CN109054533B - Polymer coating and preparation method thereof - Google Patents
Polymer coating and preparation method thereof Download PDFInfo
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- CN109054533B CN109054533B CN201810792405.1A CN201810792405A CN109054533B CN 109054533 B CN109054533 B CN 109054533B CN 201810792405 A CN201810792405 A CN 201810792405A CN 109054533 B CN109054533 B CN 109054533B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D129/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
- C09D129/02—Homopolymers or copolymers of unsaturated alcohols
- C09D129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/10—Homopolymers or copolymers of methacrylic acid esters
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/10—Homopolymers or copolymers of methacrylic acid esters
- C09D133/12—Homopolymers or copolymers of methyl methacrylate
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/04—Polymer mixtures characterised by other features containing interpenetrating networks
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Abstract
The invention discloses a ternary interpenetrating polymer network structure coating and a preparation method thereof. Introducing epoxy functional groups by graft copolymerization of glycidyl methacrylate on a polyvinyl alcohol molecular chain; then aniline molecules are introduced into an epoxy modified polyvinyl alcohol molecular chain through the reaction of an epoxy group and amino groups on aniline, and the aniline is subjected to chemical oxidation polymerization reaction to prepare polyaniline graft modified polyvinyl alcohol; and finally, adding an acrylate monomer into the polyaniline graft modification polyvinyl alcohol system, and initiating the free radical polymerization of the acrylate monomer by an initiator to prepare the polyacrylate/polyaniline-polyvinyl alcohol ternary interpenetrating polymer network structure dispersion liquid. Can be compounded with water-based polymer matrix resin, a defoaming agent, a thickening agent and a film-forming additive to prepare the environment-friendly composite anticorrosive paint. The invention has the advantages of simple preparation process, low cost, good durability, excellent comprehensive performance and the like, and has excellent application prospect and economic benefit.
Description
Technical Field
The invention relates to the technical field of preparation of environment-friendly composite coatings, and particularly relates to a polymer coating and a preparation method thereof.
Background
As a novel functional polymer material, the conductive polyaniline has a plurality of unique advantages compared with other intrinsic conductive polymers, and is considered to be one of the conductive polymers with practical application prospects. Polyaniline has excellent conductivity, reversible doping property, good redox reversibility and environmental stability, and is easy for large-scale production and synthesis. However, the shortage of PANI in terms of dispersibility and mechanical properties severely limits the large-scale popularization and application of PANI. Polyaniline is generally dark green powder, is difficult to dissolve and is generally insoluble in organic solvents, so that the mechanical property and the processing property of the polyaniline are poor. The polyaniline is compounded with the polymer matrix, so that the advantages of the polyaniline and the polymer matrix can be combined, and the processability and the mechanical property of the polyaniline are improved; but the compatibility and the compatibility of the composite material in a water-based polymer matrix are poor, and the performance of the composite material is greatly influenced.
