CN114773926A - Monohydroxy hydrogenated rosin derivative modified fluorocarbon anticorrosive paint and preparation method thereof - Google Patents
Monohydroxy hydrogenated rosin derivative modified fluorocarbon 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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- 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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Abstract
The invention discloses a monohydroxy hydrogenated rosin derivative modified fluorocarbon anticorrosive paint and a preparation method thereof, and relates to the technical field of anticorrosive paints, wherein the anticorrosive paint comprises the following components in parts by weight: hydroxy fluorocarbon resin: 10-80 parts; monohydroxy hydrogenated rosin derivatives: 2-65 parts of a solvent; pigment: 0-10 parts; filling: 0-40 parts; auxiliary agent: 1-5 parts; solvent: 15-70 parts of a solvent; curing agent: 2-40 parts; the method provided by the invention applies the renewable resource rosin derivatives to the modification of the fluorocarbon coating, and the prepared fluorocarbon anticorrosive coating has higher hardness and adhesive force, more excellent anticorrosive property, heat resistance and artificial climate aging resistance, further promotes the technical research of the green bio-based fluorocarbon anticorrosive coating, expands the application of the fluorocarbon coating in the aspect of ocean engineering, and improves the technical level of the ocean anticorrosive coating in China.
Description
Technical Field
The invention relates to the technical field of anticorrosive coatings, and particularly relates to a monohydroxy hydrogenated rosin derivative modified fluorocarbon anticorrosive coating and a preparation method thereof.
Background
Fluorocarbon anticorrosive paint is an anticorrosive paint taking fluorocarbon resin as a main film forming substance, and has the characteristics of excellent corrosion resistance, weather resistance, antifouling, self-cleaning, high hardness, ultraviolet aging resistance, stain resistance and the like, so that the fluorocarbon anticorrosive paint always occupies an important position in the anticorrosive field. However, with the rapid development of modern industry, higher requirements on corrosion resistance, weather resistance and durability of the coating are provided for marine vessels, offshore public facilities, high-rise buildings, large-scale steel frame structures and the like, and with the increasing social demand of green environment-friendly coatings, the fluorocarbon coating has the defects of inconvenient large-area construction, higher cost, higher selling price, longer curing time, poorer adhesiveness, poor wettability with pigments and fillers, high content of Volatile Organic Compounds (VOCs), large pollution, low stability, short service life and the like, so the improvement of the fluorocarbon coating is still an important research topic.
The hydrogenated rosin is a green and environment-friendly chemical raw material prepared by taking rosin which is a renewable biological resource as a raw material through a hydrogenation process. Compared with rosin, hydrogenated rosin changes a conjugated double bond structure in rosin resin acid, and double bonds tend to be saturated and become a stable state through addition of hydrogen molecules to the double bond structure of the rosin resin acid, so that the hydrogenated rosin has various advantages that rosin does not have, such as high oxidation resistance, compatibility, adhesion and aging resistance, small brittleness, high thermal stability, light color and the like, and can be widely applied to the fields of synthetic rubber, adhesives (adhesive increasing agents), soaps (light-resistant soaps), optical instruments, papermaking, coatings, lubricating oil, preservatives, waterproofing agents and the like instead of rosin.
However, the hydrogenated rosin only contains a carboxyl group as a reactive functional group in a molecular structure, and when the hydrogenated rosin is blended with a hydroxy fluorocarbon resin to prepare a modified fluorocarbon coating, the carboxyl group in the molecular structure of the hydrogenated rosin does not react with a curing agent isocyanate group, the reactivity with a hydroxyl group in the hydroxy fluorocarbon resin is also low, and the modified fluorocarbon resin is only physically modified, so that the modification of the fluorocarbon resin is limited.
Disclosure of Invention
In view of this, the invention discloses a monohydroxy hydrogenated rosin derivative modified fluorocarbon anticorrosive coating and a preparation method thereof, which further improve the hydrophobicity of the fluorocarbon coating and enhance the anticorrosive performance of the fluorocarbon coating.
