CN109054533A - A kind of ternary IPN structural paint and preparation method thereof - Google Patents
A kind of ternary IPN structural paint and preparation method thereof Download PDFInfo
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- CN109054533A CN109054533A CN201810792405.1A CN201810792405A CN109054533A CN 109054533 A CN109054533 A CN 109054533A CN 201810792405 A CN201810792405 A CN 201810792405A CN 109054533 A CN109054533 A CN 109054533A
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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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- 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
- 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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- 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
- 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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- 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
- 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 kind of ternary IPN structural paints and preparation method thereof.Pass through the graft copolymerization methacrylate ethylene oxidic ester introducing epoxy-functional on polyvinyl alcohol molecule chain；Then aniline molecule is introduced on epoxy modifying polyethylene alcohol strand with reacting for amino on aniline by epoxy group, carries out the chemical oxidising polymerisation reaction of aniline, polyaniline grafted modified polyvinylalcohol is made；Acrylate monomer finally is added into polyaniline grafted modified polyvinylalcohol system, causes the free radical polymerization of acrylate monomer by initiator, polyacrylate/polyaniline-polyvinyl alcohol ternary IPN structure disperses liquid is made.It can be with waterborne polymeric matrix resin, defoaming agent, thickener, the compound obtained environment-friendly type composite anticorrosion coating of coalescing agent.The advantages that preparation process of the present invention is simple, low in cost, and durability is good, excellent combination property has excellent application prospect and economic benefit.
Description
Technical field
The present invention relates to a kind of environment-friendly type composite coating preparation technical field, in particular to a kind of ternary interpenetrating polymer net
Network structural paint and preparation method thereof.
Background technique
Electrically conductive polyaniline is as a kind of new functional macromolecule material, compared with other intrinsically conducting macromolecules, tool
There are many unique advantages, it is considered to be most one of the conducting polymer of actual application prospect.Polyaniline has excellent lead
Electrically, reversible doping, good redox reversible, environmental stability and is easy to be mass produced synthesis.However
Deficiency of the PANI in terms of dispersibility and mechanical property, seriously limits its large-scale promotion application.Polyaniline is generally ink
Green powder, indissoluble and infusibility do not dissolve in organic solvent generally, cause its mechanical property and processing performance poor.By polyaniline
Improve the machinability and mechanical property of polyaniline in combination with the two advantage with polymer matrix bluk recombination；But it is in polymerizable aqueous
Compatibility and compatibility in object substrate is poor, can largely influence the performance of composite material.
Anti-corrosive organic coatings are the anticorrosive paints of current mainstream, and mainly based on solvent based coating.In solvent based coating
A large amount of volatile organic solvents have become and cause one of important sources of haze, high risks are generated to the mankind and environment.It is molten
The going of dosage form coating " oil " transition is imperative, and high-performance, high efficiency, the Environment-friendlyanti-corrosive anti-corrosive paint of low energy consumption and low pollution will account for
According to very important status.
Summary of the invention
Poor to solve the compatible and compatibility in current property polymeric substrate, water-based anticorrosive paint water resistance is low, long
The problems of the prior art such as antiseptic property difference are imitated, the present invention provides a kind of ternary IPN structural paints
And preparation method thereof.Method of the invention can effectively improve the compatibility and interaction between polymer；Preparation process is with water
Solvent, it is economic and environment-friendly；Coating has excellent mechanical strength, water resistance, hardness, antiseptic property etc..