The organic anticorrosive paint is the mainstream anticorrosive paint at present, and mainly takes solvent-based paint as the main material. 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
The invention provides a polymer coating and a preparation method thereof, aiming at solving the problems in the prior art that the compatibility and the compatibility in the existing polymer base material are poor, the water resistance of a water-based anticorrosive coating is low, the long-acting anticorrosive performance is poor, and the like. The method of the invention can effectively improve the compatibility and interaction among polymers; the preparation process takes water as a solvent, and is economic and environment-friendly; the coating has excellent mechanical strength, water resistance, hardness, corrosion resistance and the like.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method of preparing a polymer dispersion comprising the steps of:
a. weighing 100 parts by weight of a 10% polyvinyl alcohol aqueous solution and 4-8 parts by weight of glycidyl methacrylate, adding into a reactor, heating to 60-90 ℃, and stirring to react to form a transparent colorless solution; slowly adding acid, adjusting the pH value to 1-2, dropwise adding a ceric ammonium nitrate solution, and continuously and fully reacting to obtain a glycidyl methacrylate modified PVA solution, namely a GPVA solution;
b. dropwise adding 2-6 parts of aniline into 100 parts of GPVA solution with the mass fraction of 10%, and fully reacting at 50-70 ℃ to prepare aniline graft modified GPVA dispersion liquid;
c. reducing the temperature of the aniline grafted and modified GPVA dispersion liquid system to 0-5 ℃, adding an acid solution 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 reacting for 24-48 h to obtain a polyaniline grafted and modified GPVA dispersion liquid, namely a PANI-GPVA dispersion liquid;
d. weighing 5-10 parts by weight of soft acrylate monomer and 5-10 parts by weight of hard acrylate monomer, mixing, adding 5-20 parts by weight of water and 0.04-0.2 part by weight of surfactant, and uniformly mixing by ultrasonic to obtain a mixed solution; slowly dripping the mixed solution and the initiator solution into the prepared PANI-GPVA dispersion liquid at the same time, heating to 75-85 ℃, and fully reacting to obtain polyacrylate/polyaniline-polyvinyl alcohol polymer dispersion liquid, namely PA/PANI-GPVA dispersion liquid;
e. according to parts by weight, 100 parts of water-based polymer resin is taken as matrix resin, 1-10 parts of prepared PA/PANI-GPVA dispersion liquid, 0.05-0.2 part of thickening agent, 0.1-0.3 part of defoaming agent and 2-8 parts of film-forming assistant are added, and the mixture is uniformly mixed by adopting a physical blending method to obtain the polymer coating.
As a further improvement of the invention, the polyvinyl alcohol is of type 0588, 1088 or 1799;
the acid is hydrochloric acid, sulfuric acid, dodecyl benzene sulfonic acid, anthraquinone disulfonic acid, naphthalene sulfonic acid, citric acid or nitric acid.
As a further improvement of the invention, the oxidant is ammonium persulfate, potassium persulfate or ferric trichloride, and the molar ratio of the oxidant to the aniline is 1: (0.5-2).
As a further improvement of the invention, 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.
As a further improvement of the invention, the hard acrylate monomer is one or a mixture of more than two of methyl acrylate, methyl methacrylate and styrene in any proportion.
As a further improvement of the invention, the surfactant is one or a mixture of more than two of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, methyl orange, sodium p-toluene sulfonate, sodium didodecyl phenyl ether disulfonate, sodium dodecyl diphenyl 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 waterborne polymer resin is one or a mixture of more than two of waterborne polyurethane resin, waterborne epoxy resin, waterborne acrylate resin, waterborne alkyd resin and waterborne polyurethane-polyacrylate resin 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.
A polymer coating comprises the following components in parts by weight:
100 parts of water-based polymer resin, 1-10 parts of PA/PANI-GPVA dispersion liquid, 0.05-0.2 part of thickening agent, 0.1-0.3 part of defoaming agent and 2-8 parts of film-forming additive.
Compared with the prior art, the invention has the following beneficial technical effects:
aniline molecules are introduced through the reaction of epoxy groups and amino groups on aniline to carry out chemical oxidation polymerization reaction of aniline, so that polyaniline graft modified polyvinyl alcohol is prepared; and finally, adding an acrylate monomer into the polyaniline graft modified polyvinyl alcohol system, and initiating the free radical polymerization of the acrylate monomer by an initiator to prepare the environment-friendly polyacrylate/polyaniline-polyvinyl alcohol (PA/PANI-GPVA) polymer dispersion liquid. The dispersion can be directly used in the field of conductive coatings. The environment-friendly composite anticorrosive paint can be prepared by compounding the paint with general waterborne polymer resin, a defoaming agent, a thickening agent and a film-forming auxiliary agent. The design scheme of the ternary interpenetrating network based on molecular level fusion and covalent bond combination can improve the compatibility and interaction among polymers to the maximum extent and effectively improve the comprehensive performance of the coating; in addition, the introduction of the polyacrylate can effectively reduce the cost, has high cost performance and excellent application prospect and economic benefit.
