CN110272679B - Ultraviolet light curing paint phenolic hyperbranched super-amphiphobic anticorrosive paint and preparation method thereof - Google Patents
Ultraviolet light curing paint phenolic hyperbranched super-amphiphobic anticorrosive paint and preparation method thereof Download PDFInfo
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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Abstract
The invention discloses an ultraviolet-curing paint phenolic hyperbranched super-amphiphobic anticorrosive paint and a preparation method thereof, and the ultraviolet-curing paint phenolic hyperbranched super-amphiphobic anticorrosive paint comprises the following steps: synthesizing urushiol glycidyl ether; synthesizing unsaturated urushiol-based hyperbranched polyether resin; f, synthesizing modified unsaturated urushiol-based hyperbranched polyether resin; and (3) preparing the ultraviolet-curing paint phenol-based hyperbranched super-amphiphobic anticorrosive paint. The unsaturated lacquer phenol-based hyperbranched polyether resin synthesized by the invention has the characteristics of low viscosity, good solubility, rich active functional groups, good compatibility with nano particles and the like, effectively solves the problems of high viscosity and slow curing of natural raw lacquer, and simultaneously has excellent physical and mechanical properties and chemical medium resistance. The method is simple to operate, environment-friendly and high in safety, and is beneficial to expanding the application of urushiol in the aspect of ultraviolet curing resin.
Description
Technical Field
The invention relates to the technical field of photocureable coatings, in particular to an ultraviolet photocureable paint phenolic hyperbranched super-amphiphobic anticorrosive coating and a preparation method thereof.
Background
Raw lacquer is a physiological secretion of lacquer trees, is a high-quality natural coating, is also a renewable high-molecular monomer with important development and application values, and the main film-forming substance of the raw lacquer is urushiol derivative with long side carbon chains. The raw paint film is hard and rich in gloss, has beautiful appearance, excellent physical and mechanical properties and heat resistance, and has been widely noticed by people for thousands of years. However, the raw lacquer has many disadvantages in the practical application process, such as long time consumption and harsh conditions of the raw lacquer film obtained by laccase-catalyzed oxidative polymerization. In addition, the natural raw paint film still has the defects of poor adhesive force and toughness, weak alkali resistance and aging resistance, high viscosity and the like, and the industrial application of the natural raw paint film is influenced. How to realize quick-drying and curing of the natural raw lacquer and develop the functional paint of the raw lacquer base meets the requirements of social and economic development and further expands the application field of the natural raw lacquer, and is an important challenge facing the raw lacquer industry.
In the field of quick-drying modified raw lacquer, literature reports that at present, there are three main methods for improving the drying speed of raw lacquer, namely, the quick-drying of raw lacquer is realized by using a drier, modifying an extract of raw lacquer, and using Ultraviolet (UV) curing and other technologies. The first two methods mainly solve the problem of curing the aged paint with reduced or inactivated laccase activity, and the curing time still needs several hours. In the UV curable raw lacquer coating, charm finds that the natural raw lacquer can be rapidly cured to form a film in about 2min without an external photoinitiator, and three reactive groups of urushiol, namely, a hydroxyl group on a benzene ring, a long-side unsaturated carbon chain and hydrogen on the benzene ring, all participate in photopolymerization reaction [ ACS Applied Materials & Interfaces, 2011, 3: 482-489]. Kazuhiro Taguchi et al mix urushiol with epoxy resin, photoinitiator, can realize fast drying of paint film under ultraviolet irradiation, open up a new channel for the utilization of raw paint in the paint field [ Progress in Organic Coatings, 2007, 58: 290-295].
The application of the UV curing technology greatly improves the raw lacquer drying efficiency. However, the effects of these methods are still somewhat different from the curing time(s) of UV-curable synthetic resin coatings. Although the light-cured coating can be prepared by directly utilizing the raw lacquer or the urushiol micromolecules, the curing speed is still slow due to low monomer functionality, the viscosity is high, and the construction is difficult. At present, the main components of the raw lacquer are modified and modified, and the research on high-reactivity and low-viscosity radiation-sensitive prepolymers is less, and the control on the prepolymer reaction activity by utilizing the unique diphenol characteristics of urushiol and the structures of unsaturated long side carbon chains and benzene rings is not paid due attention.
Currently, the film-forming materials of the photo-curing coating matrix are mainly linear polymers. In recent years, research on the use of hyperbranched polymers has been rapidly advancing. Hyperbranched polymers are highly branched tree-type polymers with three-dimensional stereo structure. Because the spherical rubber has a compact structure similar to a sphere, the chain entanglement phenomenon is not easy to occur among molecules, and the viscosity is less changed along with the increase of the molecular weight; a large number of active end groups are gathered on the surface of spherical molecules, and the curing speed is much higher than that of linear oligomers with similar molecular weight; the molecule has a dense branched structure, the shrinkage rate is small during curing, and the crosslinking density is high after curing, so that the light-cured oligomer is very suitable for being used as a light-cured oligomer matrix. At present, although many studies on hyperbranched photocurable prepolymers have been made, no studies and patent documents on the development of novel hyperbranched photocurable polymers from urushiol have been found.
Based on the background, the invention provides a simple and economic preparation method of a paint for constructing a super-amphiphobic anticorrosive surface, which is characterized in that natural urushiol is used as a raw material, low-viscosity and multifunctional urushiol-based hyperbranched unsaturated polyether resin is designed and prepared from the aspect of molecular design, a fluorine-containing compound is used for modifying and preparing a low-surface-energy film forming substance, chemically modified nanoparticles are used as a resin reinforcement body and a micro/nano hierarchical coarse structure is constructed, and a multifunctional coating with a lyophobic function and an anticorrosive function coupled is prepared through high-activity thiol-vinyl click photopolymerization reaction, so that the requirements of the modern paint industry are met.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provides an ultraviolet-cured phenolic hyperbranched super-amphiphobic anticorrosive paint and a preparation method thereof.