In order to achieve the above objectives, the invention adopts the following technical scheme:
A kind of preparation method of ternary IPN structure disperses liquid, comprising the following steps:
A. by weight, polyvinyl alcohol water solution and 4~8 parts of metering systems that 100 parts of mass fractions are 10% are weighed
Acid glycidyl ester adds in reactor, and temperature rises to 60~90 DEG C, is stirred to react to formation transparent colourless solution；Then delay
It is slow that acid is added, after pH value is adjusted to 1~2, ceric ammonium nitrate solution is added dropwise, continues sufficiently reaction, it is sweet that Glycidyl methacrylate is made
Grease modified PVA solution, i.e. GPVA solution；
B. by weight, 2~6 parts of aniline are added dropwise in the GPVA solution for being 10% to 100 parts of mass fractions, 50~70
It is sufficiently reacted at DEG C, aniline graft modification GPVA dispersion liquid is made；
C. aniline graft modification GPVA dispersion liquid system temperature is down to 0~5 DEG C, acid solution is added and adjusts system pH
It is 1~2, then the redox reaction that oxidant causes aniline is added dropwise, 24~48h of reaction is made polyaniline grafted modified GPVA points
Dispersion liquid, i.e. PANI-GPVA dispersion liquid；
D. by weight, weigh 5~10 parts of soft acrylate monomers and 5~10 parts of rigid acrylate monomers are mixed
It closes, and 5~20 parts of water and 0.04-0.2 parts of surfactants is added, mixed solution is uniformly made in ultrasonic mixing；It will slowly mix
It closes solution and initiator solution instills PANI-GPVA dispersion liquid obtained above simultaneously, be warming up to 75~85 DEG C, sufficiently react,
Polyacrylate/polyaniline-polyvinyl alcohol ternary IPN structure disperses liquid, i.e. PA/PANI-GPVA dispersion is made
Liquid；
E. by weight, take 100 parts of aqueous polymer resins as matrix resin, add PA/PANI-GPVA obtained
1~10 part of dispersion liquid, 0.05~0.2 part of thickener, 0.1~0.3 part of defoaming agent, 2~8 parts of coalescing agent, using physical blending
Method is uniformly mixed, and obtains ternary IPN structural paint.
As a further improvement of the present invention, the polyvinyl alcohol model is 0588,1088 or 1799；
The acid is hydrochloric acid, sulfuric acid, dodecyl benzene sulfonic acid, anthraquinone disulfonic acid, naphthalene sulfonic acids, citric acid or nitric acid.
As a further improvement of the present invention, the oxidant is ammonium persulfate, potassium peroxydisulfate or ferric trichloride, oxidant
Molar ratio with aniline is 1:(0.5~2).
As a further improvement of the present invention, the soft acrylate monomer is butyl acrylate, methacrylic acid fourth
One or more of ester, n-octyl, Hexyl 2-propenoate, n octyl methacrylate and hexyl methacrylate
The mixture arbitrarily matched.
As a further improvement of the present invention, the rigid acrylate monomer is methyl acrylate, methyl methacrylate
The mixture that one or more of ester and styrene arbitrarily match.
As a further improvement of the present invention, the surfactant is lauryl sodium sulfate, detergent alkylate sulphur
Sour sodium, methyl orange, paratoluenesulfonic acid sodium salt, double dodecylphenyl ether sodium disulfonates, disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate and ten
The mixture that one or more of sodium dialkyl sulfate arbitrarily matches；
The initiator be one or both of potassium peroxydisulfate, ammonium persulfate and azo diisobutyl amidine hydrochloride with
The mixture of upper any proportion.
The aqueous polymer resin is waterborne polyurethane resin, aqueous epoxy resins, waterborne acrylic paint, water
The mixture that property one or more of alkyd resin and waterborne polyurethane-polyacrylate resin arbitrarily match.
The thickener is LS-112 or DL-80；
The defoaming agent is BYK-034, BYK-035 or BYK-037 of BYK company of Germany production；
The coalescing agent is decylene glycol ester, butyl glycol ether.
A kind of ternary IPN structural paint, measures by weight, is made of the following components:
100 parts of aqueous polymer resins, 1~10 part of PA/PANI-GPVA dispersion liquid, 0.05~0.2 part of thickener, defoaming
0.1~0.3 part of agent, 2~8 parts of coalescing agent.
Compared with prior art, the invention has the following beneficial technical effects:
Present invention graft copolymerization methacrylate ethylene oxidic ester on polyvinyl alcohol molecule chain introduces epoxy-functional；
Then aniline molecule is introduced on epoxy modifying polyethylene alcohol strand with reacting for amino on aniline by epoxy group, carried out
The chemical oxidising polymerisation of aniline reacts, and polyaniline grafted modified polyvinylalcohol is made；Finally to polyaniline grafted modified poly ethylene
Acrylate monomer is added in alcohol system, causes the free radical polymerization of acrylate monomer by initiator, it is poly- that environment-friendly type is made
Acrylate/polyaniline-polyvinyl alcohol (PA/PANI-GPVA) ternary IPN structure disperses liquid.The dispersion liquid can
It is directly used in conductive coating field.It is compound with general aqueous polymer resin, defoaming agent, thickener, coalescing agent
Environment-friendly type composite anticorrosion coating is made.Ternary interpenetrating networks based on molecular level fusion and Covalent bonding together of the invention are set
Meter scheme can farthest improve the compatibility and interaction between polymer, effectively improve the comprehensive performance of coating；In addition
The introducing of polyacrylate can effectively reduce cost, and cost performance is high, has excellent application prospect and economic benefit.