The invention constructs the environment-friendly polyacrylate/polyaniline-polyvinyl alcohol (PA/PANI-GPVA) polymer composite coating through molecular design based on graft copolymerization and free radical copolymerization mechanisms, effectively combines the advantages and the characteristics of the polyacrylate, the polyaniline and the polyvinyl alcohol, and comprehensively improves the water resistance, the mechanical property and the long-acting corrosion resistance of the coating. At present, related researches mainly focus on the research of polyvinyl alcohol/polyaniline composite materials or polyaniline/polyacrylate, and the preparation method mainly focuses on physical blending and in-situ polymerization. The design scheme of the ternary interpenetrating network based on molecular level fusion and covalent bond combination is not reported, and the design scheme of the invention can improve the compatibility and interaction among polymers to the maximum extent and effectively improve the comprehensive performance of the coating; in addition, the introduction of the polyacrylate can effectively reduce the cost, has high cost performance and excellent application prospect and economic benefit.
Detailed Description
The invention relates to a preparation method of a polymer coating, which comprises the following specific steps:
a. weighing 100 parts of a polyvinyl alcohol (PVA) solution with the mass fraction of 10% and 4-8 parts of glycidyl methacrylate, adding the PVA solution and the glycidyl methacrylate into a 250ml three-neck flask, heating to 60-90 ℃, and stirring to form a transparent colorless solution; and slowly adding acid, adjusting the pH value to 1-2, dropwise adding a ceric ammonium nitrate solution, and continuously reacting for 2-3 h to obtain the glycidyl methacrylate modified PVA solution (GPVA).
b. And (2) dropwise adding 2-6 parts of aniline into 100 parts of GPVA solution with the mass fraction of 10%, and reacting at 50-70 ℃ for 2-3 h to prepare the aniline grafted and modified GPVA dispersion liquid.
c. And (2) reducing the temperature of the aniline graft modification GPVA dispersion liquid system to 0-5 ℃, 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, wherein the molar ratio of the oxidant to the aniline is 0.5-2, and reacting for 24 hours to obtain the polyaniline graft modification GPVA (PANI-GPVA) dispersion liquid.
d. Weighing 5-10 parts by weight of soft acrylate monomer and 5-10 parts by weight of hard acrylate monomer, mixing, adding 5-20 parts by weight of water and 0.04-0.2 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 the PANI-GPVA dispersion liquid at the same time, heating to 80 ℃, and reacting for 4-6 h to obtain the environment-friendly polyacrylate/polyaniline-polyvinyl alcohol (PA/PANI-GPVA) polymer dispersion liquid. The polymer dispersion liquid has good conductivity, and can be directly used in the field of conductive coatings and anticorrosive coatings; the following description proceeds to prepare the coatings.
e. Taking 100 parts of water-based polymer resin as matrix resin, adding 1-10 parts of PA/PANI-GPVA dispersion liquid, 0.05-0.2 part of thickening agent, 0.1-0.3 part of defoaming agent and 2-8 parts of film-forming assistant, and uniformly mixing by adopting a physical blending method to obtain the environment-friendly polymer coating.
The present invention is described in further detail below with reference to specific examples: (in parts by weight)
Example 1:
a. weighing 100 parts of a polyvinyl alcohol (PVA 0588) aqueous solution with the mass fraction of 10% and 5 parts of glycidyl methacrylate, adding the mixture into a 250ml three-neck flask, heating the mixture to 80 ℃, and stirring the mixture until a transparent colorless solution is formed; and then slowly adding a hydrochloric acid solution, adjusting the pH value to 1, dropwise adding a ceric ammonium nitrate solution, and continuously reacting for 3 hours to obtain a glycidyl methacrylate modified PVA solution (GPVA).
b. And (2) dropwise adding 3 parts of aniline into 100 parts of GPVA solution with the mass fraction of 10%, and reacting at 60 ℃ for 2 h to obtain the aniline grafted and modified GPVA dispersion liquid.