The invention aims to provide a preparation method of an ultraviolet-cured phenolic hyperbranched super-amphiphobic anticorrosive paint, which comprises the following steps:
Reacting urushiol with epoxy chloropropane and NaOH to obtain urushiol glycidyl ether;
step 2, synthesis of unsaturated urushiol-based hyperbranched polyether resin
Reacting urushiol glycidyl ether with a trihydroxymethyl compound under the action of a catalyst to obtain unsaturated urushiol-based hyperbranched polyether resin with an end group of hydroxyl;
step 3, synthesizing fluorine modified unsaturated lacquer phenolic hyperbranched polyether resin
Reacting unsaturated urushiol-based hyperbranched polyether resin with fluoro epoxy alkylate to obtain fluorine-modified unsaturated urushiol-based hyperbranched polyether resin;
step 4, preparing the ultraviolet light curing paint phenolic hyperbranched super-amphiphobic anticorrosive paint
Uniformly mixing fluorine-modified unsaturated urushiol-based hyperbranched polyether resin, a photoinitiator, a mercapto compound and a surface silane coupling agent-modified nano reinforcement to obtain an ultraviolet-cured urushiol-based hyperbranched super-amphiphobic anticorrosive coating;
wherein the mass ratio of the fluorine-modified unsaturated lacquer phenolic hyperbranched polyether resin, the photoinitiator, the mercapto compound and the surface silane coupling agent-modified nano reinforcement is 1: 1.0% -5.0%: 1.0% -10.0%: 0.5 to 5.0 percent.
Preferably, the specific reaction conditions of step 1 are as follows:
adding epoxy chloropropane into urushiol, heating to 30-50 ℃, adding NaOH, heating to 60-80 ℃, and reacting for 3-8 hours to obtain a crude product; carrying out post-treatment on the crude product to obtain urushiol glycidyl ether;
wherein the mol ratio of urushiol, epichlorohydrin and NaOH is 1: 2-8: 1 to 3.
The post-treatment steps of the crude product in the step 1 are as follows: and adding xylene and water into the crude product, washing, standing for layering, removing inorganic matters in a water layer, repeatedly washing until no chloride ion exists, and distilling under reduced pressure to obtain urushiol glycidyl ether.
Preferably, the specific reaction conditions of step 2 are as follows:
uniformly mixing urushiol glycidyl ether and a trihydroxymethyl compound, heating to 80-100 ℃, adding a catalyst, heating to 110-120 ℃, reacting for 1-6 hours, and performing post-treatment to obtain unsaturated urushiol hyperbranched polyether resin with hydroxyl as an end group;
wherein the molar ratio of the urushiol glycidyl ether to the trihydroxymethyl compound is 1: 2-10; the dosage of the catalyst is 1.0-5.0% of the mass of the urushiol glycidyl ether.
The post-treatment step in the step 2 is as follows: adding water with the temperature of 70 ℃ which is 2-4 times the volume of the reaction solution into the reaction solution, uniformly stirring, standing for layering, and removing the upper-layer liquid; washing with hot water for 3 times;
adding a mixed solution with the same mass as the product into the product washed by hot water, stirring, standing for layering, and separating a lower layer liquid; drying the lower layer liquid by magnesium sulfate, and then removing absolute ethyl alcohol to obtain unsaturated lacquer phenol-based hyperbranched polyether resin with the end group being hydroxyl;
the mixed solution consists of ethanol and water in a volume ratio of 1: 1.
Preferably, the catalyst is one of tetra-n-butyl ammonium chloride, tetra-n-butyl ammonium bromide, benzyltrimethyl ammonium chloride, benzyltriethyl ammonium chloride, triphenylphosphine, hexadecyl trimethoxy ammonium chloride, dibutyltin dilaurate, dodecyl benzyl ammonium chloride, dodecyl trimethoxy ammonium chloride, octadecyl dimethyl hydroxyethyl ammonium nitrate, octadecyl trimethyl ammonium chloride, octadecyl dimethyl benzyl ammonium chloride and octadecyl dimethyl hydroxyethyl ammonium perchlorate;
the trimethylol compound is trimethylolethane or trimethylolpropane.
Preferably, the specific reaction conditions of step 3 are as follows:
uniformly mixing unsaturated urushiol-based hyperbranched polyether resin, fluoro epoxy alkylate and an organic solvent, dispersing at a high speed of 50-100 ℃ under the protection of nitrogen, and removing the solvent after dispersion is finished to obtain fluorine-modified unsaturated urushiol-based hyperbranched polyether resin;
the mass ratio of the unsaturated urushiol-based hyperbranched polyether resin to the fluoro epoxy alkylate is 1: 0.5 to 1.
The fluorinated epoxyalkylate is one of perfluoro-2, 3-epoxy-2-methylpentane, perfluoropropylene oxide, 1, 4-bis (2',3' -epoxypropyl) perfluorobutane, 3- (perfluoron-butane) -1, 2-propylene oxide and 3- (perfluoron-octyl) -1, 2-propylene oxide;
the organic solvent is one of dichloromethane, chloroform, tetrahydrofuran, cyclohexanone, xylene, toluene, diethyl ether, acetone, trifluorotoluene, butanone, dimethylformamide, dioxane, dimethyl sulfoxide, N-methylpyrrolidone, diphenyl ether or anisole.
Preferably, the mercapto compound in step 4 is one of 1, 2-ethanedithiol, pentaerythritol tetrakis (3-mercaptopropionate), and tetramercaptopentane;
the photoinitiator is one of 2-hydroxy-2-methyl-1-phenyl acetone, 1-hydroxy-cyclohexyl benzophenone, 2-hydroxy-2-methyl-1-p-hydroxyethyl ether phenyl acetone, 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide, 2,4, 6-trimethylbenzoyl-ethoxy-phenyl phosphine oxide, bis (2,4, 6-trimethylbenzoyl) phenyl phosphine oxide and 4-p-toluene mercapto benzophenone.