The present invention is based on graft copolymerization and free-radical polymerized mechanism, has constructed environment-friendly type polypropylene olefin(e) acid by MOLECULE DESIGN
The composite coating of ester/polyaniline-polyvinyl alcohol (PA/PANI-GPVA) ternary IPN structure effectively combines poly- third
The advantageous feature of olefin(e) acid ester, polyaniline and polyvinyl alcohol three, comprehensive water resistance, the mechanical property, long-effective corrosion for improving coating
Performance.Current related correlative study is concentrated mainly on polyvinyl alcohol/polyaniline composite material or polyaniline/polyacrylate
Research, preparation method are concentrated mainly on physical blending and in-situ polymerization.Ternary based on molecular level fusion and Covalent bonding together
The design scheme of interpenetrating networks has not been reported, and design scheme of the present invention can farthest improve the compatibility and phase between polymer
Interaction effectively improves the comprehensive performance of coating；In addition the introducing of polyacrylate can effectively reduce cost, and cost performance is high, tool
There are excellent application prospect and economic benefit.
Specific embodiment
A kind of preparation method of ternary IPN structural paint of the present invention, the specific steps are as follows:
A. it is sweet for 10% polyvinyl alcohol (PVA) solution and 4~8 parts of Glycidyl methacrylates that 100 parts of mass fractions are weighed
Grease adds in the three-necked flask of 250ml, and temperature rises to 60~90 DEG C, stirring to formation transparent colourless solution；Then slowly add
Enter acid, after pH value is adjusted to 1~2, ceric ammonium nitrate solution is added dropwise, it is sweet to can be prepared by Glycidyl methacrylate by the reaction was continued 2~3h
Grease modified PVA solution (GPVA).
B. 2~6 parts of aniline are added dropwise in the GPVA solution for being 10% to 100 parts of mass fractions, react 2 at 50~70 DEG C~
Aniline graft modification GPVA dispersion liquid is made in 3h.
C. aniline graft modification GPVA dispersion liquid system temperature is down to 0~5 DEG C, acid solution is added and adjusts system pH
It is 1~2, then the redox reaction of the oxidant initiation aniline of metering is added dropwise, the molar ratio of oxidant and aniline is 0.5~2,
Polyaniline grafted modified GPVA (PANI-GPVA) dispersion liquid is made in reaction for 24 hours.
D. by weight, weigh 5~10 parts of soft acrylate monomers and 5~10 parts of rigid acrylate monomers are mixed
It closes, and 5~20 parts of water and 0.04-0.2 parts of surfactants is added, mixed solution is made in 5~15min of ultrasound；It will slowly mix
It closes solution and initiator solution instills PANI-GPVA dispersion liquid simultaneously, be warming up to 80 DEG C, the reaction time is 4~6h, be can be prepared by
Environment-friendly polypropylene acid esters/polyaniline-polyvinyl alcohol (PA/PANI-GPVA) ternary IPN structure disperses liquid.This
Invention ternary IPN structure disperses liquid has good electric conductivity, can be directly used for conductive coating field and anti-corrosion
Coating；Following description carries out preparing coating.
E. it takes 100 parts of aqueous polymer resins as matrix resin, adds 1~10 part of PA/PANI-GPVA dispersion liquid, increase
It thick dose 0.05~0.2 part, 0.1~0.3 part of defoaming agent, 2~8 parts of coalescing agent, is uniformly mixed using physical blending process to get arriving
Environment-friendly type ternary IPN structural paint.