c. Reducing the temperature of the aniline graft modification GPVA dispersion liquid system to 0 ℃, adding a hydrochloric acid solution to adjust the pH value of the system to 1, then dropwise adding an oxidant to initiate the oxidation-reduction reaction of aniline, wherein the molar ratio of the oxidant to the aniline is 1, and reacting for 24 hours to obtain the polyaniline graft modification GPVA (PANI-GPVA) dispersion liquid.
d. Weighing 5 parts by weight of butyl methacrylate and 5 parts by weight of methyl methacrylate, mixing, adding 5 parts by weight of water and 0.04 part by weight of sodium dodecyl sulfate, and performing ultrasonic treatment for 5min to obtain a mixed solution; slowly dripping the mixed solution and a potassium persulfate initiator solution into the PANI-GPVA dispersion liquid at the same time, heating to 75 ℃, and reacting for 4 hours to obtain the environment-friendly polyacrylate/polyaniline-polyvinyl alcohol (PA/PANI-GPVA) polymer dispersion liquid. The dispersion can be directly used in the field of conductive coatings and anticorrosive coatings.
e. 100 parts of waterborne epoxy resin is taken as matrix resin, 3 parts of PA/PANI-GPVA dispersion liquid, 0.2 part of LS-112 thickening agent, 0.1 part of BYK-034 defoaming agent and 8 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 polymer coating.
Example 2:
a. weighing 100 parts of polyvinyl alcohol (PVA 1099) solution with the mass fraction of 10% and 4 parts of glycidyl methacrylate, adding the solution into a 250ml three-neck flask, heating to 80 ℃, and stirring to form a transparent colorless solution; and slowly adding a nitric acid solution, adjusting the pH value to 1, dropwise adding a ceric ammonium nitrate solution, and continuously reacting for 3 hours to obtain the glycidyl methacrylate modified PVA solution (GPVA).
b. And (2) dropwise adding 4 parts of aniline into 100 parts of GMA-PVA solution with the mass fraction of 10%, and reacting at 70 ℃ for 2.5h to prepare the aniline grafted and modified GPVA dispersion liquid.
c. Reducing the temperature of an aniline graft modification GPVA dispersion liquid system to 5 ℃, adding a sodium dodecyl benzene sulfonate solution to adjust the pH value of the system to 2, dropwise adding a metered oxidant ferric trichloride to initiate the oxidation-reduction reaction of aniline, wherein the molar ratio of the oxidant to the aniline is 1.5, and reacting for 36 hours to obtain the polyaniline graft modification GPVA (PANI-GPVA) dispersion liquid.
d. Weighing 8 parts by weight of butyl methacrylate and 8 parts by weight of methyl methacrylate, mixing, adding 15 parts by weight of water and 0.1 part by weight of surfactant, and performing ultrasonic treatment for 10min to obtain a mixed solution; slowly dripping the mixed solution and an initiator ammonium persulfate solution into the PANI-GPVA dispersion liquid at the same time, heating to 80 ℃, and reacting for 6 hours to obtain the environment-friendly polyacrylate/polyaniline-polyvinyl alcohol (PA/PANI-GPVA) polymer dispersion liquid. The dispersion can be directly used in the field of conductive coatings and anticorrosive coatings.
e. Taking 100 parts of waterborne epoxy resin as matrix resin, adding 4 parts of PA/PANI-GPVA dispersion liquid, 0.1 part of DL-80 thickening agent, 0.2 part of BYK-037 defoaming agent and 5 parts of butyl cellosolve film-forming assistant, and uniformly mixing by adopting a physical blending method to obtain the environment-friendly polymer coating.