Preferably, the preparation of the surface silane coupling agent modified nano reinforcement in the step 4 comprises the following steps:
s1, preparing a nano reinforcement suspension with the concentration of 0.5 mg/mL;
s2, dissolving a surface silane coupling agent which accounts for 5-20% of the weight of the nano reinforcement in absolute ethyl alcohol, adding the obtained solution into the nano reinforcement suspension prepared in S1, carrying out reflux reaction for 1.5h, aging at room temperature, carrying out centrifugal separation, washing and drying to obtain the nano reinforcement modified by the surface silane coupling agent;
the nano reinforcement is a silicon dioxide microsphere, an aluminum oxide microsphere, a titanium dioxide microsphere, a calcium carbonate microsphere, an iron oxide microsphere, graphene oxide, a carbon oxide nanotube, nano cellulose or a polymer nano microsphere with hydroxyl on the surface, and the particle size of the nano reinforcement is 50-1000 nm.
Preferably, the surface silane coupling agent is one of vinyl (2-methoxyethoxy) silane, (3-aminopropyl) -trimethoxysilane, (3-aminopropyl) triethoxysilane, 3-methylpropoxysilane, bis (dimethylamino) methylvinylsilane, vinyltriethoxysilane, vinyltrimethoxysilane and vinyltris (β -methoxyethoxy) silane.
The invention also provides a preparation method of the ultraviolet-curing paint phenolic hyperbranched super-amphiphobic anticorrosive paint.
Compared with the prior art, the invention has the beneficial effects that:
the invention utilizes two phenolic hydroxyl groups with strong activity on a urushiol benzene ring to perform epoxidation modification to prepare bifunctional epoxidized modified urushiol, the bifunctional epoxidized modified urushiol and a trifunctional alcohol monomer are subjected to polymerization reaction to prepare hydroxyl-terminated hyperbranched urushiol-based polyether resin, and the hydroxyl-terminated hyperbranched urushiol-based polyether resin is obtained by grafting a fluoro epoxy alkylate on the hydroxyl-terminated groups.
The unsaturated lacquer phenol-based hyperbranched polyether resin synthesized by the invention has the characteristics of low viscosity, good solubility, rich active functional groups, good compatibility with nano particles and the like, effectively solves the problems of high viscosity and slow curing of natural raw lacquer, and simultaneously has excellent physical and mechanical properties and chemical medium resistance.
The method has the advantages of simple process operation, environmental protection, low production cost and high safety, can become a new technology for industrially producing the modified raw lacquer anticorrosive paint, and is favorable for expanding the application of urushiol in the aspect of ultraviolet curing resin.
Drawings
FIG. 1 is an infrared spectrum of an unsaturated lacquer phenol-based hyperbranched polyether resin prepared in example 1;
FIG. 2 is a scanning electron microscope image of the phenol-based hyperbranched super-amphiphobic anticorrosive coating of the UV-curable paint prepared in example 1.
Detailed Description
In order to make the technical solutions of the present invention better understood and implemented by those skilled in the art, the present invention is further described below with reference to the following specific embodiments and the accompanying drawings, but the embodiments are not meant to limit the present invention.
Example 1
A preparation method of an ultraviolet light curing paint phenolic hyperbranched super-amphiphobic anticorrosive paint comprises the following steps:
Adding urushiol into a four-neck flask provided with a stirrer, a reflux condenser tube, a thermometer and a dropping funnel, wherein the molar ratio of the urushiol to the epichlorohydrin is 1:2, dripping epoxy chloropropane into a four-neck flask, stirring to uniformly mix, heating to 40 ℃, and then stirring under the condition that the molar ratio of urushiol to NaOH is 1:1, dropwise adding a NaOH solution with the concentration of 1mol/L according to the proportion of 1, heating to 60 ℃ after the dropwise adding is finished, and reacting for 4 hours at constant temperature to obtain a crude product; adding xylene and water into the crude product, washing, standing for layering, removing inorganic substances in a water layer, repeatedly washing until no chloride ion exists (the water layer is titrated by silver nitrate solution, and no chloride ion can be judged if no precipitate is generated), and distilling under reduced pressure to obtain urushiol glycidyl ether;
step 2, synthesis of unsaturated urushiol-based hyperbranched polyether resin
Urushiol glycidyl ether was reacted with trimethylolethane according to a 1:2, heating, adding tetra-n-butylammonium chloride which is 1.0 percent of the mass of urushiol glycidyl ether when the reaction temperature reaches 80 ℃, continuing heating to 110 ℃, reacting for 1h, adding deionized water which is 2 times of the volume of the reaction liquid and has the temperature of 70 ℃ into the reaction liquid, fully stirring, standing, and removing the upper liquid;
adding a mixed solution of ethanol and water with the mass ratio of 1:1 to the product which is obtained after hot water washing, fully stirring, standing for layering, removing the upper layer of liquid, and leaving the lower layer of liquid; adding excessive magnesium sulfate into the obtained lower layer liquid, drying to remove water in the product, and removing absolute ethyl alcohol to obtain unsaturated lacquer phenolic hyperbranched polyether resin with the terminal group being hydroxyl;
step 3, synthesizing fluorine modified unsaturated lacquer phenolic hyperbranched polyether resin
Adding unsaturated urushiol-based hyperbranched polyether resin, perfluoro-2, 3-epoxy-2-methylpentane with the mass being 50% of that of the unsaturated urushiol-based hyperbranched polyether resin and excessive xylene into a three-neck flask, dispersing at a high speed of 50 ℃ for 1h under the protection of nitrogen, wherein the high-speed dispersion rate is 1000r/min, and removing the xylene to obtain the fluorine-modified unsaturated urushiol-based hyperbranched polyether resin coating;
step 4, preparing the ultraviolet light curing paint phenolic hyperbranched super-amphiphobic anticorrosive paint
Adding 100 parts by weight of nano silicon dioxide microspheres with the particle size of 50nm into deionized water, and ultrasonically dispersing for 1h to prepare suspension with the concentration of 0.5 mg/mL; dissolving vinyl (2-methoxyethoxy) silane which accounts for 5 percent of the weight of the nano silicon dioxide microspheres in absolute ethyl alcohol, adding the obtained solution into the suspension, carrying out reflux reaction for 1.5h, aging at room temperature, carrying out centrifugal separation, washing, and then placing the obtained product in a vacuum drying oven for drying to obtain a nano reinforcement modified by a surface silane coupling agent;
and (3) uniformly mixing the fluorine modified unsaturated urushiol hyperbranched polyether resin obtained in the step (3) with 2-hydroxy-2-methyl-1-phenyl acetone with the mass being 1.0%, 1, 2-ethanedithiol with the mass being 5.0% and a surface silane coupling agent modified nano reinforcement with the mass being 5.0% to obtain the ultraviolet curing urushiol hyperbranched super-amphiphobic anticorrosive paint.