The invention will be described in further detail combined with specific embodiments below: (in parts by weight)
Embodiment 1:
A. polyvinyl alcohol (PVA0588) aqueous solution and 5 parts of Glycidyl methacrylates that 100 parts of mass fractions are 10% are weighed
Glyceride adds in the three-necked flask of 250ml, and temperature rises to 80 DEG C, stirring to formation transparent colourless solution；It is then slowly added into
After pH value is adjusted to 1, ceric ammonium nitrate solution is added dropwise in hydrochloric acid solution, and the reaction was continued 3h can be prepared by methyl propenoic acid glycidyl
Ester modified PVA solution (GPVA).
B. 3 parts of aniline are added dropwise in the GPVA solution for being 10% to 100 parts of mass fractions, 2h is reacted at 60 DEG C, aniline is made
Graft modification GPVA dispersion liquid.
C. aniline graft modification GPVA dispersion liquid system temperature is down to 0 DEG C, hydrochloric acid solution is added and adjusts system pH
It is 1, then the redox reaction that oxidant causes aniline is added dropwise, the molar ratio of oxidant and aniline is 1, and reaction is made poly- for 24 hours
Aniline graft modification GPVA (PANI-GPVA) dispersion liquid.
D. by weight, weigh 5 parts of butyl methacrylates to mix with 5 parts of methyl methacrylates, and be added 5 parts
Mixed solution is made in water and 0.04 part of lauryl sodium sulfate, ultrasonic 5min；Slowly by mixed solution and potassium peroxydisulfate initiator
Solution instills PANI-GPVA dispersion liquid simultaneously, is warming up to 75 DEG C, reaction time 4h, can be prepared by environment-friendly polypropylene acid esters/
Polyaniline-polyvinyl alcohol (PA/PANI-GPVA) ternary IPN structure disperses liquid.The dispersion liquid can be directly used for
Conductive coating field and anticorrosive paint.
E. it takes 100 parts of aqueous epoxy resins as matrix resin, adds 3 parts of PA/PANI-GPVA dispersion liquid, LS-112 increases
Thick dose 0.2 part, 0.1 part of BYK-034 defoaming agent, 8 parts of decylene glycol ester coalescing agent, using physical blending process be uniformly mixed to get
To environment-friendly type ternary IPN structural paint.
Embodiment 2:
A. it is sweet for 10% polyvinyl alcohol (PVA1099) solution and 4 parts of Glycidyl methacrylates that 100 parts of mass fractions are weighed
Grease adds in the three-necked flask of 250ml, and temperature rises to 80 DEG C, stirring to formation transparent colourless solution；It is then slowly added into nitre
After pH value is adjusted to 1, ceric ammonium nitrate solution is added dropwise in acid solution, and the reaction was continued 3h can be prepared by glycidyl methacrylate
Modified PVA solution (GPVA).
B. 4 parts of aniline are added dropwise in the GMA-PVA solution for being 10% to 100 parts of mass fractions, 2.5h system is reacted at 70 DEG C
Obtain aniline graft modification GPVA dispersion liquid.
C. aniline graft modification GPVA dispersion liquid system temperature is down to 5 DEG C, neopelex solution is added will
System pH is adjusted to 2, then the redox reaction of the oxidant ferric trichloride initiation aniline of metering, oxidant and aniline is added dropwise
Molar ratio be 1.5, reaction 36h polyaniline grafted modified GPVA (PANI-GPVA) dispersion liquid is made.
D. by weight, weigh 8 parts of butyl methacrylates to mix with 8 parts of methyl methacrylates, and be added 15 parts
Water and 0.1 part of surfactant, mixed solution is made in ultrasonic 10min；It is slowly that mixed solution and initiator ammonium persulfate is molten
Liquid instills PANI-GPVA dispersion liquid simultaneously, is warming up to 80 DEG C, reaction time 6h, can be prepared by environment-friendly polypropylene acid esters/poly-
Aniline-polyvinyl alcohol (PA/PANI-GPVA) ternary IPN structure disperses liquid.The dispersion liquid can be directly used for leading
Electrocoat field and anticorrosive paint.
E. it takes 100 parts of aqueous epoxy resins as matrix resin, adds 4 parts of PA/PANI-GPVA dispersion liquid, DL-80 thickening
0.1 part of agent, 0.2 part of BYK-037 defoaming agent, 5 parts of butyl glycol ether coalescing agent, using physical blending process be uniformly mixed to get
To environment-friendly type ternary IPN structural paint.