The technical scheme provided by the invention specifically comprises the following steps of firstly, providing a monohydroxy hydrogenated rosin derivative modified fluorocarbon anticorrosive paint, wherein the monohydroxy hydrogenated rosin derivative modified fluorocarbon anticorrosive paint comprises the following components in parts by weight:
hydroxy fluorocarbon resin: 10 to 80 portions of
Monohydroxy hydrogenated rosin derivatives: 2 to 65 portions of
Pigment: 0 to 10 parts of
Filling: 0 to 40 parts of
Auxiliary agent: 1 to 5 portions of
Solvent: 15 to 70 parts of
Curing agent: 2-40 parts;
wherein, the molecular side chain of the hydroxy fluorocarbon resin contains hydroxyl, which is FEVE fluorocarbon resin formed by copolymerizing fluoroolefin and alkyl vinyl ether or alkyl vinyl ester.
Preferably, the hydroxyl value of the hydroxyl fluorocarbon resin ranges from 15 mg KOH/g to 85mg KOH/g.
Preferably, the pigment is an ultraweatherable pigment;
the filler is one or a mixture of more of titanium dioxide, barium sulfate, quartz powder, mica powder, talcum powder, diatomite, calcium carbonate, bentonite, nano silicon dioxide, aerogel, nano titanium dioxide, zinc oxide and aluminum powder;
the auxiliary agent is one or a mixture of more of an antioxidant, an ultraviolet absorbent, a flatting agent, a dispersing agent, a coupling agent and a defoaming agent;
the solvent is one or more mixed solvents of toluene, xylene, tetrahydrofuran, ethyl acetate, butyl acetate, petroleum ether, dichloromethane, trichloromethane and carbon tetrachloride;
the curing agent is aliphatic diisocyanate.
In a second aspect, the invention provides a preparation method of a monohydroxy hydrogenated rosin derivative modified fluorocarbon anticorrosive paint, which is characterized by comprising the following steps:
step 1: fully and uniformly mixing hydroxy fluorocarbon resin and a solvent to obtain a hydroxy fluorocarbon resin solution;
step 2: mixing 10-50% of hydroxy fluorocarbon resin solution with an auxiliary agent according to the mass percentage, adding a filler into the mixture, and performing ball milling and mixing in a ball mill for 0.5-6 h; continuously adding the pigment into the ball mill, and carrying out ball milling and mixing for 0.5-2 h to obtain prefabricated mixed slurry;
and 3, step 3: conveying the prefabricated mixed slurry into a sand mill, and grinding and stirring until the fineness of solid particles in the prefabricated slurry meets the requirement of a product for later use;
and 4, step 4: according to the mass percentage, obtaining 50 to 90 percent of hydroxy fluorocarbon resin solution and fully mixing with monohydroxy hydrogenated rosin derivatives for later use;
and 5: filtering the prefabricated mixed slurry in a sand mill by a screen, adding the filtered prefabricated mixed slurry into 50-90% of a hydroxy fluorocarbon resin/monohydroxy hydrogenated rosin derivative mixed solution under the stirring action, fully stirring and uniformly mixing, and discharging to obtain a resin component of the anticorrosive paint;
and 6: and (3) uniformly mixing the resin component of the anticorrosive paint with a curing agent to obtain the monohydroxy hydrogenated rosin derivative modified fluorocarbon anticorrosive paint.
Preferably, the monohydroxy hydrogenated rosin derivative in the step 4 is prepared by chemically modifying hydrogenated rosin, and the preparation steps are as follows:
1) mixing the components in a mass ratio of 1: adding 1-2.5 parts of hydrogenated rosin and epoxy chloropropane into a reaction kettle, and completely dissolving the hydrogenated rosin in the epoxy chloropropane at the temperature of 50-110 ℃;
2) slowly adding a catalyst into the fully dissolved hydrogenated rosin, heating and stirring for reaction for 2-10 hours at the temperature of 70-110 ℃, finishing the reaction, and cooling to room temperature;
3) adding water into the reaction kettle under the stirring condition, stopping stirring after fully stirring, standing for layering, and pouring out most of a water layer; then, continuously adding water, repeating for 3-8 times to ensure that the catalyst can be fully dissolved in the water and removed completely to obtain a water-containing intermediate product;
4) adding an organic solvent into the aqueous intermediate product, uniformly mixing, standing, performing liquid separation treatment, and removing a water layer; after repeating for 2-6 times, removing excessive water in the intermediate product;
5) and distilling under reduced pressure at the temperature of between 20 and 40 ℃ to remove the organic solvent to obtain the faint yellow viscous monohydroxy hydrogenated rosin derivative.
