CN114806392A - Super-hydrophilic anti-fouling self-repairing coating, preparation method of coating and coating - Google Patents
Super-hydrophilic anti-fouling self-repairing coating, preparation method of coating and coating 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
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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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
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3225—Polyamines
- C08G18/3228—Polyamines acyclic
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- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- 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
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
- C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
- C08G18/6225—Polymers of esters of acrylic or methacrylic acid
- C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
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- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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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
- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6648—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6651—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
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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
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
Abstract
The invention provides a super-hydrophilic anti-fouling self-repairing coating, a preparation method of the coating and a coating, wherein the preparation method of the coating comprises the following steps: step 1, adding a solvent into a reaction container, adding an initiator, polycaprolactone-modified acrylic resin, reactive sulfonate, polyester polyol and a chain extender into a reactor under the protection of inert gas, and reacting at the temperature of 85-100 ℃ for 8-48 h to obtain synthetic resin containing carbon-carbon double bonds, wherein the reactive functional group of the reactive sulfonate at least contains the carbon-carbon double bonds; and 2, under the protection of inert gas, adding an isocyanate curing agent into the reaction container, continuously stirring for 10-30 min, filtering, removing bubbles, blade coating and drying to prepare the super-hydrophilic anti-fouling self-repairing coating, coating the coating on the surface of an object, and curing to form a film to form the coating.
Description
Technical Field
The invention belongs to the technical field of coatings, and particularly relates to a super-hydrophilic anti-fouling self-repairing coating, a preparation method of the coating and the coating.
Background
At present, many stealth car clothes and color-changing car clothes at home and abroad have self-repairing functions, the self-repairing coatings greatly improve the glossiness and the self-repairing capability of the protective film, and are continuously used in other more fields such as airplanes, helicopters, fighters or wind power blades and the like, the protective field of the surfaces is discovered in practical use, the surface protective coatings are discovered to have excellent self-repairing performance and excellent super-hydrophilic performance, and the self-cleaning and anti-fouling properties are realized, so that the glossiness and the definition of the surfaces of the coatings are improved.
The macromolecular self-repairing material can provide energy for the material in the modes of heating, illumination and the like, and then realizes the re-repairing of weak bonds by means of the reversible characteristic of molecular chemical bonds of the material. In order to improve the self-repairing capability of high molecules, in the prior art, the self-repairing is improved by improving the chemical crosslinking density, for example, in CN 110713781A, the Japanese Sichuan chemistry introduces hydroxyl into acrylic resin and then mixes the hydroxyl with some polyester polyol, and then a substance with isocyanate groups is used for crosslinking the hydroxyl with the polyester polyol to form a network structure, so that a coating with an excellent self-repairing function is prepared; in CN109354689A, the Michael addition reaction is carried out on the aminopropyl double-end-capped polydimethylsiloxane and acrylic acid; raising the temperature of the obtained oligomer, and initiating a polycondensation reaction of a system; crosslinking and curing to obtain the novel organic silicon elastomer, thereby preparing the chemically crosslinked self-repairing (self-healing) elastomer. 3M in CN109765C adopts isocyanate to cure silicon-containing fluorine-containing polymer so as to prepare self-healing and scratch-resistant paint and the like.
In the existing technical scheme of the super-hydrophilic coating, a modified acrylic polymer is mostly adopted, and organic matters such as organosilane, organic fluorosilane, a silane coupling agent and the like are added to form a super-hydrophilic surface. The common organosilicon compound improves the water resistance, weather resistance, oxidation resistance, solvent resistance, ultraviolet light resistance, service life and the like of the adhesive layer to a certain extent, but the water resistance, the weather resistance and the like of the coating layer can not be completely satisfied because the microstructure on the surface of the adhesive layer is extremely easy to damage in the using process and stable super-hydrophilicity is difficult to maintain.
Disclosure of Invention
The invention is carried out to solve the problems and aims to provide a super-hydrophilic anti-fouling self-repairing coating, a preparation method of the coating and the coating. The coating prepared by the preparation method provided by the invention has super-hydrophilicity, dirt resistance, low haze, high light transmittance and high gloss.
The invention provides a preparation method of a super-hydrophilic anti-fouling self-repairing coating, which is characterized by comprising the following steps of:
step S1, adding a solvent into a reaction container, adding an initiator, polycaprolactone-modified acrylic resin, reactive sulfonate, polyester polyol and a chain extender into the reactor under the protection of inert gas, and reacting at the temperature of 85-100 ℃ for 8-48 h to obtain synthetic resin containing carbon-carbon double bonds, wherein the reactive functional group of the reactive sulfonate at least comprises the carbon-carbon double bonds;
and step S2, adding an isocyanate curing agent into the reaction container under the protection of inert gas, continuously stirring for 10-30 min, filtering, removing bubbles, blade-coating and drying to prepare the super-hydrophilic anti-fouling self-repairing coating.
