CN109082202B - Environment-friendly high-strength polyaniline composite coating and preparation method thereof - Google Patents
Environment-friendly high-strength polyaniline composite coating and preparation method thereof Download PDFInfo
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- CN109082202B CN109082202B CN201810791623.3A CN201810791623A CN109082202B CN 109082202 B CN109082202 B CN 109082202B CN 201810791623 A CN201810791623 A CN 201810791623A CN 109082202 B CN109082202 B CN 109082202B
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- 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
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- C08F261/00—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00
- C08F261/02—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00 on to polymers of unsaturated alcohols
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Abstract
The invention discloses an environment-friendly high-strength polyaniline composite coating and a preparation method thereof. The method adopts a graft copolymerization method, and firstly adopts epichlorohydrin to modify polyvinyl alcohol. Aniline and modified polyvinyl alcohol are used as monomers, hydrochloric acid is used as a doping agent, ammonium persulfate is used as an oxidizing agent, and the polyaniline graft polyvinyl alcohol copolymer is synthesized through graft copolymerization. The method is characterized in that polyaniline grafted polyvinyl alcohol is used as a matrix, acrylate monomers are used as modifiers, and under the action of an initiator, copolymerization among the acrylate monomers and graft copolymerization of the acrylate monomers on polyaniline and polyvinyl alcohol molecular chains are initiated to form PA/PANI-PVA dispersion liquid. The high-strength modified polyaniline polyvinyl alcohol anticorrosive paint is prepared by taking a water-based polymer such as epoxy resin emulsion and the like as a matrix, taking a water-based PA/PANI-PVA dispersion liquid as a modifier, and adding a thickening agent, a defoaming agent and a film-forming assistant. The coating is economic and environment-friendly, and in addition, the product has the advantages of simple preparation process, low cost, good durability and the like, and has wide market application prospect.
Description
Technical Field
The invention relates to the technical field of preparation of environment-friendly polyaniline composite coatings, and particularly relates to an environment-friendly high-strength polyaniline composite coating and a preparation method thereof.
Background
With the rapid development of conductive polymers, new changes in environmental protection and metal corrosion protection have also emerged. The principle of corrosion prevention of the conductive polymer is mainly to form a passivation layer on the interface of metal and the polymer, so that the corrosion of the metal is slowed down, and a certain protection effect is achieved. Among many conductive polymers, polyaniline has the advantages of easy synthesis and easy availability of raw materials, and has become one of the most promising high molecular polymers at present. A large number of researches prove that the corrosion resistance of the polyaniline is relatively good; polyaniline with different oxidation degrees and doping levels can show different behaviors in different anticorrosion environments; the polyaniline anticorrosive paint also has the performances of scratch resistance and pitting resistance, and is a novel metal surface anticorrosive paint with relatively development prospect at present.