Embodiment 3:
A. it is sweet for 10% polyvinyl alcohol (PVA0588) solution and 6 parts of Glycidyl methacrylates that 100 parts of mass fractions are weighed
Grease adds in the three-necked flask of 250ml, and temperature rises to 70 DEG C, stirring to formation transparent colourless solution；It is then slowly added into sulphur
After pH value is adjusted to 1, ceric ammonium nitrate solution is added dropwise in acid solution, and the reaction was continued 3h can be prepared by glycidyl methacrylate
Modified PVA solution (GPVA).
B. 6 parts of aniline are added dropwise in the GPVA solution for being 10% to 100 parts of mass fractions, 3h is reacted at 70 DEG C, aniline is made
Graft modification GPVA dispersion liquid.
C. aniline graft modification GPVA dispersion liquid system temperature is down to 3 DEG C, citric acid solution is added by system pH tune
Section is 2, then the redox reaction of the oxidant initiation aniline of metering is added dropwise, and the molar ratio of oxidant and aniline is 1.5, reaction
Polyaniline grafted modified GPVA (PANI-GPVA) dispersion liquid is made in 48h.
D. by weight, weigh 6 parts of butyl methacrylates, 2 parts of hexyl methacrylates are mixed with 6 parts of styrene,
And mixed solution is made in the water and 0.1 part of surfactant of 10 parts of addition, ultrasonic 10min；Slowly by mixed solution and initiator
Solution instills PANI-GPVA dispersion liquid simultaneously, is warming up to 80 DEG C, reaction time 6h, can be prepared by environment-friendly polypropylene acid esters/
Polyaniline-polyvinyl alcohol (PA/PANI-GPVA) ternary IPN structure disperses liquid.The dispersion liquid can be directly used for
Conductive coating field and anticorrosive paint.
E. it takes 100 parts of aqueous epoxy resins as matrix resin, adds 10 parts of PA/PANI-GPVA dispersion liquid, DL-80 increases
It thick dose 0.1 part, 0.2 part of BYK-037 defoaming agent, 6 parts of butyl glycol ether coalescing agent, is uniformly mixed using physical blending process, i.e.,
Obtain environment-friendly type ternary IPN structural paint.
Embodiment 4:
A. weighing polyvinyl alcohol (PVA1799) solution, 50 parts of mass fractions that 50 parts of mass fractions are 10% is 10%
Polyvinyl alcohol (PVA0588) solution and 6 parts of glycidyl methacrylate, add in the three-necked flask of 250ml, temperature rises to
80 DEG C, stirring to formation transparent colourless solution；It is then slowly added into nitric acid solution, after pH value is adjusted to 2, it is molten that ammonium ceric nitrate is added dropwise
Liquid, the reaction was continued 3h can be prepared by glycidyl methacrylate modified PVA solution (GPVA).
B. 5 parts of aniline are added dropwise in the GMA-PVA solution for being 10% to 100 parts of mass fractions, 3h is reacted at 70 DEG C and is made
Aniline graft modification GPVA dispersion liquid.
C. aniline graft modification GPVA dispersion liquid system temperature is down to 5 DEG C, naphthalene sulfonic acids solution is added by system pH tune
Section is 2, then the redox reaction of the oxidant potassium peroxydisulfate initiation aniline of metering is added dropwise, and the molar ratio of oxidant and aniline is
1, polyaniline grafted modified GPVA (PANI-GPVA) dispersion liquid is made in reaction for 24 hours.
D. by weight, weigh 10 parts of butyl methacrylates to mix with 8 parts of methyl methacrylates, and be added 20 parts
Water and 0.15 part of surfactant, mixed solution is made in ultrasonic 15min；Slowly mixed solution and initiator solution are dripped simultaneously
Enter PANI-GPVA dispersion liquid, be warming up to 85 DEG C, reaction time 6h, it is poly- to can be prepared by environment-friendly polypropylene acid esters/polyaniline-
Vinyl alcohol (PA/PANI-GPVA) ternary IPN structure disperses liquid.The dispersion liquid can be directly used for conductive coating neck
Domain and anticorrosive paint.