Preferably, the hydrogenated rosin in the step 1) is one or more of perhydrogenated rosin, dihydrorosin or tetrahydrorosin;
the catalyst in the step 2) is one or a mixture of triethylamine hydrochloride, pyridine hydrochloride, tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium iodide, sodium hydroxide and potassium hydroxide.
The organic solvent in the step 4) is one or a mixture of more of dichloromethane, trichloroethylene, toluene, ethyl acetate, chloroform, carbon tetrachloride and tetrahydrofuran
The invention discloses a monohydroxy hydrogenated rosin derivative modified fluorocarbon anticorrosive paint and a preparation method thereof, the method applies renewable resource rosin derivatives to the modification of fluorocarbon paint, the addition amount can reach more than 60%, the raw material cost of the fluorocarbon paint is reduced, the prepared fluorocarbon anticorrosive paint has higher hardness and adhesive force, more excellent anticorrosive property, heat resistance and artificial weather aging resistance, the technical research of green bio-based fluorocarbon anticorrosive paint is further promoted, the application of the fluorocarbon paint in ocean engineering is expanded, and the technical level of ocean anticorrosive paint in China is improved.
It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the disclosure.
Detailed Description
Exemplary embodiments will be described in detail herein. The implementations described in the following exemplary examples do not represent all implementations consistent with the present invention. Rather, they are merely examples of systems consistent with certain aspects of the invention, as detailed in the appended claims.
In order to solve the problems that the fluorocarbon anticorrosive paint in the prior art is high in raw material cost, poor in adhesive force, not high enough in stability, difficult to meet practical requirements in service life, and the like, the embodiment provides the monohydroxy hydrogenated rosin derivative modified fluorocarbon anticorrosive paint, which comprises the following components in parts by weight:
hydroxy fluorocarbon resin: 10 to 80 portions of
Monohydroxy hydrogenated rosin derivatives: 2 to 65 portions of
Pigment: 0 to 10 parts of
Filling: 0 to 40 parts of
Auxiliary agent: 1 to 5 portions of
Solvent: 15 to 70 portions of
Curing agent: 2-40 parts.
Preferably, the hydroxy fluorocarbon resin is FEVE fluorocarbon resin which contains hydroxy in molecular side chain and is formed by copolymerizing fluoroolefin and alkyl vinyl ether or alkyl vinyl ester, and the preferable range of the hydroxy value is 15-85 mg KOH/g.
Preferably, the pigment is an ultraweatherable pigment.
Preferably, the filler is one or a mixture of more of titanium dioxide, barium sulfate, quartz powder, mica powder, talcum powder, diatomite, calcium carbonate, bentonite, nano silica, aerogel, nano titanium dioxide, zinc oxide and aluminum powder.
Preferably, the auxiliary agent is one or a mixture of more of an antioxidant, an ultraviolet absorber, a leveling agent, a dispersing agent, a coupling agent and a defoaming agent.
Preferably, the solvent is one or more of toluene, xylene, tetrahydrofuran, ethyl acetate, butyl acetate, petroleum ether, dichloromethane, chloroform and carbon tetrachloride.
Preferably, the curing agent is an aliphatic diisocyanate.