The preparation method of the organic anticorrosive paint by compounding polyaniline and a traditional polymer matrix such as epoxy resin, polyvinyl alcohol, polyurethane, polyacrylate, alkyd resin and the like is the mainstream preparation method at present, and mainly adopts solvent-based paint. A large amount of volatile organic solvents in the solvent-based paint become one of important sources for causing haze, and great harm is caused to human and environment. The oil removal transformation of the solvent type coating is imperative, and the environment-friendly anticorrosive coating with high performance, high efficiency, low energy consumption and low pollution is imperative to occupy very important position.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides an environment-friendly high-strength polyaniline composite coating and a preparation method thereof. The method effectively improves the water dispersion stability of the polyaniline, the mechanical strength, the water resistance, the hardness, the corrosion resistance and the like of the coating, and the preparation process takes water as a solvent, thereby being economic and environment-friendly.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of an environment-friendly high-strength polyaniline composite coating comprises the following steps:
a. taking 100 parts by weight of a polyvinyl alcohol aqueous solution with the mass fraction of 10%, and heating to 70-90 ℃; then slowly adding alkali, adjusting the pH value to 10-11, then slowly dropwise adding 1-4 parts of epoxy chloropropane, and continuously and fully reacting; adjusting the pH value of the system to be neutral by using acid to prepare an ECIP modified PVA solution, namely an ECIP-PVA solution;
b. weighing 1-5 parts by weight of redistilled aniline, mixing the redistilled aniline with 100 parts of ECIP-PVA, and keeping the reaction temperature at 70-90 ℃ for full reaction; then placing the system in an ice-water bath, adding acid to adjust the pH value of the system to 1-2, then dropwise adding an oxidant to initiate the oxidation-reduction reaction of aniline, and fully reacting to obtain polyaniline graft modification polyvinyl alcohol dispersion liquid; namely PANI-g-PVA dispersion liquid;
c. weighing 5-15 parts by weight of soft acrylate monomer and 5-15 parts by weight of hard acrylate monomer, mixing, adding 10-30 parts by weight of water and 0.1-0.3 part by weight of surfactant, and performing ultrasonic dispersion to obtain a mixed solution; slowly dripping the mixed solution and the initiator solution into 100 parts of PANI-g-PVA dispersion liquid at the same time, heating to 70-90 ℃, and reacting to obtain water-based polyacrylate/polyaniline-polyvinyl alcohol interpenetrating polymer network structure dispersion liquid, namely PA/PANI-PVA dispersion liquid;
d. taking 100 parts of water-based epoxy resin as matrix resin, adding 1-5 parts of PA/PANI-PVA dispersion liquid, 0.05-0.2 part of thickening agent, 0.1-0.5 part of defoaming agent and 3-10 parts of film-forming assistant, and uniformly mixing by adopting a physical blending method to obtain the environment-friendly high-strength polyaniline composite anticorrosive paint.
The polyvinyl alcohol is 0588, 1088 or 1799.
The alkali is potassium hydroxide, sodium hydroxide, potassium hydroxide or ammonia water;
the acid is hydrochloric acid, acetic acid, sulfuric acid, phosphoric acid or dodecyl benzene sulfonic acid.
The oxidant is ammonium persulfate or potassium persulfate.
The soft acrylate monomer is one or a mixture of more than two of butyl acrylate, butyl methacrylate, n-octyl acrylate, hexyl acrylate, n-octyl methacrylate and hexyl methacrylate in any proportion.
The hard acrylate monomer is one or a mixture of more than two of methyl methacrylate, methyl acrylate, methyl methacrylate and styrene in any proportion.
The surfactant is one or a mixture of more than two of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, sodium didodecyl phenyl ether disulfonate and sodium dodecyl sulfate in any proportion.
The initiator is one or a mixture of more than two of potassium persulfate, ammonium persulfate and azodiisobutyl amidine hydrochloride in any proportion.
The thickening agent is LS-112 or DL-80;
the defoaming agent is BYK-034, BYK-035 or BYK-037 produced by Germany BYK company;
the film-forming assistant is lauryl ester and ethylene glycol butyl ether.