E. it takes 100 parts of aqueous alkide resins as matrix resin, adds 5 parts of PA/PANI-GPVA dispersion liquid, LS-112 increases
Thick dose 0.1 part, 0.2 part of BYK-035 defoaming agent, 4 parts of decylene glycol ester coalescing agent, using physical blending process be uniformly mixed to get
To environment-friendly type ternary IPN structural paint.
Embodiment 5:
A. it is sweet for 10% polyvinyl alcohol (PVA1099) solution and 5 parts of Glycidyl methacrylates that 100 parts of mass fractions are weighed
Grease adds in the three-necked flask of 250ml, and temperature rises to 60~90 DEG C, stirring to formation transparent colourless solution；Then slowly add
Enter sulfuric acid solution, after pH value is adjusted to 2, ceric ammonium nitrate solution is added dropwise, it is sweet to can be prepared by Glycidyl methacrylate by the reaction was continued 3h
Grease modified PVA solution (GPVA).
B. 4 parts of aniline are added dropwise in the GPVA solution for being 10% to 100 parts of mass fractions, 2h is reacted at 70 DEG C, aniline is made
Graft modification GPVA dispersion liquid.
C. aniline graft modification GPVA dispersion liquid system temperature is down to 5 DEG C, anthraquinone disulfonic acid solution is added by system pH
Value is adjusted to 2, then the redox reaction of the oxidant ammonium persulfate initiation aniline of metering, mole of oxidant and aniline is added dropwise
Than being 1, polyaniline grafted modified GPVA (PANI-GPVA) dispersion liquid is made in reaction 48h.
D. by weight, weigh 9 parts of butyl acrylates to mix with 8 parts of methyl methacrylates, and 20 parts of water is added
With 0.2 part of surfactant, mixed solution is made in ultrasonic 15min；Slowly mixed solution and initiator solution are instilled simultaneously
PANI-GPVA dispersion liquid is warming up to 80 DEG C, reaction time 5h, can be prepared by environment-friendly polypropylene acid esters/polyaniline-polyethylene
Alcohol (PA/PANI-GPVA) ternary IPN structure disperses liquid.The dispersion liquid can be directly used for conductive coating field and
Anticorrosive paint.
E. it takes 100 parts of aqueous polymer resins as matrix resin, adds 4 parts of PA/PANI-GPVA dispersion liquid, thickener
It 0.1 part, 0.2 part of defoaming agent, 5 parts of coalescing agent, is uniformly mixed using physical blending process and is polymerize to get to environment-friendly type ternary interpenetrating
Object network structure coating.
Using and test:
Environment-friendly type ternary IPN structural paint prepared by the present invention is made to be coated on metal tinplate table
Face is compared with blank sample, and the test of chemical property is carried out to product, and specific antiseptic property parameter is as shown in table 1.
Table 1 is different embodiment environment-friendly polypropylene acid esters/polyaniline-polyvinyl alcohol composite materials and coating items physical and chemical performance
And antiseptic property.
Table 1
As can be seen from Table 1, ternary IPN structure disperses liquid prepared by the present invention be applied to coating in,
Every physical chemistry is excellent, and antiseptic property is good, is a kind of environment-friendly type coating of excellent combination property.
Embodiment 6:
A. weighing polyvinyl alcohol (PVA1799) solution, 50 parts of mass fractions that 50 parts of mass fractions are 10% is 10%
Polyvinyl alcohol (PVA0588) solution and 4 parts of glycidyl methacrylate, add in the three-necked flask of 250ml, temperature rises to
60 DEG C, stirring to formation transparent colourless solution；It is then slowly added into nitric acid solution, after pH value is adjusted to 1, it is molten that ammonium ceric nitrate is added dropwise
Liquid, the reaction was continued 2h can be prepared by glycidyl methacrylate modified PVA solution (GPVA).
B. 2 parts of aniline are added dropwise in the GMA-PVA solution for being 10% to 100 parts of mass fractions, 2h is reacted at 50 DEG C and is made
Aniline graft modification GPVA dispersion liquid.
C. aniline graft modification GPVA dispersion liquid system temperature is down to 0 DEG C, naphthalene sulfonic acids solution is added by system pH tune
Section is 1, then the redox reaction of the oxidant potassium peroxydisulfate initiation aniline of metering is added dropwise, and the molar ratio of oxidant and aniline is
0.5, polyaniline grafted modified GPVA (PANI-GPVA) dispersion liquid is made in reaction for 24 hours.