On the other hand, the embodiment also provides a method for preparing the modified fluorocarbon anticorrosive paint, which comprises the following steps:
step 1: fully and uniformly mixing the hydroxy fluorocarbon resin with a solvent to obtain a hydroxy fluorocarbon resin solution;
step 2: mixing 10-50% of hydroxyl fluorocarbon resin solution with an auxiliary agent according to the mass percentage, adding a filler, and performing ball milling and mixing in a ball mill for 0.5-6 h; continuously adding the pigment into the ball mill, and carrying out ball milling and mixing for 0.5-2 h to obtain prefabricated mixed slurry;
and step 3: conveying the prefabricated mixed slurry into a sand mill, and grinding and stirring until the fineness of solid particles in the prefabricated slurry meets the requirement of a product for later use;
and 4, step 4: fully mixing the remaining 50-90% of hydroxy fluorocarbon resin solution with monohydroxy hydrogenated rosin derivatives for later use;
and 5: filtering the prefabricated mixed slurry in a sand mill by a screen, adding the filtered prefabricated mixed slurry into the remaining 50-90% of the hydroxy fluorocarbon resin/monohydroxy hydrogenated rosin derivative mixed solution under the stirring action, and discharging the mixture after fully stirring and uniformly mixing to obtain a resin component of the anticorrosive paint;
step 6: and (3) uniformly mixing the resin component of the anticorrosive paint with a curing agent to obtain the monohydroxy hydrogenated rosin derivative modified fluorocarbon anticorrosive paint.
The monohydroxy hydrogenated rosin derivative is prepared by chemically modifying hydrogenated rosin, and the preparation method comprises the following specific steps:
1) mixing the components in a mass ratio of 1: adding 1-2.5 parts of hydrogenated rosin and epoxy chloropropane into a reaction kettle, and completely dissolving the hydrogenated rosin in the epoxy chloropropane at the temperature of 50-110 ℃;
2) slowly adding a catalyst into the fully dissolved hydrogenated rosin, heating and stirring for reaction for 2-10 hours at the temperature of 70-110 ℃, finishing the reaction, and cooling to room temperature;
3) adding water into the reaction kettle under the stirring condition, stopping stirring after fully stirring, standing for layering, and pouring out most of a water layer; then, continuously adding water, repeating for 3-8 times to ensure that the catalyst can be fully dissolved in the water and removed completely to obtain a water-containing intermediate product;
4) adding an organic solvent into the aqueous intermediate product, uniformly mixing, standing, carrying out liquid separation treatment, and removing a water layer; after repeating for 2-6 times, removing excessive water in the intermediate product;
5) and distilling under reduced pressure at the temperature of 20-40 ℃ to remove the organic solvent to obtain the pale yellow viscous monohydroxy hydrogenated rosin derivative.
Preferably, the hydrogenated rosin in the step 1) is one or more of a perhydro rosin, a dihydro rosin or a tetrahydro rosin, and is preferably perhydro rosin.
Preferably, the catalyst in step 2) is one or more of triethylamine hydrochloride, pyridine hydrochloride, tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium iodide, sodium hydroxide and potassium hydroxide.
Preferably, the organic solvent in step 4) is one or more of dichloromethane, trichloroethylene, toluene, ethyl acetate, chloroform, carbon tetrachloride and tetrahydrofuran.
In the embodiment, the carboxyl of the hydrogenated rosin is introduced into hydroxyl through chemical reaction to obtain the hydrogenated rosin derivative containing hydroxyl, which can react with the fluorocarbon coating isocyanate curing agent and can realize chemical modification when added into a system, thereby improving the comprehensive properties of the fluorocarbon coating, such as stability, corrosion resistance, aging resistance, oxidation resistance, adhesive force and the like.
In the embodiment, the carboxyl of the hydrogenated rosin is introduced into hydroxyl through chemical reaction to obtain the hydrogenated rosin derivative containing hydroxyl, which can react with the fluorocarbon coating isocyanate curing agent and can realize chemical modification when added into a system, thereby improving the comprehensive properties of the fluorocarbon coating, such as stability, corrosion resistance, aging resistance, oxidation resistance, adhesive force and the like.