An environment-friendly high-strength polyaniline composite coating comprises the following components in parts by weight:
100 parts of water-based epoxy resin, 1-5 parts of PA/PANI-PVA dispersion liquid, 0.05-0.2 part of thickening agent, 0.1-0.5 part of defoaming agent and 3-10 parts of film-forming additive.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention adopts a graft copolymerization method, and firstly adopts epichlorohydrin to modify polyvinyl alcohol. Aniline and modified polyvinyl alcohol are used as monomers, hydrochloric acid is used as a doping agent, ammonium persulfate is used as an oxidizing agent, and the polyaniline graft polyvinyl alcohol copolymer is synthesized through graft copolymerization. Polyaniline grafted polyvinyl alcohol is used as a matrix, acrylate monomers are used as modifiers, and under the action of an initiator, copolymerization among the acrylate monomers and graft copolymerization of the acrylate monomers on polyaniline and polyvinyl alcohol molecular chains are initiated to form a water-based polyacrylate/polyaniline-polyvinyl alcohol (PA/PANI-PVA) nano composite system. The high-strength modified polyaniline polyvinyl alcohol anticorrosive paint is prepared by taking a water-based polymer such as epoxy resin emulsion and the like as a matrix, taking a water-based PA/PANI-PVA dispersion liquid as a modifier, and adding a thickening agent, a defoaming agent and a film-forming assistant. Firstly, introducing an epoxy group on a polyvinyl alcohol molecular chain, and bonding polyaniline to the polyvinyl alcohol molecular chain through a chemical bond by chemical graft copolymerization, so that the dispersion stability of the polyaniline in water can be effectively enhanced, and the polyaniline is prevented from settling and condensing; then, taking polyaniline graft modified polyvinyl alcohol dispersion liquid as a matrix, introducing acrylate monomers, and adding an initiator to initiate polymerization among the acrylate monomers and graft polymerization of the acrylate monomers on a polyvinyl alcohol molecular chain to prepare the aqueous polyacrylate/polyaniline-polyvinyl alcohol (PA/PANI/PVA) interpenetrating polymer structure dispersion liquid. The method enables polyaniline molecules, polyacrylate molecules and polyvinyl alcohol molecules to be mutually entangled together through the forced compatibility effect, and effectively increases the compatibility and interaction among the molecules. The water-based polyacrylate/polyaniline-polyvinyl alcohol (PA/PANI/PVA) can be compounded with water-based epoxy resin to form a three-dimensional cross-linked network structure with an inter-network cross-linked structure, so that the composite high-strength anticorrosive coating with good mechanical property, water resistance and anticorrosive property is prepared. The preparation process of the product of the invention uses water as a solvent and introduces polyacrylate resin, thus being economic and environment-friendly.
According to the invention, polyaniline is graft copolymerized on an epoxy modified polyvinyl alcohol molecular chain through graft copolymerization, then a vinyl monomer is introduced to carry out free radical polymerization reaction, and the interpenetrating polymer network structure material of polyacrylate and polyaniline graft modified polyvinyl alcohol is formed. The product of the invention has good dispersion stability in water and good compatibility with matrix resins such as waterborne epoxy resin, waterborne alkyd resin, waterborne polyurethane resin and the like. The introduction of the polyacrylate can effectively reduce the product cost; and the polyacrylate has good mechanical property, film-forming property, bonding strength, water resistance and the like, and can effectively improve the defects of the polyaniline material. Therefore, the water-based polyacrylate interpenetrating modified polyaniline polyvinyl alcohol (PA/PANI/PVA) nano composite coating has excellent mechanical property, water resistance and long-acting corrosion resistance. The coating is economic and environment-friendly, and in addition, the product has the advantages of simple preparation process, low cost, good durability and the like, and has wide market application prospect.
Detailed Description
An environment-friendly high-strength polyaniline composite coating and a preparation method thereof, comprising the following steps:
a. adding 100 parts of 10 mass percent polyvinyl alcohol (PVA) solution into a 250ml three-neck flask, and heating to 70-90 ℃; then slowly adding an alkaline solution, adjusting the pH value to 10-11, then slowly dropwise adding 1-4 parts of Epoxy Chloropropane (ECIP), and continuing to react for 1 h; and (3) adjusting the pH value of the system to be neutral by using acid to prepare the ECIP modified PVA solution (ECIP-PVA).
b. Weighing 1-5 parts of redistilled aniline and 100 parts of ECIP-PVA according to the parts by weight, keeping the reaction temperature at 80 ℃, and mixing the redistilled aniline and 100 parts of ECIP-PVA for 2 hours. And then placing the system in an ice-water bath, adding an acid solution to adjust the pH value of the system to 1-2, dropwise adding a metered oxidant to initiate the oxidation-reduction reaction of aniline, and reacting for 12-48 hours to obtain a polyaniline graft modified polyvinyl alcohol (PANI-g-PVA) dispersion liquid.
