CN110183948A - A kind of preparation method of alkylated polyphenyls amine/aqueous alkide resin composite anticorrosion coating - Google Patents
A kind of preparation method of alkylated polyphenyls amine/aqueous alkide resin composite anticorrosion coating Download PDFInfo
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- CN110183948A CN110183948A CN201910562414.6A CN201910562414A CN110183948A CN 110183948 A CN110183948 A CN 110183948A CN 201910562414 A CN201910562414 A CN 201910562414A CN 110183948 A CN110183948 A CN 110183948A
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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
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/08—Polyesters modified with higher fatty oils or their acids, or with natural resins or resin 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
- 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
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
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Abstract
The invention discloses a kind of preparation methods of alkylated polyphenyls amine/aqueous alkide resin composite anticorrosion coating.Aniline and high molecular surfactant are dissolved in dilute hydrochloric acid, sequentially add the dilute hydrochloric acid containing water soluble starter, p-phenylenediamine/ethanol solution is reacted.Reaction solution is filtered by vacuum and is washed to neutrality, polyaniline is obtained；Polyaniline is added in the dimethyl sulfoxide of dissolution sodium hydride and is reacted, brominated alkanes are then added, and the reaction was continued.By the solution vacuum filtration after reaction, cleaning, drying obtain alkylated polyphenyls amine；Alkyd resin is thoroughly dissolved in the organic solvent that oil-soluble initiator is added, the vinyl monomer that dissolution oil-soluble initiator is slowly added dropwise is reacted, then organic base is sequentially added to be neutralized, drier and the organic solvent containing alkylated polyphenyls amine is added, finally plus water dispersion obtains composite anticorrosion coating.For Metal surface anti-corrosion, anti-corrosion capability, water resistance of metal etc. can be greatly improved.
Description
Technical field
The invention belongs to anticorrosive paint field, in particular to a kind of alkylated polyphenyls amine/aqueous alkide resin composite anti-corrosive
The preparation method of coating.
Background technique
Alkyd resin have superior adhesion strength and film forming, can be applied to anti-corrosion of metal field, if but metal only
Alkyd resin is coated, anti-corrosion effect is not fine.Alkyd resin can be sent out with compound polyphenylamine, polyaniline in metal surface
Raw redox reaction forms one layer of fine and close oxidation film, to play anti-corrosion protection to metal.Exist to solve polyaniline
The problems such as dissolubility and poor mechanical property, will be modified polyaniline, using dibromoalkane hydrocarbon modified polyaniline and be used for
The research for preparing alkylated polyphenyls amine has not been reported substantially.
Summary of the invention
The purpose of the present invention is to provide alkylated polyphenyls amine/aqueous alkide resin composite anticorrosion coating preparation methods.
Product of the present invention can realize that anticorrosive paint compatibility, rigidity and adhesion strength are unified, solve polyaniline/aqueous alkide resin
The industries common technology problems such as composite anticorrosion coating stability is poor, water resistance is low, adhesive force is bad are used for Metal surface anti-corrosion,
Anti-corrosion capability, the water resistance etc. of metal can be greatly improved.
To achieve the above object, present invention provide the technical scheme that
A kind of preparation method of alkylated polyphenyls amine/aqueous alkide resin composite anticorrosion coating, includes the following steps:
Aniline and high molecular surfactant are dissolved in hydrochloric acid, sequentially added under condition of ice bath containing water soluble starter
Hydrochloric acid, p-phenylenediamine ethanol solution reacted；After reaction solution is filtered and washed, filter residue and drying obtains polyaniline；
Polyaniline is added in the dimethyl sulfoxide of dissolution sodium hydride and is reacted, brominated alkanes are then added and continue instead
It answers；Solution after reaction is filtered, filter residue and drying after cleaning obtains alkylated polyphenyls amine；
Alkyd resin is dissolved in the organic solvent that oil-soluble initiator is added, dissolution oil-soluble initiator is slowly added dropwise
Vinyl monomer reacted, sequentially add organic base and neutralized, drier and having containing alkylated polyphenyls amine is added
Solvent；Water dispersion is added to obtain alkylated polyphenyls amine/aqueous alkide resin composite anticorrosion coating.