D. by weight, weigh 5 parts of butyl methacrylates to mix with 5 parts of methyl methacrylates, and be added 5 parts
Mixed solution is made in water and 0.04 part of surfactant, ultrasonic 5min；Slowly mixed solution and initiator solution are instilled simultaneously
PANI-GPVA dispersion liquid is warming up to 80 DEG C, reaction time 4h, can be prepared by environment-friendly polypropylene acid esters/poly- second of polyaniline-
Enol (PA/PANI-GPVA) ternary IPN structure disperses liquid.The dispersion liquid can be directly used for conductive coating field
And anticorrosive paint.
E. it takes 100 parts of aqueous alkide resins as matrix resin, adds 0.05 part of PA/PANI-GPVA dispersion liquid, LS-112
It 0.1 part of thickener, 0.1 part of BYK-035 defoaming agent, 2 parts of decylene glycol ester coalescing agent, is uniformly mixed using physical blending process, i.e.,
Obtain environment-friendly type ternary IPN structural paint.
Embodiment 7:
A. it is sweet for 10% polyvinyl alcohol (PVA1099) solution and 8 parts of Glycidyl methacrylates that 100 parts of mass fractions are weighed
Grease adds in the three-necked flask of 250ml, and temperature rises to 60~90 DEG C, stirring to formation transparent colourless solution；Then slowly add
Enter sulfuric acid solution, after pH value is adjusted to 2, ceric ammonium nitrate solution is added dropwise, it is sweet to can be prepared by Glycidyl methacrylate by the reaction was continued 3h
Grease modified PVA solution (GPVA).
B. 6 parts of aniline are added dropwise in the GPVA solution for being 10% to 100 parts of mass fractions, 2h is reacted at 70 DEG C, aniline is made
Graft modification GPVA dispersion liquid.
C. aniline graft modification GPVA dispersion liquid system temperature is down to 4 DEG C, anthraquinone disulfonic acid solution is added by system pH
Value is adjusted to 2, then the redox reaction of the oxidant ammonium persulfate initiation aniline of metering, mole of oxidant and aniline is added dropwise
Than being 1, polyaniline grafted modified GPVA (PANI-GPVA) dispersion liquid is made in reaction 48h.
D. by weight, weigh 10 parts of butyl acrylates to mix with 10 parts of methyl methacrylates, and be added 15 parts
Mixed solution is made in water and 0.1 part of surfactant, ultrasonic 15min；Slowly mixed solution and initiator solution are instilled simultaneously
PANI-GPVA dispersion liquid is warming up to 80 DEG C, reaction time 5h, can be prepared by environment-friendly polypropylene acid esters/polyaniline-polyethylene
Alcohol (PA/PANI-GPVA) ternary IPN structure disperses liquid.The dispersion liquid can be directly used for conductive coating field and
Anticorrosive paint.
E. it takes 100 parts of aqueous polymer resins as matrix resin, adds 4 parts of PA/PANI-GPVA dispersion liquid, thickener
It 0.2 part, 0.3 part of defoaming agent, 8 parts of coalescing agent, is uniformly mixed using physical blending process and is polymerize to get to environment-friendly type ternary interpenetrating
Object network structure coating.
The above content is a further detailed description of the present invention in conjunction with specific preferred embodiments, and it cannot be said that
A specific embodiment of the invention is only limitted to this, for those of ordinary skill in the art to which the present invention belongs, not every
Under the premise of from present inventive concept, several simple deduction or replace can also be made, the present invention is all shall be regarded as belonging to and is mentioned
Claims of friendship determine scope of patent protection.