Example 2
A preparation method of an ultraviolet light curing paint phenolic hyperbranched super-amphiphobic anticorrosive paint comprises the following steps:
Adding urushiol into a four-neck flask provided with a stirrer, a reflux condenser tube, a thermometer and a dropping funnel, wherein the molar ratio of the urushiol to the epichlorohydrin is 1:3, dropwise adding epoxy chloropropane into a four-neck flask according to the proportion of 3, stirring to uniformly mix, heating to 50 ℃, dropwise adding 1mol/L NaOH solution according to the molar ratio of urushiol to NaOH of 1:2 under the stirring condition, heating to 70 ℃ after dropwise adding, reacting for 5 hours at constant temperature to obtain a crude product, adding xylene and water into the crude product, washing, standing for layering, removing inorganic substances in a water layer, repeatedly washing until no chloride ion exists, and distilling under reduced pressure to obtain urushiol glycidyl ether;
step 2, synthesis of unsaturated urushiol-based hyperbranched polyether resin
Adding urushiol glycidyl ether and trimethylolpropane into a four-neck round-bottom flask according to a molar ratio of 1:3, heating, adding tetra-n-butylammonium bromide with the mass of 2.0 percent of the urushiol glycidyl ether when the reaction temperature reaches 90 ℃, continuously heating to 120 ℃, after reacting for 2 hours, adding deionized water with the temperature of 70 ℃ which is 2 times the volume of the reaction liquid into the reaction liquid, fully stirring, standing, and removing the upper layer liquid;
adding a mixed solution of ethanol and water with the mass ratio of 1:1 to the product which is obtained after hot water washing, fully stirring, standing for layering, removing the upper layer of liquid, and leaving the lower layer of liquid; adding excessive magnesium sulfate into the obtained lower layer liquid, drying to remove water in the product, and removing absolute ethyl alcohol to obtain unsaturated lacquer phenolic hyperbranched polyether resin with the terminal group being hydroxyl;
step 3, synthesizing fluorine modified unsaturated lacquer phenolic hyperbranched polyether resin
Adding unsaturated urushiol-based hyperbranched polyether resin, perfluoroepoxypropane with the mass being 70% of that of the unsaturated urushiol-based hyperbranched polyether resin and excessive chloroform into a three-neck flask, dispersing at a high speed of 2000r/min for 2h at 70 ℃ under the protection of nitrogen, and removing chloroform as a solvent to obtain a fluorine-modified unsaturated urushiol-based hyperbranched polyether resin coating;
step 4, preparing the ultraviolet light curing paint phenolic hyperbranched super-amphiphobic anticorrosive paint
Adding 100 parts by weight of graphene oxide with the particle size of 100nm into deionized water, and ultrasonically dispersing for 1h to prepare a suspension with the concentration of 0.5 mg/mL; dissolving (3-aminopropyl) -trimethoxy silane which accounts for 5 percent of the weight of the graphene oxide in absolute ethyl alcohol, adding the obtained solution into the suspension, carrying out reflux reaction for 1.5h, aging at room temperature, carrying out centrifugal separation, washing, and then placing the obtained product in a vacuum drying oven for drying to obtain the surface silane coupling agent modified nano reinforcement;
and (3) uniformly mixing the fluorine-modified unsaturated urushiol hyperbranched polyether resin obtained in the step (3), 1-hydroxy-cyclohexyl benzophenone with the mass being 1.0%, pentaerythritol tetra (3-mercaptopropionate) ester with the mass being 5.0% and a surface silane coupling agent-modified nano-enhancer with the mass being 0.5% to obtain the ultraviolet curing urushiol hyperbranched super-amphiphobic anticorrosive paint.