Example 3:
a. weighing 100 parts of polyvinyl alcohol (PVA 0588) solution with the mass fraction of 10% and 6 parts of glycidyl methacrylate, adding into a 250ml three-neck flask, heating to 70 ℃, and stirring to form a transparent colorless solution; and then slowly adding a sulfuric acid solution, adjusting the pH value to 1, dropwise adding a ceric ammonium nitrate solution, and continuously reacting for 3 hours to obtain a glycidyl methacrylate modified PVA solution (GPVA).
b. And (2) dropwise adding 6 parts of aniline into 100 parts of GPVA solution with the mass fraction of 10%, and reacting at 70 ℃ for 3 hours to obtain the aniline grafted and modified GPVA dispersion liquid.
c. And (2) reducing the temperature of the aniline graft modification GPVA dispersion liquid system to 3 ℃, adding a citric acid solution to adjust the pH value of the system to 2, dropwise adding a metered oxidant to initiate the oxidation-reduction reaction of aniline, wherein the molar ratio of the oxidant to the aniline is 1.5, and reacting for 48 hours to obtain the polyaniline graft modification GPVA (PANI-GPVA) dispersion liquid.
d. Weighing 6 parts by weight of butyl methacrylate, 2 parts by weight of hexyl methacrylate and 6 parts by weight of styrene, mixing, adding 10 parts by weight of water and 0.1 part by weight of surfactant, and performing ultrasonic treatment for 10min to obtain a mixed solution; slowly dripping the mixed solution and the initiator solution into the PANI-GPVA dispersion liquid at the same time, heating to 80 ℃, and reacting for 6 hours to obtain the environment-friendly polyacrylate/polyaniline-polyvinyl alcohol (PA/PANI-GPVA) polymer dispersion liquid. The dispersion can be directly used in the field of conductive coatings and anticorrosive coatings.
e. Taking 100 parts of waterborne epoxy resin as matrix resin, adding 10 parts of PA/PANI-GPVA dispersion liquid, 0.1 part of DL-80 thickening agent, 0.2 part of BYK-037 defoaming agent and 6 parts of butyl cellosolve film-forming assistant, and uniformly mixing by adopting a physical blending method to obtain the environment-friendly polymer coating.
Example 4:
a. weighing 50 parts of a polyvinyl alcohol (PVA 1799) solution with the mass fraction of 10%, 50 parts of a polyvinyl alcohol (PVA 0588) solution with the mass fraction of 10% and 6 parts of glycidyl methacrylate, adding the mixture into a 250ml three-neck flask, heating to 80 ℃, and stirring to form a transparent colorless solution; and slowly adding a nitric acid solution, adjusting the pH value to 2, dropwise adding a ceric ammonium nitrate solution, and continuously reacting for 3 hours to obtain the glycidyl methacrylate modified PVA solution (GPVA).
b. And (2) dropwise adding 5 parts of aniline into 100 parts of GMA-PVA solution with the mass fraction of 10%, and reacting at 70 ℃ for 3 h to prepare the aniline grafted and modified GPVA dispersion liquid.
c. Reducing the temperature of an aniline graft modification GPVA dispersion liquid system to 5 ℃, adding a naphthalene sulfonic acid solution to adjust the pH value of the system to 2, dropwise adding metered potassium persulfate as an oxidant to initiate the oxidation-reduction reaction of aniline, wherein the molar ratio of the oxidant to the aniline is 1, and reacting for 24 hours to obtain the polyaniline graft modification GPVA (PANI-GPVA) dispersion liquid.
d. Weighing 10 parts by weight of butyl methacrylate and 8 parts by weight of methyl methacrylate, mixing, adding 20 parts by weight of water and 0.15 part by weight of surfactant, and carrying out ultrasonic treatment for 15 min to obtain a mixed solution; slowly dripping the mixed solution and the initiator solution into the PANI-GPVA dispersion liquid at the same time, heating to 85 ℃, and reacting for 6 hours to obtain the environment-friendly polyacrylate/polyaniline-polyvinyl alcohol (PA/PANI-GPVA) polymer dispersion liquid. The dispersion can be directly used in the field of conductive coatings and anticorrosive coatings.
e. Taking 100 parts of water-based alkyd resin as matrix resin, adding 5 parts of PA/PANI-GPVA dispersion liquid, 0.1 part of LS-112 thickening agent, 0.2 part of BYK-035 antifoaming agent and 4 parts of dodecanol ester film-forming aid, and uniformly mixing by adopting a physical blending method to obtain the environment-friendly polymer coating.