The invention introduces reactive sulfonate on a polyurethane-acrylic resin chain, and the sulfonate has high hydrophilicity, so the hydrophilicity of the coating can be improved, and the reactive sulfonate can be subjected to polymerization reaction with unsaturated bond acrylic acid groups and isocyanate groups in resin base under certain conditions due to reactive functional groups in a molecular structure and is combined into a polymer molecular chain in a chemical bond mode to form stable chemical combination, and when the reactive sulfonate is contacted with water, a microstructure formed by the hydrophilic groups on the surface of the coating is not easy to damage, so that the hydrophilicity of the coating is further improved. The carbon-carbon double bond on the reactive sulfonate provides energy for the material under the photo initiation or thermal initiation, and then the material is re-repaired by re-bonding through the reversible characteristic of the chemical bond of the material molecule.
Further, the preparation method of the super-hydrophilic anti-fouling self-repairing coating provided by the invention can also have the following characteristics: the reactive functional group of the reactive sulfonate further comprises one or more of an acid group, an epoxy group, and a hydroxyl group. When the reactive sulfonate is introduced into the polyurethane-acrylic resin chain, acid groups, epoxy groups and hydroxyl groups in the reactive sulfonate participate in the reaction with acrylic groups and isocyanate groups in a resin base, and the reactive sulfonate is connected onto the resin chemical chain, so that the consumption of carbon-carbon double bonds can be reduced, the repairability of the introduced carbon-carbon double bonds in the sulfonate can be exerted to the maximum extent, and the self-repairing capability of the coating is improved.
Further, the preparation method of the super-hydrophilic anti-fouling self-repairing coating provided by the invention can also have the following characteristics: the reactive sulfonate is fatty alcohol-polyoxyethylene ether sulfonate, OH-R- (CH) 2 CH 2 O)n-SO 3 M, wherein n is 2-5, R is an unsaturated hydrocarbon group of 12-18, and M is a cation forming a salt; a sulfonate salt of an alkyl allyl succinate, a sulfonic acid salt of an alkyl allyl succinate,
wherein n is 0 to 100, R is an alkyl group of 10 or more, and M is a cation forming a salt. The fatty alcohol polyoxyethylene ether sulfonate and the alkyl allyl succinate sulfonate are introduced into the resin, so that the coating has good self-repairing capability and simultaneously keeps high elongation at break. Because the hydroxyl, epoxy and acid groups in the introduced reactive sulfonate participate in chemical bonding reaction with acrylic groups, isocyanate and the like in the resin to link the reactive sulfonate on a resin molecular chain, the consumption of carbon-carbon double bonds is reduced, so that the repairability of the unsaturated bond C-C can be exerted to the maximum extent, and the self-repairing capability of the coating is enhanced. And because the fatty alcohol polyoxyethylene ether sulfonate and the alkyl allyl succinate sulfonate both have long lengthThe hydrocarbon structure of the chain, therefore, enables the coating to have excellent elongation at break and enhances the flexibility of the polyurethane-acrylic resin.
Further, the preparation method of the super-hydrophilic anti-fouling self-repairing coating provided by the invention can also have the following characteristics: the super-hydrophilic anti-fouling self-repairing coating is prepared from the following raw materials in parts by mass: the mass fraction of the polycaprolactone modified acrylic resin is 1-20%, the mass fraction of the reactive sulfonate is 0.5-2%, the mass fraction of the polyester polyol is 5-25%, the mass fraction of the isocyanate curing agent is 5-39%, the mass fraction of the chain extender is 1-5%, the mass fraction of the initiator is 1-5%, and the mass fraction of the solvent is 20-85%.
Further, the preparation method of the super-hydrophilic anti-fouling self-repairing coating provided by the invention can also have the following characteristics: the polycaprolactone-modified acrylic resin is a mixture of polycaprolactone-modified hydroxyalkyl (meth) acrylate and hydroxyl-containing (meth) acrylate, and the mass ratio of the polycaprolactone-modified hydroxyalkyl (meth) acrylate to the hydroxyl-containing (meth) acrylate is (3-8): 1.
further, the preparation method of the super-hydrophilic anti-fouling self-repairing coating provided by the invention can also have the following characteristics: the polyester polyol is any one of polyester diol, polycaprolactone polyol and polycarbonate diol. The polycaprolactone polyol containing 2 or more hydroxyl groups is preferably selected.