Example 3
A preparation method of an ultraviolet light curing paint phenolic hyperbranched super-amphiphobic anticorrosive paint comprises the following steps:
Adding urushiol into a four-neck flask provided with a stirrer, a reflux condenser tube, a thermometer and a dropping funnel, wherein the molar ratio of the urushiol to the epichlorohydrin is 1:4, dropwise adding epoxy chloropropane into a four-neck flask according to the proportion of 4, stirring to uniformly mix, heating to 30 ℃, dropwise adding 1mol/L NaOH solution according to the molar ratio of urushiol to NaOH of 1:2 under the stirring condition, heating to 80 ℃ after dropwise adding, and reacting at constant temperature for 4 hours to obtain a crude product; adding xylene and water into the crude product, washing, standing for layering, removing inorganic matters in a water layer, repeatedly washing until no chloride ion exists, and distilling under reduced pressure to obtain urushiol glycidyl ether;
step 2, synthesis of unsaturated urushiol-based hyperbranched polyether resin
Adding urushiol glycidyl ether and trimethylolethane into a four-neck round-bottom flask according to a molar ratio of 1:3, heating, adding benzyltriethylammonium chloride which is 4.0 percent of the mass of the urushiol glycidyl ether when the reaction temperature reaches 100 ℃, continuously heating to 120 ℃, reacting for 6 hours, adding deionized water which is 3 times of the volume of the reaction solution and has the temperature of 70 ℃ into the reaction solution, fully stirring, standing, and removing the upper layer of liquid;
adding a mixed solution of ethanol and water with the mass ratio of 1:1 to the product which is obtained after hot water washing, fully stirring, standing for layering, removing the upper layer of liquid, and leaving the lower layer of liquid; adding excessive magnesium sulfate into the obtained lower layer liquid, drying to remove water in the product, and removing absolute ethyl alcohol to obtain unsaturated lacquer phenolic hyperbranched polyether resin with the terminal group being hydroxyl;
step 3, synthesizing fluorine modified unsaturated lacquer phenolic hyperbranched polyether resin
Adding unsaturated urushiol-based hyperbranched polyether resin, 1, 4-bis (2',3' -epoxypropyl) perfluorobutane with the mass equivalent to 80% of that of the unsaturated urushiol-based hyperbranched polyether resin and excessive toluene into a three-neck flask, dispersing at a high speed of 1000r/min for 3h at 80 ℃ under the protection of nitrogen, and removing the toluene to obtain a fluorine-modified unsaturated urushiol-based hyperbranched polyether resin coating;
step 4, preparing the ultraviolet light curing paint phenolic hyperbranched super-amphiphobic anticorrosive paint
Adding 100 parts by weight of nano calcium carbonate microspheres with the particle size of 1000nm into deionized water, performing ultrasonic dispersion for 1 hour to prepare a suspension with the concentration of 0.5mg/mL, dissolving 5% of vinyltriethoxysilane by weight of the nano calcium carbonate microspheres in absolute ethyl alcohol, adding the suspension into the suspension, performing reflux reaction for 1.5 hours, aging at room temperature, performing centrifugal separation, washing, and then placing in a vacuum drying oven for drying to obtain a nano reinforcement modified by a surface silane coupling agent;
and (3) uniformly mixing the fluorine-modified unsaturated urushiol hyperbranched polyether resin obtained in the step (3), 1.0% by mass of 2-hydroxy-2-methyl-1-p-hydroxyethyl ether phenyl acetone, 5.0% by mass of tetramercapto pentanes and 1.0% by mass of surface silane coupling agent modified nano reinforcer to obtain the ultraviolet curing urushiol hyperbranched super-amphiphobic anticorrosive coating.
Example 4
A preparation method of an ultraviolet light curing paint phenolic hyperbranched super-amphiphobic anticorrosive paint comprises the following steps:
Adding urushiol into a four-neck flask provided with a stirrer, a reflux condenser tube, a thermometer and a dropping funnel, wherein the molar ratio of the urushiol to the epichlorohydrin is 1:5, dripping epoxy chloropropane into a four-neck flask, stirring to uniformly mix, heating to 50 ℃, and stirring at a molar ratio of urushiol to NaOH of 1:3, dropwise adding 1mol/L NaOH solution according to the proportion of 3, heating to 70 ℃ after dropwise adding, and reacting at constant temperature for 5 hours to obtain a crude product; adding xylene and water into the crude product, washing, standing for layering, removing inorganic matters in a water layer, repeatedly washing until no chloride ion exists, and distilling under reduced pressure to obtain urushiol glycidyl ether;
step 2, synthesis of unsaturated urushiol-based hyperbranched polyether resin
Adding urushiol glycidyl ether and trimethylolpropane into a four-neck round-bottom flask according to a molar ratio of 1:4, heating, adding hexadecyl trimethoxy ammonium chloride which is 5.0 percent of the mass of the urushiol glycidyl ether when the reaction temperature reaches 80 ℃, continuously heating to 110 ℃, after reacting for 5 hours, adding deionized water which is 4 times the volume of the reaction liquid and has the temperature of 70 ℃ into the reaction liquid, fully stirring, then standing, and removing the upper liquid;
adding a mixed solution of ethanol and water with the mass ratio of 1:1 to the product which is obtained after hot water washing, fully stirring, standing for layering, removing the upper layer of liquid, and leaving the lower layer of liquid; adding excessive magnesium sulfate into the obtained lower layer liquid, drying to remove water in the product, and removing absolute ethyl alcohol to obtain unsaturated lacquer phenolic hyperbranched polyether resin with the terminal group being hydroxyl;
step 3, synthesizing fluorine modified unsaturated lacquer phenolic hyperbranched polyether resin
Adding unsaturated urushiol-based hyperbranched polyether resin, 3- (perfluoron-butane) -1, 2-epoxypropane with the mass equivalent to 80% of that of the unsaturated urushiol-based hyperbranched polyether resin and excessive tetrahydrofuran into a three-neck flask, dispersing at a high speed of 1500r/min for 2h at the temperature of 80 ℃ under the protection of nitrogen, and removing the tetrahydrofuran to obtain the fluorine-modified unsaturated urushiol-based hyperbranched polyether resin coating;
step 4, preparing the ultraviolet light curing paint phenolic hyperbranched super-amphiphobic anticorrosive paint
Adding 100 parts by weight of alumina microspheres with the particle size of 500nm into deionized water, performing ultrasonic dispersion for 1 hour to prepare a suspension with the concentration of 0.5mg/mL, dissolving 10% of 3-methyl propoxy silane in the weight of the alumina microspheres in absolute ethyl alcohol, adding the suspension into the suspension, performing reflux reaction for 1.5 hours, aging at room temperature, performing centrifugal separation, washing, and then placing in a vacuum drying oven for drying to obtain a nano reinforcement modified by a surface silane coupling agent;
and (3) uniformly mixing the fluorine-modified unsaturated urushiol-based hyperbranched polyether resin obtained in the step (3), 5.0% by mass of bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide, 10.0% by mass of tetramercaptopentane and 0.5% by mass of surface silane coupling agent-modified nano reinforcer to obtain the ultraviolet-curing urushiol-based hyperbranched super-amphiphobic anticorrosive coating.