Specifically, in the preparation method, the monohydroxy hydrogenated rosin derivative which is a renewable resource is introduced into a hydroxy fluorocarbon resin system as an active modification component, and under the action of a diisocyanate bifunctional group, the monohydroxy hydrogenated rosin derivative is grafted to a side chain of the hydroxy fluorocarbon resin, so that the monohydroxy hydrogenated rosin derivative has large cycloalkyl steric hindrance, is favorable for improving the hardness, adhesive force and heat resistance of a film-formed material, and protects a main chain carbon chain; the introduction of the three-membered ring structure of the hydrogenated rosin further improves the hydrophobicity of the fluorocarbon coating and enhances the corrosion resistance of the fluorocarbon coating, so that the prepared modified fluorocarbon anticorrosive coating has more excellent comprehensive performance than the common fluorocarbon coating.
The present invention will be further illustrated by the following examples, but the scope of the present invention is not limited thereto.
Example 1
Mixing the materials in a mass ratio of 1: adding the dihydrorosin of 1 and epoxy chloropropane into a reaction kettle, and completely dissolving the dihydrorosin in the epoxy chloropropane at the temperature of 60 ℃; slowly adding tetrabutyl ammonium chloride with the mass percentage of 1.5% into the fully dissolved dihydrorosin, heating and stirring the mixture for reaction for 8 hours at the temperature of 100 ℃, finishing the reaction, and cooling the mixture to room temperature; adding water into the reaction kettle under the stirring condition, stopping stirring after fully stirring, standing for layering, and pouring out most of a water layer; then, continuously adding water, repeating for 4 times to ensure that the tetrabutyl ammonium chloride can be fully dissolved in the water and removed completely to obtain a water-containing intermediate product; adding tetrahydrofuran into the aqueous intermediate product, uniformly mixing, standing, carrying out liquid separation treatment, and removing a water layer; after repeating for 3 times, removing redundant water in the intermediate product; at the temperature of 40 ℃, tetrahydrofuran is removed by reduced pressure distillation to obtain a pale yellow viscous monohydroxy hydrogenated rosin derivative for later use.
According to the weight parts, 50 parts of hydroxy fluorocarbon resin with the hydroxyl value of 40mg KOH/g, 25 parts of dimethylbenzene and 25 parts of butyl acetate are fully and uniformly mixed to obtain 100 parts of hydroxy fluorocarbon resin solution; adding 30% of 100 parts of hydroxy fluorocarbon resin solution and 1 part of KH792 silane coupling agent into 5 parts of nano silicon dioxide, and ball-milling and mixing for 1 hour in a ball mill; adding 5 parts of titanium dioxide and 5 parts of calcium carbonate into a ball mill, and continuing ball milling and mixing for 2 hours; then, adding 1 part of BYK-170 dispersant, mixing, continuously adding 3 parts of aerogel and 1 part of weather-resistant inorganic pigment in sequence, and performing ball milling and mixing for 0.5h to obtain prefabricated mixed slurry; and (4) conveying the prefabricated mixed slurry into a sand mill, and grinding and stirring until the fineness of solid particles in the prefabricated slurry is less than 25um for later use. Fully mixing the residual 70 percent of hydroxyl fluorocarbon resin solution with 5 parts of monohydroxy hydrogenated rosin derivative for later use; filtering the prefabricated mixed slurry in the sand mill by a screen, adding the filtered prefabricated mixed slurry into the residual 70 percent of the hydroxyl fluorocarbon resin/monohydroxy hydrogenated rosin derivative mixed solution under the stirring action, fully stirring and uniformly mixing, and discharging to obtain the resin component of the anticorrosive paint. When in use, the resin component of the anticorrosive paint is uniformly mixed with 16 parts of cyclohexylmethane-4, 4' -diisocyanate curing agent to obtain the monohydroxy hydrogenated rosin derivative modified fluorocarbon anticorrosive paint.
Referring to the chemical industry standard HG/T3792-.