Further, the preparation method of the super-hydrophilic anti-fouling self-repairing coating provided by the invention can also have the following characteristics: the isocyanate curing agent is one or more of Toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI), Hexamethylene Diisocyanate (HDI) and Lysine Diisocyanate (LDI).
Further, the preparation method of the super-hydrophilic anti-fouling self-repairing coating provided by the invention can also have the following characteristics: the initiator is at least one of organic peroxide, azo compounds, photoinitiators and cationic initiators. Specifically, the initiator is at least one of dibenzoyl peroxide, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, cumene hydroperoxide, azobisisobutyronitrile, azobisisoheptonitrile, 2-hydroxy-2-methyl-1-phenyl acetone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-propanone, 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide, ferrocenyl hexaflourophosphate or sulfonium hexafluoroantimonate.
Further, the preparation method of the super-hydrophilic anti-fouling self-repairing coating provided by the invention can also have the following characteristics: the chain extender is any one of low molecular weight polyol, polyamine or active hydrogen-containing compound.
Further, the preparation method of the super-hydrophilic anti-fouling self-repairing coating provided by the invention can also have the following characteristics: the solvent is any one of acetone, ethyl acetate, N-dimethylformamide, butanone, tetrahydrofuran, xylene, toluene, dichloromethane and butyl acetate.
The invention also provides a preparation method of the super-hydrophilic anti-fouling self-repairing coating, which is characterized by comprising the following steps of: the super-hydrophilic anti-fouling self-repairing coating is coated on the surface of an object, and the super-hydrophilic anti-fouling self-repairing coating is formed after the coating is cured to form a film. Specifically, after the super-hydrophilic anti-fouling self-repairing coating is coated on the surface of an object, drying is carried out for 2-10 minutes at the temperature of 35-110 ℃; aging for 1-7 days at 10-60 ℃.
The invention also provides a super-hydrophilic anti-fouling self-repairing coating, which is characterized in that: the super-hydrophilic anti-fouling self-repairing coating is prepared by adopting the preparation method of the super-hydrophilic anti-fouling self-repairing coating.
The invention has the following advantages:
the invention introduces reactive sulfonate on a polyurethane-acrylic resin chain, and the sulfonate has high hydrophilicity, so the hydrophilicity of the coating can be improved, and the reactive sulfonate can be polymerized with unsaturated bond acrylic acid group and isocyanate group in resin base under a certain condition due to reactive functional group in a molecular structure and is combined into a polymer molecular chain in a chemical bond mode to form stable chemical combination, and when the reactive sulfonate is contacted with water, the microstructure formed by the hydrophilic group on the surface of the coating is not easy to damage, so the hydrophilicity of the coating is further improved. The carbon-carbon double bond on the reactive sulfonate provides energy for the material under the photo initiation or thermal initiation, and then the material is re-repaired by re-bonding through the reversible characteristic of the chemical bond of the material molecule.
The coating prepared by the invention has super-hydrophilicity, dirt resistance, low haze, high light transmittance and glossiness, and has a satisfactory appearance.
Detailed Description
In order to make the technical means, creation characteristics, achievement purposes and effects of the present invention easy to understand, the following examples are adopted to specifically describe the super-hydrophilic anti-fouling self-repairing coating, the preparation method of the coating and the coating.
The super-hydrophilic anti-fouling self-repairing coating can be coated on the surface of a base material such as TPU, PVC, glass and the like to form a self-repairing coating, and the self-repairing coating can be coated on the surface of one side of the base material and can also be coated on the two surfaces of the base material.
Example 1A
In this example, the initiator was Azobisisoheptonitrile (AVBN), a cyasa chemistry. The polycaprolactone-modified acrylic resin is polycaprolactone-modified methacrylate and hydroxyethyl methacrylate, wherein the mass ratio of the polycaprolactone-modified methacrylate to the hydroxyethyl methacrylate is 12:4, and the polycaprolactone-modified polyhydroxyethyl methacrylate (HEMA-PCL) is a Xianqie organism; hydroxyethyl methacrylate (HEMA), alatin. The polyester polyol is polycaprolactone triol PCL2000, Basff. The reactive sulfonate was alkyl allyl succinate sulfonate, eleminiol JS20, sanyo japan. The chain extender is 1, 4-butanediol. The isocyanate curing agent is an HDI tripolymer curing agent, and the HDI tripolymer curing agent is Desmodur N3600 of Germany Corsikon group.