c. Weighing 5-15 parts by weight of soft acrylate monomer and 5-15 parts by weight of hard acrylate monomer, mixing, adding 10-30 parts by weight of water and 0.1-0.3 part by weight of surfactant, and performing ultrasonic treatment for 5-15 min to obtain a mixed solution; slowly dripping the mixed solution and the initiator solution into 100 parts of PANI-g-PVA dispersion liquid at the same time, heating to 80 ℃, and reacting for 6 hours to obtain the aqueous polyacrylate/polyaniline-polyvinyl alcohol (PA/PANI-PVA) interpenetrating polymer network structure dispersion liquid.
d. Taking 100 parts of water-based epoxy resin as matrix resin, adding 1-5 parts of PA/PANI-PVA dispersion liquid, 0.05-0.2 part of thickening agent, 0.1-0.5 part of defoaming agent and 3-10 parts of film-forming assistant, and uniformly mixing by adopting a physical blending method to obtain the environment-friendly high-strength polyaniline composite anticorrosive paint.
The present invention is described in further detail below with reference to specific examples: (in parts by weight)
Example 1:
a. adding 100 parts of 10% polyvinyl alcohol solution (PVA0588) into a 250ml three-neck flask, and heating to 80 ℃; then slowly adding a potassium hydroxide solution, adjusting the pH value to 11, then slowly dropwise adding 2 parts of Epichlorohydrin (ECIP), and continuously reacting for 1 h; and (3) regulating the pH value of the system to be neutral by using hydrochloric acid to prepare the ECIP modified PVA solution (ECIP-PVA).
b. The reaction temperature was maintained at 80 ℃ by weight, 1 part of redistilled aniline was first weighed and mixed with 100 parts of ECIP-PVA for 2 hours. And then placing the system in an ice-water bath, adding a hydrochloric acid solution to adjust the pH value of the system to 2, dropwise adding an oxidant ammonium persulfate to initiate the redox reaction of aniline, and reacting for 24 hours to obtain the polyaniline graft modified polyvinyl alcohol (PANI-g-PVA) dispersion liquid.
c. Weighing 5.5 parts of butyl methacrylate and 5.5 parts of methyl methacrylate, mixing, adding 20 parts of water and 0.1 part of surfactant sodium dodecyl sulfate, and performing ultrasonic treatment for 5min to obtain a mixed solution; slowly dripping the mixed solution and an initiator potassium persulfate solution into 100 parts of PANI-g-PVA dispersion liquid at the same time, heating to 80 ℃, and reacting for 6 hours to obtain the aqueous polyacrylate/polyaniline-polyvinyl alcohol (PA/PANI-PVA) interpenetrating polymer network structure dispersion liquid.
d. 100 parts of waterborne epoxy resin is taken as matrix resin, 1 part of PA/PANI-PVA dispersion liquid, 0.1 part of LS-112 thickening agent, 0.3 part of BYK-034 defoaming agent and 5 parts of dodecanol ester film-forming assistant are added, and the mixture is uniformly mixed by a physical blending method to obtain the environment-friendly high-strength polyaniline composite anticorrosive coating.
Example 2:
a. adding 100 parts of 10% polyvinyl alcohol solution (PVA1799) into a 250ml three-neck flask, and heating to 90 ℃; then slowly adding a sodium hydroxide solution, adjusting the pH value to 10, then slowly dropwise adding 4 parts of Epichlorohydrin (ECIP), and continuously reacting for 1 h; adjusting the pH value of the system to be neutral by using acetic acid to prepare the ECIP modified PVA solution (ECIP-PVA).
b. Measured in parts by weight, the reaction temperature was kept at 90 ℃, 2 parts of redistilled aniline were first weighed and mixed with 100 parts of ECIP-PVA for 2 hours. And then placing the system in an ice-water bath, adding a hydrochloric acid solution to adjust the pH value of the system to 1, dropwise adding an oxidant potassium persulfate to initiate the oxidation-reduction reaction of aniline, and reacting for 36 hours to obtain the polyaniline graft modified polyvinyl alcohol (PANI-g-PVA) dispersion liquid.