Example 5
A preparation method of an ultraviolet light curing paint phenolic hyperbranched super-amphiphobic anticorrosive paint comprises the following steps:
Adding urushiol into a four-neck flask provided with a stirrer, a reflux condenser tube, a thermometer and a dropping funnel, wherein the molar ratio of the urushiol to the epichlorohydrin is 1: 6, dripping epoxy chloropropane into a four-neck flask, stirring to uniformly mix, heating to 40 ℃, and stirring at a molar ratio of urushiol to NaOH of 1:2, dropwise adding 1mol/L NaOH solution according to the proportion of 2, heating to 80 ℃ after the dropwise adding is finished, and reacting for 3 hours at constant temperature to obtain a crude product; adding xylene and water into the crude product, washing, standing for layering, removing inorganic matters in a water layer, repeatedly washing until no chloride ion exists, and distilling under reduced pressure to obtain urushiol glycidyl ether;
step 2, synthesis of unsaturated urushiol-based hyperbranched polyether resin
Adding urushiol glycidyl ether and trimethylolethane into a four-neck round-bottom flask according to a molar ratio of 1:5, heating, adding octadecyl trimethyl ammonium chloride which is 4.0 percent of the mass of the urushiol glycidyl ether when the reaction temperature reaches 100 ℃, continuously heating to 110 ℃, reacting for 6 hours, adding deionized water which is 4 times the volume of the reaction solution and has the temperature of 70 ℃ into the reaction solution, fully stirring, standing, and removing the upper layer liquid;
adding a mixed solution of ethanol and water with the mass ratio of 1:1 to the product which is obtained after hot water washing, fully stirring, standing for layering, removing the upper layer of liquid, and leaving the lower layer of liquid; adding excessive magnesium sulfate into the obtained lower layer liquid, drying to remove water in the product, and removing absolute ethyl alcohol to obtain unsaturated lacquer phenolic hyperbranched polyether resin with the terminal group being hydroxyl;
step 3, synthesizing fluorine modified unsaturated lacquer phenolic hyperbranched polyether resin
Adding unsaturated urushiol-based hyperbranched polyether resin, perfluoro-2, 3-epoxy-2-methylpentane with the mass being 100% of that of the unsaturated urushiol-based hyperbranched polyether resin and excessive acetone into a three-neck flask, dispersing at a high speed of 3000r/min for 1h at 100 ℃ under the protection of nitrogen, and removing the acetone to obtain a fluorine-modified unsaturated urushiol-based hyperbranched polyether resin coating;
step 4, preparing the ultraviolet light curing paint phenolic hyperbranched super-amphiphobic anticorrosive paint
Adding 100 parts of titanium dioxide microspheres with the particle size of 100nm in parts by weight into deionized water, performing ultrasonic dispersion for 1 hour to prepare a suspension with the concentration of 0.5mg/ml, dissolving bis (dimethylamino) methylvinylsilane accounting for 20 percent of the weight of the titanium dioxide microspheres in absolute ethyl alcohol, adding the suspension into the suspension, performing reflux reaction for 1.5 hours, aging at room temperature, performing centrifugal separation, washing, and then placing in a vacuum drying oven for drying to obtain a nano reinforcement modified by a surface silane coupling agent;
and (3) uniformly mixing the fluorine-modified unsaturated urushiol-based hyperbranched polyether resin obtained in the step (3), 4.0% by mass of 2,4, 6-trimethylbenzoyl-ethoxy-phenylphosphine oxide, 8.0% by mass of 1, 2-ethanedithiol and 4.0% by mass of surface silane coupling agent-modified nano reinforcement to obtain the ultraviolet light-cured urushiol-based hyperbranched super-amphiphobic anticorrosive paint.
Example 6
A preparation method of an ultraviolet light curing paint phenolic hyperbranched super-amphiphobic anticorrosive paint comprises the following steps:
Adding urushiol into a four-neck flask provided with a stirrer, a reflux condenser tube, a thermometer and a dropping funnel, wherein the molar ratio of the urushiol to the epichlorohydrin is 1: 8, dropwise adding epoxy chloropropane into a four-neck flask, stirring to uniformly mix, heating to 30 ℃, dropwise adding 1mol/L NaOH solution according to the molar ratio of urushiol to NaOH being 1:1 under the stirring condition, heating to 60 ℃ after dropwise adding, and reacting at constant temperature for 8 hours to obtain a crude product; adding xylene and water into the crude product paint, washing, standing for layering, removing inorganic matters in a water layer, repeatedly washing until no chloride ions exist, and distilling under reduced pressure to obtain urushiol glycidyl ether;
step 2, synthesis of unsaturated urushiol-based hyperbranched polyether resin
Adding urushiol glycidyl ether and trimethylolethane into a four-neck round-bottom flask according to a molar ratio of 1:10, heating, adding octadecyl dimethyl benzyl ammonium chloride which is 3.0 percent of the mass of the urushiol glycidyl ether when the reaction temperature reaches 90 ℃, continuously heating to 120 ℃, reacting for 2 hours, adding deionized water which is 3 times of the volume of the reaction solution and has the temperature of 70 ℃ into the reaction solution, fully stirring, standing, and removing the upper layer liquid;
adding a mixed solution of ethanol and water with the mass ratio of 1:1 to the product which is obtained after hot water washing, fully stirring, standing for layering, removing the upper layer of liquid, and leaving the lower layer of liquid; adding excessive magnesium sulfate into the obtained lower layer liquid, drying to remove water in the product, and removing absolute ethyl alcohol to obtain unsaturated lacquer phenolic hyperbranched polyether resin with the terminal group being hydroxyl;
step 3, synthesizing fluorine modified unsaturated lacquer phenolic hyperbranched polyether resin
Adding saturated urushiol-based hyperbranched polyether resin, 3- (perfluoron-butane) -1, 2-epoxypropane with the mass being 50% of that of the saturated urushiol-based hyperbranched polyether resin and excessive butanone into a three-neck flask, dispersing at a high speed of 1000r/min for 3h at 70 ℃ under the protection of nitrogen, and removing the butanone to obtain the fluorine-modified unsaturated urushiol-based hyperbranched polyether resin coating;
step 4, preparing the ultraviolet light curing paint phenolic hyperbranched super-amphiphobic anticorrosive paint
Adding 100 parts by weight of nano-cellulose with the particle size of 50nm into deionized water, performing ultrasonic dispersion for 1 hour to prepare a suspension with the concentration of 0.5mg/mL, dissolving vinyl tri (beta-methoxyethoxy) silane accounting for 15 percent of the weight of the nano-cellulose into absolute ethyl alcohol, adding the suspension into the suspension, performing reflux reaction for 1.5 hours, aging at room temperature, performing centrifugal separation, washing, and then placing in a vacuum drying oven for drying to obtain a nano reinforcement modified by a surface silane coupling agent;
and (3) uniformly mixing the fluorine-modified unsaturated urushiol-based hyperbranched polyether resin obtained in the step (3), 1.0 mass percent of 4-p-toluene mercapto benzophenone, 1.0 mass percent of pentaerythritol tetra (3-mercaptopropionic acid) ester and 1.0 mass percent of surface silane coupling agent-modified nano reinforcer to obtain the ultraviolet light curing urushiol-based hyperbranched super-amphiphobic anticorrosive paint.