The preparation method of the super-hydrophilic anti-fouling self-repairing coating comprises the following steps:
step S1, adding 40g of ethyl acetate into a reaction container, adding 4g of Azodiisoheptanonitrile (AVBN), 12g of polycaprolactone-modified polyhydroxyethyl methacrylate (HEMA-PCL), 4g of hydroxyethyl methacrylate, 1.5g of alkyl allyl succinate sulfonate, 18.5g of polycaprolactone triol, 4g of 1 and 4-butanediol into the reactor under the protection of nitrogen, and reacting at the temperature of 90 ℃ for 10 hours to obtain the synthetic resin containing carbon-carbon double bonds.
And step S2, under the protection of inert gas, adding 10g of curing agent Desmodur N3600 and 6g of ethyl acetate into the reaction container, continuously stirring for 20min, filtering, removing bubbles, blade coating and drying to prepare the super-hydrophilic anti-fouling self-repairing coating.
And (3) coating the super-hydrophilic anti-fouling self-repairing coating on a TPU substrate through a wire rod, wherein the coating thickness is 12 microns, drying at the temperature of 85 ℃ for 2 minutes, and curing at the temperature of 50 ℃ for 48 hours to obtain the super-hydrophilic anti-fouling self-repairing coating.
Example 1B
The same portions of embodiment 1B as those of embodiment 1A are omitted from the same description, and embodiment 1B is different from embodiment 1A in that: the isocyanate curing agent is HXDI trimer curing agent, and the HXDI trimer curing agent is specifically TAKENATE D-120N of Mitsui chemical Co. In step S2, 5g of curing agent TAKENATED-120N and 11g of ethyl acetate were added.
Example 2A
The same portions of embodiment 2A as those of embodiment 1A are omitted from the same description, and embodiment 2A is different from embodiment 1A in that: the reactive sulfonate is fatty alcohol-polyoxyethylene ether sulfonate, and the fatty alcohol-polyoxyethylene ether sulfonate is produced by the Hubei Xingsheng Hengye technology.
Example 2B
The same portions of embodiment 2B as those of embodiment 2A are omitted from the same description, and embodiment 2B is different from embodiment 2A in that: the isocyanate curing agent is HXDI trimer curing agent, and the HXDI trimer curing agent is specifically TAKENATE D-120N of Mitsui chemical Co. In step S2, 5g of curing agent TAKENATED-120N and 11g of ethyl acetate were added.
Example 3A
The same portions of embodiment 3A as those of embodiment 1A are omitted from the same description, and embodiment 3A is different from embodiment 1A in that: the reactive sulfonate is styrene sulfonate, and the styrene sulfonate is a far-reaching fine chemical production.
Example 3B
The same portions of embodiment 3B as those of embodiment 3A are omitted from the same description, and embodiment 3B is different from embodiment 3A in that: the isocyanate curing agent is HXDI trimer curing agent, and the HXDI trimer curing agent is specifically TAKENATE D-120N of Mitsui chemical Co. In step S2, 5g of curing agent TAKENATED-120N and 11g of ethyl acetate were added.
Example 4
The same portions of embodiment 4 as those of embodiment 2A are omitted from the same description, and embodiment 4 is different from embodiment 2A in that: the initiator adopts dibenzoyl peroxide, the solvent adopts butyl acetate, the polyester polyol adopts polyester glycol, and the chain extender adopts ethylenediamine.
Example 5
The same portions of embodiment 5 as those of embodiment 2A are omitted from the same description, and embodiment 5 is different from embodiment 2A in that: the initiator adopts 1-hydroxycyclohexyl phenyl ketone, the solvent adopts acetone, and the polyester polyol adopts polycarbonate diol.
Example 6
In this embodiment, the polycaprolactone-modified acrylic resin is polycaprolactone-modified methacrylate and trihydroxy monoacrylic resin, and the mass ratio of the polycaprolactone-modified methacrylate to the trihydroxy monoacrylic resin is 4: 1.
The preparation method of the super-hydrophilic anti-fouling self-repairing coating comprises the following steps:
step S1, adding 70g of ethyl acetate into a reaction container, adding 1g of Azodiisoheptanonitrile (AVBN), 2g of polycaprolactone-modified polyhydroxyethyl methacrylate (HEMA-PCL), 0.5g of trihydroxy monoacrylic acid resin, 0.5g of fatty alcohol polyoxyethylene ether sulfonate, 5g of polycaprolactone triol, 4g of 1 and 4-butanediol into the reactor under the protection of nitrogen, and reacting at the temperature of 90 ℃ for 15 hours to obtain the synthetic resin containing carbon-carbon double bonds.
And step S2, under the protection of inert gas, adding 5g of curing agent Desmodur N3600 and 15g of ethyl acetate into the reaction container, continuously stirring for 30min, filtering, removing bubbles, blade coating and drying to prepare the super-hydrophilic anti-fouling self-repairing coating.