Example 5:
a. weighing 100 parts of a polyvinyl alcohol (PVA 1099) solution with the mass fraction of 10% and 5 parts of glycidyl methacrylate, adding the solution into a 250ml three-neck flask, heating to 60-90 ℃, and stirring to form a transparent colorless solution; and then slowly adding a sulfuric acid solution, adjusting the pH value to 2, dropwise adding a ceric ammonium nitrate solution, and continuously reacting for 3 hours to obtain a glycidyl methacrylate modified PVA solution (GPVA).
b. And (2) dropwise adding 4 parts of aniline into 100 parts of GPVA solution with the mass fraction of 10%, and reacting at 70 ℃ for 2 h to obtain the aniline grafted and modified GPVA dispersion liquid.
c. And (2) reducing the temperature of the aniline graft modification GPVA dispersion liquid system to 5 ℃, adding an anthraquinone disulfonic acid solution to adjust the pH value of the system to 2, dropwise adding a metered oxidant ammonium persulfate to initiate the redox reaction of aniline, wherein the molar ratio of the oxidant to the aniline is 1, and reacting for 48 hours to obtain the polyaniline graft modification GPVA (PANI-GPVA) dispersion liquid.
d. Weighing 9 parts of butyl acrylate and 8 parts of methyl methacrylate, mixing, adding 20 parts of water and 0.2 part of surfactant, and performing ultrasonic treatment for 15 min to obtain a mixed solution; slowly dripping the mixed solution and the initiator solution into the PANI-GPVA dispersion liquid at the same time, heating to 80 ℃, and reacting for 5 hours to obtain the environment-friendly polyacrylate/polyaniline-polyvinyl alcohol (PA/PANI-GPVA) polymer dispersion liquid. The dispersion can be directly used in the field of conductive coatings and anticorrosive coatings.
e. Taking 100 parts of water-based polymer resin as matrix resin, adding 4 parts of PA/PANI-GPVA dispersion liquid, 0.1 part of thickening agent, 0.2 part of defoaming agent and 5 parts of film-forming additive, and uniformly mixing by adopting a physical blending method to obtain the environment-friendly polymer coating.
Application and testing:
the environment-friendly polymer coating prepared by the invention is coated on the surface of a metal tinplate, and compared with a blank sample, the electrochemical performance of the product is tested, and the specific anti-corrosion performance parameters are shown in table 1. Table 1 shows the physical and chemical properties and corrosion resistance of the environment-friendly polyacrylate/polyaniline-polyvinyl alcohol composite material and the coating in different embodiments.
TABLE 1
| Detecting items | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 |
| Tensile strength | 39.23MPa | 44.47MPa | 33.1MPa | 34.79MPa | 32.56MPa |
| Electric conductivity | 1.56S/cm | 3.82S/cm | 5.12S/cm | 7.04S/cm | 3.06S/cm |
| Elongation at break | 42.1% | 50.43% | 39.09% | 53.87% | 50.42% |
| Impedance value | 2.41×107 Ωcm2 | 7.33×108 Ωcm2 | 7.92×108 Ωcm2 | 2.15×107 Ωcm2 | 8.38×107 Ωcm2 |
| Corrosion voltage | -0.43V | -0.23V | -0.31V | -0.46V | -0.30V |
| Corrosion current | 2.01×10-7 A·cm-2 | 4.6×10-10 A·cm-2 | 1.41×10-9 A·cm-2 | 2.93×10-7 A·cm-2 | 1.14×10-9 A·cm-2 |
As can be seen from Table 1, the polymer dispersion prepared by the invention has excellent physical and chemical properties and good corrosion resistance when being applied to coatings, and is an environment-friendly coating with excellent comprehensive properties.