c. Weighing 15 parts of butyl acrylate and 15 parts of methyl methacrylate monomer, mixing, adding 30 parts of water and 0.2 part of surface active agent sodium didodecyl phenyl ether disulfonate, and performing ultrasonic treatment for 15min to obtain a mixed solution; slowly dripping the mixed solution and the azodiisobutyl amidine hydrochloride solution into 100 parts of PANI-g-PVA dispersion liquid at the same time, heating to 80 ℃, and reacting for 6 hours to obtain the aqueous polyacrylate/polyaniline-polyvinyl alcohol (PA/PANI-PVA) interpenetrating polymer network structure dispersion liquid.
d. 100 parts of waterborne epoxy resin is taken as matrix resin, 2 parts of PA/PANI-PVA dispersion liquid, 0.05 part of thickening agent, 0.4 part of defoaming agent and 10 parts of film-forming additive are added, and the mixture is uniformly mixed by a physical blending method to obtain the environment-friendly high-strength polyaniline composite anticorrosive coating.
Example 3:
a. adding 100 parts of 10% polyvinyl alcohol solution (PVA1099) into a 250ml three-neck flask, and heating to 70 ℃; then slowly adding sodium hydroxide alkaline solution, adjusting the pH value to 11, then slowly dropwise adding 2 parts of Epichlorohydrin (ECIP), and continuing to react for 1 h; adjusting the pH value of the system to be neutral by using sulfuric acid to prepare the ECIP modified PVA solution (ECIP-PVA).
b. The reaction temperature was maintained at 80 ℃ by weight, 3 parts of redistilled aniline were first weighed and mixed with 100 parts of ECIP-PVA for 2 hours. And then placing the system in an ice-water bath, adding a phosphoric acid solution to adjust the pH value of the system to 2, dropwise adding an oxidant ammonium persulfate to initiate the redox reaction of aniline, and reacting for 36 hours to obtain the polyaniline graft modified polyvinyl alcohol (PANI-g-PVA) dispersion liquid.
c. Weighing 8 parts of butyl methacrylate, 2 parts of n-octyl acrylate and 10 parts of methyl methacrylate, mixing, adding 20 parts of water and 0.2 part of surfactant, and performing ultrasonic treatment for 10min to obtain a mixed solution; slowly dripping the mixed solution and ammonium persulfate initiator solution into 100 parts of PANI-g-PVA dispersion liquid at the same time, heating to 80 ℃, and reacting for 6 hours to obtain the aqueous polyacrylate/polyaniline-polyvinyl alcohol (PA/PANI-PVA) interpenetrating polymer network structure dispersion liquid.
d. Taking 100 parts of waterborne epoxy resin as matrix resin, adding 2 parts of PA/PANI-PVA dispersion liquid, 0.1 part of DL-80 thickening agent, 0.3 part of BYK-037 defoaming agent and 4 parts of butyl cellosolve film-forming assistant, and uniformly mixing by adopting a physical blending method to obtain the environment-friendly high-strength polyaniline composite anticorrosive coating.
Example 4:
a. adding 100 parts of 10% polyvinyl alcohol solution (PVA0588) into a 250ml three-neck flask, and heating to 80 ℃; then slowly adding an alkaline solution, adjusting the pH value to 10, then slowly dropwise adding 1 part of Epichlorohydrin (ECIP), and continuously reacting for 1 h; and (3) regulating the pH value of the system to be neutral by using hydrochloric acid to prepare the ECIP modified PVA solution (ECIP-PVA).
b. The reaction temperature was maintained at 80 ℃ by weight, 2 parts of redistilled aniline were first weighed and mixed with 100 parts of ECIP-PVA for 2 hours. And then placing the system in an ice-water bath, adding a hydrochloric acid solution to adjust the pH value of the system to 1, dropwise adding an oxidant potassium persulfate to initiate the oxidation-reduction reaction of aniline, and reacting for 24 hours to obtain the polyaniline graft modified polyvinyl alcohol (PANI-g-PVA) dispersion liquid.