And (3) coating the super-hydrophilic anti-fouling self-repairing coating on a TPU substrate through a wire rod, wherein the coating thickness is 12 microns, drying at the temperature of 110 ℃ for 2 minutes, and curing at the temperature of 40 ℃ for 3 days to obtain the super-hydrophilic anti-fouling self-repairing coating.
Example 7
In this embodiment, the polycaprolactone-modified acrylic resin is polycaprolactone-modified methacrylate, hydroxyethyl methacrylate (HEMA), and trihydroxy monoacrylic resin, and the mass ratio of the polycaprolactone-modified methacrylate: hydroxyethyl methacrylate: trihydroxy monoacrylic resin ═ 16:1: 1.
The preparation method of the super-hydrophilic anti-fouling self-repairing coating comprises the following steps:
step S1, adding 30g of ethyl acetate into a reaction container, adding 5g of Azodiisoheptanonitrile (AVBN), 16g of polycaprolactone-modified polyhydroxyethyl methacrylate (HEMA-PCL), 1g of hydroxyethyl methacrylate (HEMA), 1g of trihydroxy monoacrylic acid resin, 2g of fatty alcohol polyoxyethylene ether sulfonate, 25g of polycaprolactone triol, 5g of 1 and 4-butanediol into the reactor under the protection of nitrogen, and reacting at the temperature of 100 ℃ for 8 hours to obtain the synthetic resin containing carbon-carbon double bonds.
And step S2, under the protection of inert gas, adding 10g of curing agent Desmodur N3600 and 5g of ethyl acetate into the reaction container, continuously stirring for 30min, filtering, removing bubbles, blade coating and drying to prepare the super-hydrophilic anti-fouling self-repairing coating.
And (2) coating the super-hydrophilic anti-fouling self-repairing coating on a TPU substrate through a wire rod, wherein the coating thickness is 12 microns, drying at the temperature of 35 ℃ for 10 minutes, and curing at the temperature of 60 ℃ for 1 day to obtain the super-hydrophilic anti-fouling self-repairing coating.
Example 8
In this embodiment, the polycaprolactone-modified acrylic resin is polycaprolactone-modified methacrylate, hydroxyethyl methacrylate (HEMA), and trihydroxy monoacrylic resin, and the mass ratio of the polycaprolactone-modified methacrylate: hydroxyethyl methacrylate: trihydroxy monoacrylic resin ═ 17:2: 1.
The preparation method of the super-hydrophilic anti-fouling self-repairing coating comprises the following steps:
step S1, adding 30g of ethyl acetate into a reaction container, adding 3g of Azodiisoheptanonitrile (AVBN), 17g of polycaprolactone-modified polyhydroxyethyl methacrylate (HEMA-PCL), 2g of hydroxyethyl methacrylate (HEMA), 1g of trihydroxy monoacrylic acid resin, 1.5g of fatty alcohol polyoxyethylene ether sulfonate, 20g of polycaprolactone triol, 3g of 1 and 4-butanediol into the reactor under the protection of nitrogen, and reacting at 85 ℃ for 48 hours to obtain the synthetic resin containing carbon-carbon double bonds.
And step S2, under the protection of inert gas, adding 15g of curing agent Desmodur N3600 and 7.5g of ethyl acetate into the reaction container, continuously stirring for 10min, filtering, removing bubbles, blade-coating and drying to prepare the super-hydrophilic anti-fouling self-repairing coating.
And (3) coating the super-hydrophilic anti-fouling self-repairing coating on a TPU substrate through a wire rod, wherein the coating thickness is 12 microns, drying at the temperature of 85 ℃ for 2 minutes, and curing at the temperature of 10 ℃ for 7 days to obtain the super-hydrophilic anti-fouling self-repairing coating.
Example 9
In this embodiment, the polycaprolactone-modified acrylic resin is polycaprolactone-modified methacrylate and hydroxyethyl methacrylate (HEMA), and the mass ratio of the polycaprolactone-modified methacrylate to the hydroxyethyl methacrylate is 4: 1.
The preparation method of the super-hydrophilic anti-fouling self-repairing coating comprises the following steps:
step S1, adding 70g of ethyl acetate into a reaction container, adding 1g of Azodiisoheptanonitrile (AVBN), 0.8g of polycaprolactone-modified polyhydroxyethyl methacrylate (HEMA-PCL), 0.2g of hydroxyethyl methacrylate (HEMA), 0.5g of fatty alcohol polyoxyethylene ether sulfonate, 7g of polycaprolactone triol, 1g of 1 and 4-butanediol into the reactor under the protection of nitrogen, and reacting at 85 ℃ for 30 hours to obtain the synthetic resin containing carbon-carbon double bonds.