Example 6:
a. weighing 50 parts of a polyvinyl alcohol (PVA 1799) solution with the mass fraction of 10%, 50 parts of a polyvinyl alcohol (PVA 0588) solution with the mass fraction of 10% and 4 parts of glycidyl methacrylate, adding the mixture into a 250ml three-neck flask, heating to 60 ℃, and stirring to form a transparent colorless solution; and then slowly adding a nitric acid solution, adjusting the pH value to 1, dropwise adding a ceric ammonium nitrate solution, and continuously reacting for 2 hours to obtain the glycidyl methacrylate modified PVA solution (GPVA).
b. And (2) dropwise adding 2 parts of aniline into 100 parts of GMA-PVA solution with the mass fraction of 10%, and reacting at 50 ℃ for 2 h to prepare the aniline grafted and modified GPVA dispersion liquid.
c. Reducing the temperature of an aniline graft modification GPVA dispersion liquid system to 0 ℃, adding a naphthalene sulfonic acid solution to adjust the pH value of the system to 1, dropwise adding metered potassium persulfate as an oxidant to initiate the oxidation-reduction reaction of aniline, wherein the molar ratio of the oxidant to the aniline is 0.5, and reacting for 24 hours to obtain the polyaniline graft modification GPVA (PANI-GPVA) dispersion liquid.
d. Weighing 5 parts by weight of butyl methacrylate and 5 parts by weight of methyl methacrylate, mixing, adding 5 parts by weight of water and 0.04 part by weight of surfactant, and performing ultrasonic treatment for 5min to obtain a mixed solution; slowly dripping the mixed solution and the initiator solution into the PANI-GPVA dispersion liquid at the same time, heating to 80 ℃, and reacting for 4 hours to obtain the environment-friendly polyacrylate/polyaniline-polyvinyl alcohol (PA/PANI-GPVA) polymer dispersion liquid. The dispersion can be directly used in the field of conductive coatings and anticorrosive coatings.
e. Taking 100 parts of waterborne alkyd resin as matrix resin, adding 0.05 part of PA/PANI-GPVA dispersion liquid, 0.1 part of LS-112 thickening agent, 0.1 part of BYK-035 defoaming agent and 2 parts of dodecanol ester film-forming aid, and uniformly mixing by adopting a physical blending method to obtain the environment-friendly polymer coating.
Example 7:
a. weighing 100 parts of a polyvinyl alcohol (PVA 1099) solution with the mass fraction of 10% and 8 parts of glycidyl methacrylate, adding the solution into a 250ml three-neck flask, heating to 60-90 ℃, and stirring to form a transparent colorless solution; and then slowly adding a sulfuric acid solution, adjusting the pH value to 2, dropwise adding a ceric ammonium nitrate solution, and continuously reacting for 3 hours to obtain a glycidyl methacrylate modified PVA solution (GPVA).
b. And (2) dropwise adding 6 parts of aniline into 100 parts of GPVA solution with the mass fraction of 10%, and reacting at 70 ℃ for 2 h to obtain the aniline grafted and modified GPVA dispersion liquid.
c. And (2) reducing the temperature of the aniline graft modification GPVA dispersion liquid system to 4 ℃, adding an anthraquinone disulfonic acid solution to adjust the pH value of the system to 2, dropwise adding a metered oxidant ammonium persulfate to initiate the redox reaction of aniline, wherein the molar ratio of the oxidant to the aniline is 1, and reacting for 48 hours to obtain the polyaniline graft modification GPVA (PANI-GPVA) dispersion liquid.
d. Weighing 10 parts by weight of butyl acrylate and 10 parts by weight of methyl methacrylate, mixing, adding 15 parts by weight of water and 0.1 part by weight of surfactant, and carrying out ultrasonic treatment for 15 min to obtain a mixed solution; slowly dripping the mixed solution and the initiator solution into the PANI-GPVA dispersion liquid at the same time, heating to 80 ℃, and reacting for 5 hours to obtain the environment-friendly polyacrylate/polyaniline-polyvinyl alcohol (PA/PANI-GPVA) polymer dispersion liquid. The dispersion can be directly used in the field of conductive coatings and anticorrosive coatings.