c. Weighing 10 parts by weight of butyl methacrylate, 1 part by weight of n-octyl methacrylate and 10 parts by weight of methyl methacrylate, mixing, adding 10-30 parts by weight of water and 0.1-0.3 part by weight of surfactant, and carrying out ultrasonic treatment for 5-15 min to obtain a mixed solution; slowly dripping the mixed solution and the initiator solution into 100 parts of PANI-g-PVA dispersion liquid at the same time, heating to 80 ℃, and reacting for 6 hours to obtain the aqueous polyacrylate/polyaniline-polyvinyl alcohol (PA/PANI-PVA) interpenetrating polymer network structure dispersion liquid.
d. 100 parts of waterborne epoxy resin is taken as matrix resin, 2 parts of PA/PANI-PVA dispersion liquid, 0.1 part of LS-112 thickening agent, 0.2 part of BYK-034 defoaming agent and 6 parts of dodecanol ester film-forming assistant are added, and the mixture is uniformly mixed by a physical blending method to obtain the environment-friendly high-strength polyaniline composite anticorrosive coating.
Application and testing:
the epoxy chloropropane polyvinyl alcohol-aniline-acrylate copolymer anticorrosive paint prepared by the invention is used as a filler, added into epoxy resin E-44 to prepare an organic paint, coated on the surface of a metal tinplate, compared with a blank sample, tested for electrochemical performance, compared with an electrochemical alternating current impedance spectrum curve of the product, and evaluated for the anticorrosive performance. Table 1 shows the physical and chemical properties of the water-based polyacrylate/polyaniline-polyvinyl alcohol (PA/PANI-PVA) interpenetrating polymer network material and the anticorrosive property of the anticorrosive coating in different examples.
TABLE 1
Example 5:
a. adding 100 parts of 10% polyvinyl alcohol solution (PVA1799) into a 250ml three-neck flask, and heating to 70 ℃; then slowly adding a sodium hydroxide solution, adjusting the pH value to 10, then slowly dropwise adding 1 part of Epichlorohydrin (ECIP), and continuously reacting for 1 h; adjusting the pH value of the system to be neutral by using acetic acid to prepare the ECIP modified PVA solution (ECIP-PVA).
b. Measured in parts by weight, the reaction temperature was kept at 90 ℃, 1 part of redistilled aniline was first weighed and mixed with 100 parts of ECIP-PVA for 2 hours. And then placing the system in an ice-water bath, adding a hydrochloric acid solution to adjust the pH value of the system to 1, dropwise adding an oxidant potassium persulfate to initiate the oxidation-reduction reaction of aniline, and reacting for 12 hours to obtain the polyaniline graft modified polyvinyl alcohol (PANI-g-PVA) dispersion liquid.
c. Weighing 5 parts of butyl acrylate and 5 parts of methyl methacrylate monomer, mixing, adding 10 parts of water and 0.1 part of surface active agent sodium didodecyl phenyl ether disulfonate, and performing ultrasonic treatment for 15min to obtain a mixed solution; slowly dripping the mixed solution and the azodiisobutyl amidine hydrochloride solution into 100 parts of PANI-g-PVA dispersion liquid at the same time, heating to 80 ℃, and reacting for 6 hours to obtain the aqueous polyacrylate/polyaniline-polyvinyl alcohol (PA/PANI-PVA) interpenetrating polymer network structure dispersion liquid.
d. 100 parts of waterborne epoxy resin is taken as matrix resin, 1 part of PA/PANI-PVA dispersion liquid, 0.05 part of thickening agent, 0.1 part of defoaming agent and 3 parts of film-forming additive are added, and the mixture is uniformly mixed by adopting a physical blending method to obtain the environment-friendly high-strength polyaniline composite anticorrosive paint.