And step S2, under the protection of inert gas, adding 5g of curing agent Desmodur N3600 and 14.5g of ethyl acetate into the reaction container, continuously stirring for 20min, filtering, removing bubbles, blade-coating and drying to prepare the super-hydrophilic anti-fouling self-repairing coating.
And (3) coating the super-hydrophilic anti-fouling self-repairing coating on a TPU substrate through a wire rod, wherein the coating thickness is 12 microns, drying at the temperature of 75 ℃ for 5 minutes, and curing at the temperature of 50 ℃ for 2 days to obtain the super-hydrophilic anti-fouling self-repairing coating.
Example 10
In this embodiment, the polycaprolactone-modified acrylic resin is polycaprolactone-modified methacrylate, hydroxyethyl methacrylate (HEMA), and trihydroxy monoacrylic resin, and the mass ratio of the polycaprolactone-modified methacrylate: hydroxyethyl methacrylate: trihydroxy monoacrylic resin ═ 16:1: 2.
The preparation method of the super-hydrophilic anti-fouling self-repairing coating comprises the following steps:
step S1, adding 18g of ethyl acetate into a reaction container, adding 1g of Azodiisoheptanonitrile (AVBN), 16g of polycaprolactone-modified polyhydroxyethyl methacrylate (HEMA-PCL), 1g of hydroxyethyl methacrylate (HEMA), 2g of trihydroxy monoacrylic acid resin, 1g of fatty alcohol polyoxyethylene ether sulfonate, 18g of polycaprolactone triol, 2g of 1 and 4-butanediol into the reactor under the protection of nitrogen, and reacting at the temperature of 85 ℃ for 30 hours to obtain the synthetic resin containing carbon-carbon double bonds.
And step S2, under the protection of inert gas, adding 39g of Desmodur N3600 curing agent and 2g of ethyl acetate into the reaction container, continuously stirring for 20min, filtering, removing bubbles, blade-coating and drying to prepare the super-hydrophilic anti-fouling self-repairing coating.
And (2) coating the super-hydrophilic anti-fouling self-repairing coating on a TPU substrate through a wire rod, wherein the coating thickness is 12 microns, drying at the temperature of 85 ℃ for 2 minutes, and curing at the temperature of 50 ℃ for 2 days to obtain the super-hydrophilic anti-fouling self-repairing coating.
Comparative example 1A
The same portions of comparative example 1A as those of example 1A are omitted from the description, and comparative example 1A is different from example 1A in that: no sulfonate was added, and in step S2, 7.5g of ethyl acetate was added.
Comparative example 1B
The same portions of comparative example 1B as those of comparative example 1A are omitted from the description, and comparative example 1B is different from comparative example 1A in that: the isocyanate curing agent is HXDI trimer curing agent, and the HXDI trimer curing agent is specifically TAKENATE D-120N of Mitsui chemical Co. In step S2, 5g of curative TAKENATED-120N and 12.5g of ethyl acetate were added.
Comparative example 2A
The same portions of comparative example 2A as those of example 1A are omitted from the description, and comparative example 2A is different from example 1A in that: the sulfonate added is a common dodecyl sulfonate, a nonreactive sulfonate.
Comparative example 2B
The same portions of comparative example 2B as those of comparative example 2A are omitted from the description, and comparative example 2B is different from comparative example 2A in that: the isocyanate curing agent is HXDI trimer curing agent, and the HXDI trimer curing agent is specifically TAKENATE D-120N of Mitsui chemical Co. In step S2, 5g of curing agent TAKENATED-120N and 11g of ethyl acetate were added.
The amounts of the raw materials used in the respective examples are shown in tables 1 and 2.
Table 1.
Table 2.
And (3) testing and characterizing:
the coatings prepared in each example and comparative example were subjected to self-repair ability evaluation, gloss test, haze test, visible light transmittance test, elongation at break test, stain resistance test, and water drop angle test. The test results are shown in table 3.
Self-repair capability evaluation: the specimens were evaluated by placing them at 60 ℃ for 5 minutes after 10 times of reciprocating brushes (manufactured by Suzuwang Co., Ltd.) at 25 ℃ to make a clear scratch. Among them, the score of repairing more than 80% of scratches is excellent, and the score of repairing less than 50% of scratches is poor among the scores of repairing 50% -80%.
Gloss testing: gloss is the gloss value of a protective film coated with a self-healing coating, according to the test standard GBT 8807-1988.