The ultraviolet-curable paint phenolic hyperbranched super-amphiphobic anticorrosive paint and the natural raw paint prepared in the embodiments 1 to 6 of the invention are respectively coated on a glass plate and a tinplate by a 50-micrometer coater. The coatings obtained in examples 1 to 6 were dried in an ultraviolet curing machine, while the raw lacquer coating was dried in a temperature and humidity control cabinet (T: 30 ℃ and RH: 80%), and the physical and mechanical properties and corrosion resistance of the cured lacquer film were measured.
The device and the method for characterizing the ultraviolet-cured paint phenol-based hyperbranched super-amphiphobic anticorrosive coating layer are as follows:
preparation of the film: according to GB/T1727-: 10cm, the experiment was carried out in air.
Conventional physical and mechanical properties: the prepared sample is uniformly coated on a tinplate, and the conventional physical mechanical property and the corrosion resistance of the cured film are respectively tested by adopting the following national standards: the drying time of a paint film is determined according to GB/T1728-.
The IR spectrum of the sample was measured using a NICOLET6700 FT-IR spectrometer.
And (3) adopting a contact angle measuring instrument JY-PHb to characterize the wetting characteristic of the surface of the sample and measuring the static contact angle of the liquid drop.
The results are shown in Table 1.
TABLE 1 test results of drying time, physical and mechanical properties and corrosion resistance of paint film
As can be seen from Table 1, compared with the natural raw lacquer, the ultraviolet-curing paint prepared in the examples 1-6 of the invention has the advantages of short curing time, and greatly improved physical and mechanical properties and corrosion resistance.
FIG. 1 is an infrared spectrum of the unsaturated lacquer phenolic hyperbranched polyether resin prepared in example 1, which can be seen from FIG. 1, and is located at 3300-3500 cm-1The left and right absorption peaks are attributed to the characteristic peak of O-H stretching vibration, 1150cm-1Is a characteristic peak of stretching vibration of C-O-C, and shows that the polymer contains ether bonds, 2925cm-1And 2850cm-1The characteristic peak of stretching vibration corresponding to C-H shows that the polymer contains methyl, methylene and methine, 1644cm-1The stretching vibration peak of C ═ C, and it was found by infrared spectroscopic analysis that the kind of functional group in the product obtained in example 1 was consistent with that in the intended product.
Fig. 2 is a scanning electron microscope image of the ultraviolet curing paint phenol-based hyperbranched super-amphiphobic anticorrosive coating layer prepared in example 1, and it can be known from fig. 2 that nano-silica is uniformly dispersed in the coating matrix, thereby being beneficial to improving the physical and mechanical properties and lyophobic and anticorrosive properties of the coating.
The present invention describes preferred embodiments and effects thereof. Additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. A preparation method of an ultraviolet light curing paint phenol-based hyperbranched super-amphiphobic anticorrosive paint is characterized by comprising the following steps:
step 1, synthesis of urushiol glycidyl ether
Reacting urushiol with epoxy chloropropane and NaOH to obtain urushiol glycidyl ether;
step 2, synthesis of unsaturated urushiol-based hyperbranched polyether resin
Reacting urushiol glycidyl ether with a trihydroxymethyl compound under the action of a catalyst to obtain unsaturated urushiol-based hyperbranched polyether resin with an end group of hydroxyl;
step 3, synthesizing fluorine modified unsaturated lacquer phenolic hyperbranched polyether resin
Reacting unsaturated urushiol-based hyperbranched polyether resin with fluoro epoxy alkylate to obtain fluorine-modified unsaturated urushiol-based hyperbranched polyether resin;
step 4, preparing the ultraviolet light curing paint phenolic hyperbranched super-amphiphobic anticorrosive paint
Uniformly mixing fluorine-modified unsaturated urushiol-based hyperbranched polyether resin, a photoinitiator, a mercapto compound and a surface silane coupling agent-modified nano reinforcement to obtain an ultraviolet-cured urushiol-based hyperbranched super-amphiphobic anticorrosive coating;
wherein the mass ratio of the fluorine-modified unsaturated lacquer phenolic hyperbranched polyether resin, the photoinitiator, the mercapto compound and the surface silane coupling agent-modified nano reinforcement is 1: 1.0% -5.0%: 1.0% -10.0%: 0.5 to 5.0 percent.