e. Taking 100 parts of water-based polymer resin as matrix resin, adding 4 parts of PA/PANI-GPVA dispersion liquid, 0.2 part of thickening agent, 0.3 part of defoaming agent and 8 parts of film-forming aid, and uniformly mixing by adopting a physical blending method to obtain the environment-friendly polymer 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 (7)
1. A preparation method of a polymer coating is characterized by comprising the following steps:
a. weighing 100 parts by weight of a 10% polyvinyl alcohol aqueous solution and 4-8 parts by weight of glycidyl methacrylate, adding into a reactor, heating to 60-90 ℃, and stirring to react to form a transparent colorless solution; slowly adding acid, adjusting the pH value to 1-2, dropwise adding a ceric ammonium nitrate solution, and continuously and fully reacting to obtain a glycidyl methacrylate modified PVA solution, namely a GPVA solution;
the polyvinyl alcohol is 0588, 1088 or 1799;
b. dropwise adding 2-6 parts of aniline into 100 parts of GPVA solution with the mass fraction of 10%, fully reacting at 50-70 ℃, and introducing aniline molecules through the reaction of epoxy groups and amino groups on the aniline to prepare aniline graft modified GPVA dispersion liquid;
c. reducing the temperature of the aniline graft modified GPVA dispersion liquid system to 0-5 ℃, adding an acid solution to adjust the pH value of the system to 1-2, then dropwise adding an oxidant to initiate the redox reaction of aniline, reacting for 24-48 h, and initiating the free radical polymerization of an acrylate monomer through an initiator to prepare a polyaniline graft modified GPVA dispersion liquid, namely PANI-GPVA dispersion liquid;
d. weighing 5-10 parts by weight of soft acrylate monomer and 5-10 parts by weight of hard acrylate monomer, mixing, adding 5-20 parts by weight of water and 0.04-0.2 part by weight of surfactant, and uniformly mixing by ultrasonic to obtain a mixed solution; slowly dripping the mixed solution and the initiator solution into the prepared PANI-GPVA dispersion liquid at the same time, heating to 75-85 ℃, and fully reacting to obtain polyacrylate/polyaniline-polyvinyl alcohol polymer dispersion liquid, namely PA/PANI-GPVA dispersion liquid;
e. taking 100 parts by weight of water-based polymer resin as matrix resin, adding 1-10 parts by weight of prepared PA/PANI-GPVA dispersion liquid, 0.05-0.2 part by weight of thickening agent, 0.1-0.3 part by weight of defoaming agent and 2-8 parts by weight of film-forming auxiliary agent, and uniformly mixing by adopting a physical blending method to obtain a polymer coating; the polymer coating is used for conductive coating;
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 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 p-toluene sulfonate, sodium didodecyl phenyl ether disulfonate, sodium dodecyl diphenyl ether disulfonate and sodium dodecyl sulfate in any proportion.
2. The method of claim 1, wherein:
the acid is hydrochloric acid, sulfuric acid, dodecyl benzene sulfonic acid, anthraquinone disulfonic acid, naphthalene sulfonic acid, citric acid or nitric acid.
3. The method of claim 1, wherein: the oxidant is ammonium persulfate, potassium persulfate or ferric trichloride, and the molar ratio of the oxidant to the aniline is 1: (0.5-2).
4. The method of claim 1, wherein: the initiator is one or a mixture of more than two of potassium persulfate, ammonium persulfate and azodiisobutyl amidine hydrochloride in any proportion.
5. The method of claim 1, wherein: the waterborne polymer resin is one or a mixture of more than two of waterborne polyurethane resin, waterborne epoxy resin, waterborne acrylate resin, waterborne alkyd resin and waterborne polyurethane-polyacrylate resin in any proportion.
6. The method of 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.
7. A polymeric coating characterized by: the composition comprises the following components in parts by weight:
100 parts of water-based polymer resin, 1-10 parts of PA/PANI-GPVA dispersion liquid, 0.05-0.2 part of thickening agent, 0.1-0.3 part of defoaming agent and 2-8 parts of film-forming additive;
the coating is prepared by the method of any one of claims 1 to 6.
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