Haze: the haze is the haze value of the protective film coated with the self-repairing coating stuck on the glass substrate, and the test is carried out according to the equipment and the procedure of GB/T2410.
Visible light transmittance: the visible light spectrum range is 380 nm-780 nm. Samples were prepared using glass as the substrate and tested according to the equipment and procedure of GB/T2680.
Elongation at break: coating cracks of the protective film containing the self-repairing coating under the stretching of a mechanical stretching machine are observed, a stress-strain curve is obtained under the constant-speed force application, the elongation at break value is calculated, and the test is carried out according to the method and the device of GB/T1040.1-2006 and GB/T1040.3-2006.
Stain resistance chooses for use morning light black oily marking pen (specifically be morning light double-jie pen black) as the pollutant, writes respectively on scribbling the protection film of selfreparing coating, washs with the cotton flannel that has the alcohol after one minute, notes the vestige condition, and the vestige condition divide into: none, small amount, large amount. The test method refers to a scrawling resistance test method in appendix A of the scrawling-preventing and pasting-resisting coating for the building JG/T304-2011.
Water drop angle test a water drop angle tester was used to test the contact angle of a liquid drop on a self-healing layer with it.
Table 3.
Table 4.
As can be seen from the test results of tables 3 and 4, the water drop angle of the coating of comparative examples 1A and 1B, in which no reactive sulfonate was added, was much higher than that of the sulfonate-added coating, indicating that the sulfonate increased the hydrophilicity and soil resistance of the resin. Comparative examples 2A and 2B added with the common sulfonate, the water drop angle of the coating was reduced compared to comparative examples 1A and 1B, which shows that the common sulfonate improves the hydrophilicity of the resin coating to some extent, but the effect is slightly poor (the stability is poor because the common sulfonate depends only on the interaction force between groups rather than chemical bonds), and the self-repairing ability is also poor. In examples 3A and 3B, styrene sulfonate with only carbon-carbon double bonds as reactive functional groups is added, the water drop angle of the coating is reduced compared with comparative examples 1A and 1B, 2A and 2B, the hydrophilicity is improved, the dirt resistance is improved, and the self-repairing capability is improved, which indicates that sulfonate and resin matrix form stable chemical bonding, but the self-repairing capability is comparatively deviated (the self-repairing capability is influenced by more carbon-carbon double bonds consumed by the reaction), and in addition, the elongation at break of examples 3A and 3B is low, mainly because the introduced styrene sulfonate contains benzene rings and the carbon chains are shorter, the rigidity of the resin is increased. Examples 1A and 1B, and examples 2A and 2B, and examples 4 to 10, in which alkyl allyl succinate sulfonate having a carbon-carbon double bond and an acid group is added, and fatty alcohol polyoxyethylene ether sulfonate having a carbon-carbon double bond and an epoxy group is added, have low water drop angle, good anti-fouling ability, and strong self-repairing ability of the coating, and compared with examples 3A and 3B, the self-repairing ability is improved, which indicates that the reactive functional group and the resin base form stable chemical bonding, more carbon-carbon double bonds are retained, the retained carbon-carbon double bonds have stronger self-repairing ability under hot air or hot water, and in examples 1A, 1B, 2A, 2B, and examples 4 to 10, the difference of elongation at break is not great, but is greatly improved compared with examples 3A and 3B, indicating that different formulations and reaction conditions have little influence on the elongation at break of the coating, but the introduced long-chain alkyl structure can improve the elongation at break.
In addition, the haze of the coatings of examples 1A-3A, 1B-3B, and 4-10 is reduced and the light transmittance and gloss are improved relative to the coatings of comparative examples 1A, 1B, 2A, and 2B.
The above embodiments are preferred examples of the present invention, and are not intended to limit the scope of the present invention.
Claims (12)
1. A preparation method of a super-hydrophilic anti-fouling self-repairing coating is characterized by comprising the following steps:
step S1, adding a solvent into a reaction container, adding an initiator, polycaprolactone-modified acrylic resin, reactive sulfonate, polyester polyol and a chain extender into the reactor under the protection of inert gas, and reacting at the temperature of 85-100 ℃ for 8-48 h to obtain the resin containing carbon-carbon double bonds, wherein the reactive functional group of the reactive sulfonate at least comprises the carbon-carbon double bonds;
and step S2, adding an isocyanate curing agent into the reaction container under the protection of inert gas, continuously stirring for 10-30 min, filtering, removing bubbles, blade-coating and drying to prepare the super-hydrophilic anti-fouling self-repairing coating.