2. The preparation method of the ultraviolet-curing phenolic hyperbranched super-amphiphobic anticorrosive paint of the paint as claimed in claim 1, wherein the specific reaction conditions in step 1 are as follows:
adding epoxy chloropropane into urushiol, heating to 30-50 ℃, adding NaOH, heating to 60-80 ℃, and reacting for 3-8 hours to obtain a crude product; carrying out post-treatment on the crude product to obtain urushiol glycidyl ether;
wherein the mol ratio of urushiol, epichlorohydrin and NaOH is 1: 2-8: 1 to 3.
3. The preparation method of the ultraviolet-curing phenolic hyperbranched super-amphiphobic anticorrosive paint of the paint as claimed in claim 1, wherein the specific reaction conditions in step 2 are as follows:
uniformly mixing urushiol glycidyl ether and a trihydroxymethyl compound, heating to 80-100 ℃, adding a catalyst, heating to 110-120 ℃, reacting for 1-6 hours, and performing post-treatment to obtain unsaturated urushiol hyperbranched polyether resin with hydroxyl as an end group;
wherein the molar ratio of the urushiol glycidyl ether to the trihydroxymethyl compound is 1: 2-10; the dosage of the catalyst is 1.0-5.0% of the mass of the urushiol glycidyl ether.
4. The method for preparing the ultra-violet curing paint phenolic hyperbranched super-amphiphobic anticorrosive paint as claimed in claim 3, wherein the catalyst is one of tetra-n-butyl ammonium chloride, tetra-n-butyl ammonium bromide, benzyltrimethyl ammonium chloride, benzyltriethyl ammonium chloride, triphenylphosphine, hexadecyl trimethoxy ammonium chloride, dibutyltin dilaurate, dodecyl benzyl ammonium chloride, dodecyl trimethoxy ammonium chloride, octadecyl dimethyl hydroxyethyl ammonium nitrate, octadecyl trimethyl ammonium chloride, octadecyl dimethyl benzyl ammonium chloride, octadecyl dimethyl hydroxyethyl ammonium perchlorate;
the trimethylol compound is trimethylolethane or trimethylolpropane.
5. The preparation method of the ultraviolet-curing phenolic hyperbranched super-amphiphobic anticorrosive paint of the paint as claimed in claim 1, wherein the specific reaction conditions in step 3 are as follows:
uniformly mixing unsaturated urushiol-based hyperbranched polyether resin, fluoro epoxy alkylate and an organic solvent, dispersing at a high speed of 50-100 ℃ under the protection of nitrogen, and removing the solvent after dispersion is finished to obtain fluorine-modified unsaturated urushiol-based hyperbranched polyether resin;
the mass ratio of the unsaturated urushiol-based hyperbranched polyether resin to the fluoro epoxy alkylate is 1: 0.5 to 1.
6. The method for preparing the ultraviolet curing paint phenolic hyperbranched super-amphiphobic anticorrosive paint as claimed in claim 5, wherein the fluoro epoxy alkylate is one of perfluoro-2, 3-epoxy-2-methylpentane, perfluoro propylene oxide, 1, 4-bis (2',3' -epoxypropyl) perfluorobutane, 3- (perfluoro-n-butane) -1, 2-propylene oxide and 3- (perfluoro-n-octyl) -1, 2-propylene oxide;
the organic solvent is one of dichloromethane, chloroform, tetrahydrofuran, cyclohexanone, xylene, toluene, diethyl ether, acetone, trifluorotoluene, butanone, dimethylformamide, dioxane, dimethyl sulfoxide, N-methylpyrrolidone, diphenyl ether or anisole.
7. The method for preparing the ultraviolet-curing phenolic hyperbranched super-amphiphobic anticorrosive paint of the paint as claimed in claim 1, wherein the mercapto compound in the step 4 is one of 1, 2-ethanedithiol, pentaerythritol tetra (3-mercaptopropionic acid) ester and tetramercapto-pentaerythrine;
the photoinitiator is one of 2-hydroxy-2-methyl-1-phenyl acetone, 1-hydroxy-cyclohexyl benzophenone, 2-hydroxy-2-methyl-1-p-hydroxyethyl ether phenyl acetone, 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide, 2,4, 6-trimethylbenzoyl-ethoxy-phenyl phosphine oxide, bis (2,4, 6-trimethylbenzoyl) phenyl phosphine oxide and 4-p-toluene mercapto benzophenone.
8. The preparation method of the ultraviolet-curing paint phenolic hyperbranched super-amphiphobic anticorrosive paint according to claim 1, wherein the preparation steps of the nano-reinforcement modified by the surface silane coupling agent in the step 4 are as follows:
s1, preparing a nano reinforcement suspension with the concentration of 0.5 mg/mL;
s2, dissolving a surface silane coupling agent which accounts for 5-20% of the weight of the nano reinforcement in absolute ethyl alcohol, adding the obtained solution into the nano reinforcement suspension prepared in S1, carrying out reflux reaction for 1.5h, aging at room temperature, carrying out centrifugal separation, washing and drying to obtain the nano reinforcement modified by the surface silane coupling agent;
the nano reinforcement is a silicon dioxide microsphere, an aluminum oxide microsphere, a titanium dioxide microsphere, a calcium carbonate microsphere, an iron oxide microsphere, graphene oxide, a carbon oxide nanotube, nano cellulose or a polymer nano microsphere with hydroxyl on the surface, and the particle size of the nano reinforcement is 50-1000 nm.
9. The method for preparing the phenolic hyperbranched super-amphiphobic anticorrosive paint of the ultraviolet-curing paint as claimed in claim 8, wherein the surface silane coupling agent is one of vinyl (2-methoxyethoxy) silane, (3-aminopropyl) -trimethoxysilane, (3-aminopropyl) triethoxysilane, 3-methylpropoxysilane, bis (dimethylamino) methylvinylsilane, vinyltriethoxysilane, vinyltrimethoxysilane and vinyltris (beta-methoxyethoxy) silane.
10. An ultraviolet light curing phenolic hyperbranched super-amphiphobic anticorrosive paint prepared by the method of any one of claims 1 to 9.
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