Example 6:
a. adding 100 parts of 10% polyvinyl alcohol solution (PVA1099) into a 250ml three-neck flask, and heating to 80 ℃; then slowly adding sodium hydroxide alkaline solution, adjusting the pH value to 11, then slowly dropwise adding 4 parts of Epichlorohydrin (ECIP), and continuing to react for 1 h; adjusting the pH value of the system to be neutral by using sulfuric acid to prepare the ECIP modified PVA solution (ECIP-PVA).
b. Measured in parts by weight, the reaction temperature was kept at 75 ℃, 5 parts of redistilled aniline were first weighed and mixed with 100 parts of ECIP-PVA for 2 hours. And then placing the system in an ice-water bath, adding a phosphoric acid solution to adjust the pH value of the system to 2, dropwise adding an oxidant ammonium persulfate to initiate the redox reaction of aniline, and reacting for 48 hours to obtain the polyaniline graft modified polyvinyl alcohol (PANI-g-PVA) dispersion liquid.
c. Weighing 10 parts by weight of butyl methacrylate, 5 parts by weight of n-octyl acrylate and 15 parts by weight of methyl methacrylate, mixing, adding 30 parts by weight of water and 0.3 part by weight of surfactant, and performing ultrasonic treatment for 15min to obtain a mixed solution; slowly dripping the mixed solution and ammonium persulfate initiator solution into 100 parts of PANI-g-PVA dispersion liquid at the same time, heating to 80 ℃, and reacting for 6 hours to obtain the aqueous polyacrylate/polyaniline-polyvinyl alcohol (PA/PANI-PVA) interpenetrating polymer network structure dispersion liquid.
d. 100 parts of waterborne epoxy resin is taken as matrix resin, 5 parts of PA/PANI-PVA dispersion liquid, 0.2 part of DL-80 thickening agent, 0.5 part of BYK-037 defoaming agent and 10 parts of butyl cellosolve film-forming assistant are added, and the mixture is uniformly mixed by a physical blending method to obtain the environment-friendly high-strength polyaniline composite anticorrosive coating.
The above is a detailed description of the present invention with reference to specific preferred embodiments, which should not be construed as limiting the present invention, but rather as a person of ordinary skill in the art to which the present invention pertains may make several simple deductions or substitutions without departing from the spirit of the present invention, which should be construed as belonging to the patent protection scope defined by the claims filed with the present invention.
Claims (6)
1. A preparation method of an environment-friendly high-strength polyaniline composite coating is characterized by comprising the following steps:
a. taking 100 parts by weight of a polyvinyl alcohol aqueous solution with the mass fraction of 10%, and heating to 70-90 ℃; then slowly adding alkali, adjusting the pH value to 10-11, then slowly dropwise adding 1-4 parts of epoxy chloropropane, and continuously and fully reacting; adjusting the pH value of the system to be neutral by using acid to prepare an ECIP modified PVA solution, namely an ECIP-PVA solution;
b. weighing 1-5 parts by weight of redistilled aniline, mixing the redistilled aniline with 100 parts of ECIP-PVA, and keeping the reaction temperature at 70-90 ℃ for full reaction; then placing the system in an ice-water bath, adding acid to adjust the pH value of the system to 1-2, then dropwise adding an oxidant to initiate the oxidation-reduction reaction of aniline, and fully reacting to obtain polyaniline graft modification polyvinyl alcohol dispersion liquid; namely PANI-g-PVA dispersion liquid;
c. weighing 5-15 parts by weight of soft acrylate monomer and 5-15 parts by weight of hard acrylate monomer, mixing, adding 10-30 parts by weight of water and 0.1-0.3 part by weight of surfactant, and performing ultrasonic dispersion to obtain a mixed solution; slowly dripping the mixed solution and the initiator solution into 100 parts of PANI-g-PVA dispersion liquid at the same time, heating to 70-90 ℃, and reacting to obtain water-based polyacrylate/polyaniline-polyvinyl alcohol interpenetrating polymer network structure dispersion liquid, namely PA/PANI-PVA dispersion liquid;