Claims (10)
1. a kind of preparation method of ternary IPN structural paint, which comprises the following steps:
A. by weight, the polyvinyl alcohol water solution and 4~8 parts of methacrylic acid contractings that 100 parts of mass fractions are 10% are weighed
Water glyceride, adds in reactor, and temperature rises to 60~90 DEG C, is stirred to react to formation transparent colourless solution；Then slowly add
Enter acid, after pH value is adjusted to 1~2, ceric ammonium nitrate solution is added dropwise, continues sufficiently reaction, glycidyl methacrylate is made
Modified PVA solution, i.e. GPVA solution；
B. by weight, 2~6 parts of aniline are added dropwise in the GPVA solution for being 10% to 100 parts of mass fractions, at 50~70 DEG C
Aniline graft modification GPVA dispersion liquid is made in sufficiently reaction；
C. aniline graft modification GPVA dispersion liquid system temperature is down to 0~5 DEG C, acid solution is added by system pH and is adjusted to 1
~2, then the redox reaction that oxidant causes aniline is added dropwise, polyaniline grafted modified GPVA dispersion is made in 24~48h of reaction
Liquid, i.e. PANI-GPVA dispersion liquid；
D. by weight, 5~10 parts of soft acrylate monomers are weighed to mix with 5~10 parts of rigid acrylate monomers, and
5~20 parts of water and 0.04-0.2 parts of surfactants is added, mixed solution is uniformly made in ultrasonic mixing；Slowly by mixed solution
PANI-GPVA dispersion liquid obtained above is instilled simultaneously with initiator solution, 75~85 DEG C is warming up to, sufficiently reacts, is made poly-
Acrylate/polyaniline-polyvinyl alcohol ternary IPN structure disperses liquid, i.e. PA/PANI-GPVA dispersion liquid；
E. by weight, take 100 parts of aqueous polymer resins as matrix resin, add PA/PANI-GPVA dispersion obtained
It is 1~10 part of liquid, 0.05~0.2 part of thickener, 0.1~0.3 part of defoaming agent, 2~8 parts of coalescing agent, mixed using physical blending process
It closes uniformly, obtains ternary IPN structural paint.
2. a kind of preparation method of ternary IPN structural paint according to claim 1, it is characterised in that:
The polyvinyl alcohol model is 0588,1088 or 1799；
The acid is hydrochloric acid, sulfuric acid, dodecyl benzene sulfonic acid, anthraquinone disulfonic acid, naphthalene sulfonic acids, citric acid or nitric acid.
3. a kind of preparation method of ternary IPN structural paint according to claim 1, it is characterised in that:
The oxidant is ammonium persulfate, potassium peroxydisulfate or ferric trichloride, and the molar ratio of oxidant and aniline is 1:(0.5~2).
4. a kind of preparation method of ternary IPN structural paint according to claim 1, it is characterised in that:
The soft acrylate monomer is butyl acrylate, butyl methacrylate, n-octyl, Hexyl 2-propenoate, methyl
The mixture that one or more of n-octyl and hexyl methacrylate arbitrarily match.
5. a kind of preparation method of ternary IPN structural paint according to claim 1, it is characterised in that:
The hardness acrylate monomer is that one or more of methyl acrylate, methyl methacrylate and styrene are any
The mixture of proportion.
6. a kind of preparation method of ternary IPN structural paint according to claim 1, it is characterised in that:
The surfactant is lauryl sodium sulfate, neopelex, methyl orange, paratoluenesulfonic acid sodium salt, double 12
One or more of alkyl phenyl ether sodium disulfonate, disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate and lauryl sodium sulfate are appointed
The mixture for proportion of anticipating.
7. a kind of preparation method of ternary IPN structural paint according to claim 1, it is characterised in that:
The initiator is that one or more of potassium peroxydisulfate, ammonium persulfate and azo diisobutyl amidine hydrochloride are arbitrarily matched
The mixture of ratio.
8. a kind of preparation method of ternary IPN structural paint according to claim 1, it is characterised in that:
The aqueous polymer resin is waterborne polyurethane resin, aqueous epoxy resins, waterborne acrylic paint, water alcohol acid tree
The mixture that one or more of rouge and waterborne polyurethane-polyacrylate resin arbitrarily match.
9. a kind of preparation method of ternary IPN structural paint according to claim 1, it is characterised in that:
The thickener is LS-112 or DL-80；
The defoaming agent is BYK-034, BYK-035 or BYK-037 of BYK company of Germany production；
The coalescing agent is decylene glycol ester, butyl glycol ether.
10. a kind of ternary IPN structural paint, it is characterised in that: measure, be made of the following components by weight:
100 parts of aqueous polymer resins, 1~10 part of PA/PANI-GPVA dispersion liquid, 0.05~0.2 part of thickener, defoaming agent 0.1
~0.3 part, 2~8 parts of coalescing agent.
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