Example 2
Mixing the components in a mass ratio of 1: 2, adding the perhydrogenated rosin and epoxy chloropropane into a reaction kettle, and completely dissolving the perhydrogenated rosin in the epoxy chloropropane at the temperature of 90 ℃; slowly adding tetrabutylammonium bromide with the mass percentage of 0.8% into the fully-hydrogenated rosin after the fully-dissolved tetrabutylammonium bromide is fully dissolved, heating and stirring the mixture for reaction for 4 hours at the temperature of 95 ℃, finishing the reaction, and cooling the mixture to room temperature; adding water into the reaction kettle under the stirring condition, stopping stirring after fully stirring, standing for layering, and pouring out most of a water layer; then, continuously adding water, repeating for 5 times to ensure that tetrabutylammonium bromide can be fully dissolved in the water to be completely removed to obtain a water-containing intermediate product; adding dichloromethane into the aqueous intermediate product, uniformly mixing, standing, performing liquid separation treatment, and removing a water layer; after repeating for 5 times, removing excessive water in the intermediate product; and distilling under reduced pressure at the temperature of 25 ℃ to remove the dichloromethane to obtain a pale yellow viscous monohydroxy hydrogenated rosin derivative for later use.
According to the weight parts, 65 parts of hydroxy fluorocarbon resin with the hydroxyl value of 50mg KOH/g, 15 parts of dimethylbenzene and 20 parts of ethyl acetate are fully and uniformly mixed to obtain 100 parts of hydroxy fluorocarbon resin solution; mixing 20% of 100 parts of hydroxy fluorocarbon resin solution with 1 part of KH550 silane coupling agent, 2 parts of dispersing agent and 1 part of defoaming agent, adding 3 parts of calcium carbonate and 5 parts of bentonite into a ball mill, and continuously ball-milling and mixing for 2 hours; then, continuously adding 5 parts of weather-resistant gray inorganic pigment, and performing ball milling and mixing for 1h to obtain prefabricated mixed slurry; and (4) conveying the prefabricated mixed slurry into a sand mill, and grinding and stirring until the fineness of solid particles in the prefabricated slurry is less than 25um for later use. Fully mixing the remaining 80 percent of hydroxyl fluorocarbon resin solution with 15 parts of monohydroxy hydrogenated rosin derivative for later use; filtering the prefabricated mixed slurry in the sand mill by a screen, adding the filtered prefabricated mixed slurry into the residual 80 percent of hydroxy fluorocarbon resin/monohydroxy hydrogenated rosin derivative mixed solution under the stirring action, and discharging the mixture after fully stirring and uniformly mixing to obtain a resin component of the anticorrosive paint; when in use, the resin component of the anticorrosive paint is uniformly mixed with 18 parts of hexamethylene diisocyanate curing agent to obtain the monohydroxy hydrogenated rosin derivative modified fluorocarbon anticorrosive paint.
Referring to the chemical industry standard HG/T3792-.
Example 3
Mixing the components in a mass ratio of 1: 2.5, adding the tetrahydrorosin and epoxy chloropropane into a reaction kettle, and completely dissolving the tetrahydrorosin in the epoxy chloropropane at the temperature of 100 ℃; slowly adding 1.0 mass percent of tetrabutylammonium bromide and 1.5 mass percent of tetrabutylammonium iodide into the fully dissolved tetrahydrorosin, heating and stirring the mixture at the temperature of 85 ℃ for reacting for 6 hours, finishing the reaction, and cooling the reaction to room temperature; adding water into the reaction kettle under the stirring condition, stopping stirring after fully stirring, standing for layering, and pouring out most of a water layer; then, continuously adding water, repeating for 8 times to ensure that the catalyst can be fully dissolved in the water and removed completely to obtain a water-containing intermediate product; adding dichloromethane and trichloroethylene in a volume ratio of 1:1 into the aqueous intermediate product, uniformly mixing, standing, carrying out liquid separation treatment, and removing a water layer; after repeating for 3 times, removing excessive water in the intermediate product; and (3) distilling under reduced pressure at the temperature of 35 ℃ to remove dichloromethane and trichloroethylene to obtain a light yellow viscous monohydroxy hydrogenated rosin derivative for later use.
