levelling agent, antifoaming agent, anticrater agent, drier, anti-sagging agent, thickener, scratching resistant.
4. hydrophobic anti-corrosion hydridization protective coating according to claim 1, it is characterised in that：The diluent is methanol, second
Alcohol, isopropanol, n-butanol, neopentyl alcohol, methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, glycol monoethyl ether,
Ethylene glycol monoethyl ether, ethylene glycol ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol list second
One or more combination in ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol methyl ether acetate, dimethyl carbonate.
5. a kind of method preparing hydrophobic anti-corrosion hydridization protective coating described in claim 1, which is characterized in that including following step
Suddenly：Isocyanates polymer is added in hybrid collosol under stirring, auxiliary agent is then added, is eventually adding diluent simultaneously
It stirs evenly to get to hydrophobic anti-corrosion hydridization protective coating.
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| CN108727943B (en) * | 2018-04-27 | 2021-06-08 | 中科院广州化学有限公司南雄材料生产基地 | Organic silicon fluorine modified epoxy resin, organic silicon fluorine sol furfural acetone composite modified epoxy coating material and preparation method thereof |
| CN108795128B (en) * | 2018-05-12 | 2021-06-22 | 浙江大学 | Double-layer compact metal anticorrosive coating formed by low-temperature sintering, and preparation method and application thereof |
| CN109868047A (en) * | 2019-03-15 | 2019-06-11 | 常州穗时新材料有限公司 | A kind of middle low-temperature setting organosilicon-modified acrylic polyurethane water-based paint and preparation method thereof |
| CN114230231B (en) * | 2022-02-24 | 2022-05-03 | 天津冶建特种材料有限公司 | Hybrid concrete curing-protecting agent and preparation method thereof |
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