2. The preparation method of the super-hydrophilic anti-fouling self-repairing coating according to claim 1, characterized by comprising the following steps:
the reactive functional group of the reactive sulfonate further comprises one or more of an acid group, an epoxy group, and a hydroxyl group.
3. The preparation method of the super-hydrophilic anti-fouling self-repairing coating according to claim 2, characterized by comprising the following steps:
the reactive sulfonate is fatty alcohol-polyoxyethylene ether sulfonate, OH-R- (CH) 2 CH 2 O)n-SO 3 M, wherein n is 2-5, R is 12-18 unsaturated alkyl, and M is a cation forming a salt; a sulfonate salt of an alkyl allyl succinate, a sulfonic acid salt of an alkyl allyl succinate,
wherein n is 0 to 100, R is an alkyl group of 10 or more, and M is a cation forming a salt.
4. The preparation method of the super-hydrophilic anti-fouling self-repairing coating according to claim 1, characterized by comprising the following steps:
the super-hydrophilic anti-fouling self-repairing coating is prepared from the following raw materials in parts by mass: the mass fraction of the polycaprolactone modified acrylic resin is 1-20%, the mass fraction of the reactive sulfonate is 0.5-2%, the mass fraction of the polyester polyol is 5-25%, the mass fraction of the isocyanate curing agent is 5-39%, the mass fraction of the chain extender is 1-5%, the mass fraction of the initiator is 1-5%, and the mass fraction of the solvent is 20-85%.
5. The preparation method of the super-hydrophilic anti-fouling self-repairing coating according to claim 1, characterized by comprising the following steps:
the polycaprolactone-modified acrylic resin is a mixture of polycaprolactone-modified hydroxyalkyl (meth) acrylate and hydroxyl-containing (meth) acrylate, and the mass ratio of the polycaprolactone-modified hydroxyalkyl (meth) acrylate to the hydroxyl-containing (meth) acrylate is (3-8): 1.
6. the preparation method of the super-hydrophilic anti-fouling self-repairing coating according to claim 1, characterized by comprising the following steps:
the polyester polyol is any one of polyester diol, polycaprolactone polyol and polycarbonate diol.
7. The preparation method of the super-hydrophilic anti-fouling self-repairing coating according to claim 1, characterized by comprising the following steps:
the isocyanate curing agent is one or more of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate and lysine diisocyanate.
8. The preparation method of the super-hydrophilic anti-fouling self-repairing coating according to claim 1, characterized by comprising the following steps:
the initiator is at least one of organic peroxide, azo compounds, photoinitiators and cationic initiators.
9. The preparation method of the super-hydrophilic anti-fouling self-repairing coating according to claim 1, characterized by comprising the following steps:
the chain extender is any one of low molecular weight polyol, polyamine or active hydrogen-containing compound.
10. The preparation method of the superhydrophilic antifouling self-repairing coating of claim 1, wherein the method comprises the following steps:
the solvent is any one of acetone, ethyl acetate, N-dimethylformamide, butanone, tetrahydrofuran, xylene, toluene, dichloromethane and butyl acetate.
11. A preparation method of a super-hydrophilic anti-fouling self-repairing coating is characterized by comprising the following steps:
the super-hydrophilic anti-fouling self-repairing coating as claimed in any one of claims 1 to 10 is coated on the surface of an object, and after being cured into a film, the super-hydrophilic anti-fouling self-repairing coating is formed.
12. A super-hydrophilic anti-fouling self-repairing coating is characterized in that:
the super-hydrophilic anti-fouling self-repairing coating is prepared by the preparation method of the super-hydrophilic anti-fouling self-repairing coating as claimed in claim 11.
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| CN112409547A (en) * | 2020-12-01 | 2021-02-26 | 合肥小陀螺新材料科技有限公司 | Self-repairing waterborne polyurethane-polyacrylic acid emulsion and preparation method thereof |
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| JP2017133006A (en) * | 2016-01-25 | 2017-08-03 | ナトコ株式会社 | Urethane curable paint and use thereof |
| CN106867388A (en) * | 2017-01-18 | 2017-06-20 | 华南理工大学 | A kind of selfreparing anti-dazzle aqueous polyurethane coating and preparation method thereof |
| CN108752563A (en) * | 2018-05-24 | 2018-11-06 | 哈尔滨工业大学无锡新材料研究院 | Aqueous hyperbranched structurally-modified polyether polyols of one kind and preparation method thereof and selfreparing diffusing reflection coating composition |
| CN112409547A (en) * | 2020-12-01 | 2021-02-26 | 合肥小陀螺新材料科技有限公司 | Self-repairing waterborne polyurethane-polyacrylic acid emulsion and preparation method thereof |
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