According to the weight parts, 40 parts of hydroxy fluorocarbon resin with the hydroxyl value of 65mg KOH/g, 20 parts of toluene, 20 parts of ethyl acetate and 10 parts of dichloromethane are fully and uniformly mixed to obtain 90 parts of hydroxy fluorocarbon resin solution; mixing 50% of 90 parts of hydroxyl fluorocarbon resin solution with 2 parts of KH570 silane coupling agent, 0.5 part of ultraviolet absorbent, 1 part of dispersing agent, 0.5 part of defoaming agent and 1 part of flatting agent, adding 15 parts of titanium dioxide and 10 parts of calcium carbonate into a ball mill, and ball-milling and mixing for 2 hours; then, continuously adding 2 parts of aerogel, and carrying out ball milling and mixing for 2 hours to obtain prefabricated mixed slurry; conveying the prefabricated mixed slurry into a sand mill, and grinding and stirring until the fineness of solid particles in the prefabricated slurry is less than 25um for later use; fully mixing the remaining 50 percent of hydroxy fluorocarbon resin solution with 40 parts of monohydroxy hydrogenated rosin derivative for later use; filtering the prefabricated mixed slurry in a sand mill by a screen, adding the filtered prefabricated mixed slurry into the remaining 50% of the hydroxy fluorocarbon resin/monohydroxy hydrogenated rosin derivative mixed solution under the stirring action, fully stirring and uniformly mixing, and discharging to obtain a resin component of the anticorrosive paint; when in use, the resin component of the anticorrosive paint is uniformly mixed with 22 parts of isophorone diisocyanate curing agent to obtain the monohydroxy hydrogenated rosin derivative modified fluorocarbon anticorrosive paint.
By referring to the chemical industry standard HG/T3792-.
TABLE 1 comparison of common fluorocarbon coatings with example coatings Performance
| Sample (I) | Ordinary fluorocarbon paint | Example one | Example two | EXAMPLE III |
| Pencil hardness (H) | 2 | 3 | 4 | 4 |
| Adhesion (MPa) | 7.6 | 12.4 | 14.2 | 18.7 |
The embodiment provides a monohydroxy hydrogenated rosin derivative modified fluorocarbon anticorrosive paint and a preparation method thereof, renewable resource rosin derivatives are applied to fluorocarbon paint modification, the addition amount of the rosin derivatives can reach more than 60%, the raw material cost of the fluorocarbon paint is reduced, and the prepared fluorocarbon anticorrosive paint has higher hardness and adhesive force, more excellent anticorrosive property, heat resistance and artificial weather aging resistance, further promotes the technical research of green bio-based fluorocarbon anticorrosive paint, expands the application of the fluorocarbon paint in the aspect of ocean engineering, and improves the technical level of ocean anticorrosive paint in China.
Other embodiments of the invention will be apparent to those skilled in the art from consideration of the specification and practice of the invention disclosed herein. This application is intended to cover any variations, uses, or adaptations of the invention following, in general, the principles of the invention and including such departures from the present disclosure as come within known or customary practice within the art to which the invention pertains. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the invention being indicated by the following claims.
Claims (6)
1. The monohydroxy hydrogenated rosin derivative modified fluorocarbon anticorrosive paint is characterized by comprising the following components in parts by weight:
hydroxy fluorocarbon resin: 10 to 80 portions of
Monohydroxy hydrogenated rosin derivatives: 2 to 65 portions of
Pigment: 0 to 10 parts of
Filling: 0 to 40 parts of
Auxiliary agent: 1 to 5 portions of
Solvent: 15 to 70 parts of
Curing agent: 2-40 parts;
wherein, the molecular side chain of the hydroxy fluorocarbon resin contains hydroxyl, which is FEVE fluorocarbon resin formed by copolymerizing fluoroolefin and alkyl vinyl ether or alkyl vinyl ester.
2. The monohydroxy hydrogenated rosin derivative modified fluorocarbon anticorrosive paint according to claim 1, wherein the hydroxyl value in the hydroxy fluorocarbon resin is in the range of 15 to 85mg KOH/g.