introducing an epoxy group into a polyvinyl alcohol molecular chain, and bonding polyaniline to the polyvinyl alcohol molecular chain through a chemical bond by chemical graft copolymerization; then, taking polyaniline graft modified polyvinyl alcohol dispersion liquid as a matrix, introducing acrylate monomers, and adding an initiator to initiate polymerization among the acrylate monomers and graft polymerization of the acrylate monomers on polyvinyl alcohol molecular chains to prepare aqueous polyacrylate/polyaniline-polyvinyl alcohol interpenetrating polymer structure dispersion liquid;
d. taking 100 parts of waterborne epoxy resin as matrix resin, adding 1-5 parts of PA/PANI-PVA dispersion liquid, 0.05-0.2 part of thickening agent, 0.1-0.5 part of defoaming agent and 3-10 parts of film-forming assistant, and uniformly mixing by adopting a physical blending method to obtain the environment-friendly high-strength polyaniline composite anticorrosive paint;
the soft acrylate monomer is one or a mixture of more than two of butyl acrylate, butyl methacrylate, n-octyl acrylate, hexyl acrylate, n-octyl methacrylate and hexyl methacrylate in any proportion;
the hard acrylate monomer is one or a mixture of more than two of methyl methacrylate, methyl acrylate, methyl methacrylate and styrene in any proportion;
the oxidant is ammonium persulfate or potassium persulfate;
the initiator is one or a mixture of more than two of potassium persulfate, ammonium persulfate and azodiisobutyl amidine hydrochloride in any proportion.
2. The preparation method of the environment-friendly high-strength polyaniline composite coating as claimed in claim 1, wherein: the polyvinyl alcohol is 0588, 1088 or 1799.
3. The preparation method of the environment-friendly high-strength polyaniline composite coating as claimed in claim 1, wherein: the alkali is potassium hydroxide, sodium hydroxide, potassium hydroxide or ammonia water;
the acid is hydrochloric acid, acetic acid, sulfuric acid, phosphoric acid or dodecyl benzene sulfonic acid.
4. The preparation method of the environment-friendly high-strength polyaniline composite coating as claimed in claim 1, wherein: the surfactant is one or a mixture of more than two of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, sodium didodecyl phenyl ether disulfonate and sodium dodecyl sulfate in any proportion.
5. The preparation method of the environment-friendly high-strength polyaniline composite coating as claimed in claim 1, wherein:
the thickening agent is LS-112 or DL-80;
the defoaming agent is BYK-034, BYK-035 or BYK-037 produced by Germany BYK company;
the film-forming assistant is lauryl ester and ethylene glycol butyl ether.
6. An environment-friendly high-strength polyaniline composite coating, which is characterized by being prepared by the preparation method of any one of claims 1 to 5 and comprising the following components in parts by weight:
100 parts of water-based epoxy resin, 1-5 parts of PA/PANI-PVA dispersion liquid, 0.05-0.2 part of thickening agent, 0.1-0.5 part of defoaming agent and 3-10 parts of film-forming additive.
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| CN111607223B (en) * | 2020-05-19 | 2023-02-17 | 广东德星聚合物薄膜材料研究有限公司 | Anti-static packaging film and preparation method thereof |
| CN111644077B (en) * | 2020-06-15 | 2022-04-29 | 上海迅江科技有限公司 | Hydrophilic polyvinylidene fluoride nanofiltration membrane and preparation method thereof |
| CN112608496A (en) * | 2020-12-02 | 2021-04-06 | 丁林贞 | Preparation method of conductive polyaniline phosphorylated polyvinyl alcohol nano colloidal particles |
| CN113307984B (en) * | 2021-04-29 | 2023-04-21 | 广西桂林荣鑫新材料科技有限公司 | Preparation method of aqueous epoxy resin dispersion |
| CN113861741A (en) * | 2021-10-29 | 2021-12-31 | 深圳市晓帆宇科技有限公司 | Preparation method of acrylate composite conductive material |
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