3. The monohydroxy hydrogenated rosin derivative modified fluorocarbon anticorrosive paint according to claim 1, wherein the pigment is an ultra-weatherable pigment;
the filler is one or a mixture of more of titanium dioxide, barium sulfate, quartz powder, mica powder, talcum powder, diatomite, calcium carbonate, bentonite, nano silicon dioxide, aerogel, nano titanium dioxide, zinc oxide and aluminum powder;
the auxiliary agent is one or a mixture of more of an antioxidant, an ultraviolet absorbent, a flatting agent, a dispersing agent, a coupling agent and a defoaming agent;
the solvent is one or more mixed solvents of toluene, xylene, tetrahydrofuran, ethyl acetate, butyl acetate, petroleum ether, dichloromethane, trichloromethane and carbon tetrachloride;
the curing agent is aliphatic diisocyanate.
4. A preparation method of monohydroxy hydrogenated rosin derivative modified fluorocarbon anticorrosive paint is characterized by comprising the following steps:
step 1: fully and uniformly mixing the hydroxy fluorocarbon resin with a solvent to obtain a hydroxy fluorocarbon resin solution;
step 2: mixing 10-50% of hydroxy fluorocarbon resin solution with an auxiliary agent according to the mass percentage, adding a filler into the mixture, and performing ball milling and mixing in a ball mill for 0.5-6 h; continuously adding the pigment into the ball mill, and performing ball milling and mixing for 0.5-2 hours to obtain prefabricated mixed slurry;
and step 3: conveying the prefabricated mixed slurry into a sand mill, grinding and stirring until the fineness of solid particles in the prefabricated slurry meets the product requirement for later use;
and 4, step 4: according to the mass percentage, obtaining 50-90% of hydroxyl fluorocarbon resin solution and fully mixing the hydroxyl fluorocarbon resin solution with monohydroxy hydrogenated rosin derivatives for later use;
and 5: filtering the prefabricated mixed slurry in a sand mill by a screen, adding the filtered prefabricated mixed slurry into 50-90% of a hydroxy fluorocarbon resin/monohydroxy hydrogenated rosin derivative mixed solution under the stirring action, and discharging the mixture after fully stirring and uniformly mixing to obtain a resin component of the anticorrosive paint;
step 6: and (3) uniformly mixing the resin component of the anticorrosive paint with a curing agent to obtain the monohydroxy hydrogenated rosin derivative modified fluorocarbon anticorrosive paint.
5. The preparation method of the monohydroxy hydrogenated rosin derivative modified fluorocarbon anticorrosive paint according to claim 4, wherein the monohydroxy hydrogenated rosin derivative in step 4 is prepared by chemically modifying hydrogenated rosin, and the preparation method specifically comprises the following steps:
1) mixing the materials in a mass ratio of 1: adding 1-2.5 parts of hydrogenated rosin and epoxy chloropropane into a reaction kettle, and completely dissolving the hydrogenated rosin in the epoxy chloropropane at the temperature of 50-110 ℃;
2) slowly adding a catalyst into the fully dissolved hydrogenated rosin, heating and stirring for reaction for 2-10 hours at the temperature of 70-110 ℃, finishing the reaction, and cooling to room temperature;
3) adding water into the reaction kettle under the stirring condition, stopping stirring after fully stirring, standing for layering, and pouring out most of a water layer; then, continuously adding water, repeating for 3-8 times to ensure that the catalyst can be fully dissolved in the water and removed completely to obtain a water-containing intermediate product;
4) adding an organic solvent into the aqueous intermediate product, uniformly mixing, standing, performing liquid separation treatment, and removing a water layer; after repeating for 2-6 times, removing excessive water in the intermediate product;
5) and distilling under reduced pressure at the temperature of 20-40 ℃ to remove the organic solvent to obtain the pale yellow viscous monohydroxy hydrogenated rosin derivative.
6. The method for preparing monohydroxy hydrogenated rosin derivative modified fluorocarbon anticorrosive paint according to claim 5, wherein the hydrogenated rosin in step 1) is one or more of perhydro rosin, dihydro rosin and tetrahydro rosin;
the catalyst in the step 2) is one or a mixture of triethylamine hydrochloride, pyridine hydrochloride, tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium iodide, sodium hydroxide and potassium hydroxide.
In the step 4), the organic solvent is one or a mixture of more of dichloromethane, trichloroethylene, toluene, ethyl acetate, chloroform, carbon tetrachloride and tetrahydrofuran.
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