As a further improvement of the present invention, in the preparation process of the polyaniline, the additional proportion of raw material are as follows:
In parts by mass, every 5 parts of aniline be added 5~10 portions of high molecular surfactants, 5~10 parts of water soluble starters,
0.2~0.4 part of p-phenylenediamine.
As a further improvement of the present invention, small in 0~5 DEG C of reaction 1-2 after the hydrochloric acid containing water soluble starter being added
When, p-phenylenediamine ethanol solution is then added, the reaction was continued 4 hours.
As a further improvement of the present invention, in the preparation process of the alkylated polyphenyls amine, the additional proportion of raw material
Are as follows:
In parts by mass, 5~10 parts of anhydrous dimethyl sulphoxides of every 0.5~1 part of sodium hydride addition, 1 part of polyaniline and 1-3 parts
Brominated alkanes.
As a further improvement of the present invention, polyaniline is added in the dimethyl sulfoxide of dissolution sodium hydride and is warming up to 60 DEG C,
It is added after polyaniline reacts 4 hours and is cooled to 35~45 DEG C, brominated alkanes are then added, and the reaction was continued 14~18 hours.
As a further improvement of the present invention, alkylated polyphenyls amine/aqueous alkide resin composite anticorrosion coating process is obtained
In, the additional proportion of raw material are as follows:
In parts by mass, it is molten that 1 part of oil-soluble initiator, 15 parts of alkyd resins, 0.1 part of oil is added in every 15 parts of vinyl monomers
Property initiator, 2-4 parts of organic bases, 0.5-1.5 parts of drier and 0.015~0.15 part of alkylated polyphenyls amine.
As a further improvement of the present invention, alkyd resin, oil-soluble initiator are dissolved at 65-85 DEG C organic molten
In agent, then starts the vinyl monomer that dissolution oil-soluble initiator is added dropwise, drip off within 2-3 hours, it is small to drip off subsequent continuation of insurance temperature 3-4
When.
As a further improvement of the present invention, water dispersion is added to be dispersed to the effective matter of system using 80-90 DEG C of deionized water
Amount score is 45-50%.
As a further improvement of the present invention, the high molecular surfactant is polyoxethylene octylphenyl phenol ether -10, alkane
Base alcohol polyoxyethylene (3) ammonium sulfate, two sulphur of allyloxy Nonyl pheno (10) ether ammonium sulfate and dodecyl diphenyl oxide
One of sour sodium or a variety of mixtures arbitrarily matched；
The water soluble starter is one of potassium peroxydisulfate, sodium peroxydisulfate, ammonium persulfate or a variety of any proportions
Mixture；
The brominated alkanes are bis- bromooctane of 1,8-, bis- bromo certain herbaceous plants with big flowers alkane of 1,10-, bis- bromododecane of 1,12- and 1,14-
One of two bromotetradecanes or a variety of mixtures arbitrarily matched.
As a further improvement of the present invention, the organic solvent is n,N-Dimethylformamide or N- crassitude
The mixture that one or both of ketone arbitrarily matches；
The vinyl monomer is acrylic acid, butyl acrylate, methyl methacrylate, ethyl acrylate, methyl-prop
One of olefin(e) acid ethyl ester, styrene, α-methylstyrene or a variety of mixtures arbitrarily matched；
The oil-soluble initiator is azodiisobutyronitrile, azobisisoheptonitrile, azo-bis-iso-dimethyl, peroxidating
Benzoyl, one of tert-butyl hydroperoxide or a variety of mixtures arbitrarily matched；
The organic base are as follows: ethylenediamine, triethylamine, dimethylethanolamine, triethanolamine, diethanol amine, in ethanol amine
One or more mixtures arbitrarily matched；
The drier is one of cobalt naphthenate, manganese naphthenate, cobalt iso-octoate, manganese iso-octoate or a variety of arbitrarily matches
The mixture of ratio.
Compared with prior art, the invention has the following beneficial effects:
It is compound anti-that the present invention uses dibromoalkane hydrocarbon modified polyaniline to be used to prepare alkylated polyphenyls amine/aqueous alkide resin
Rotten coating.Polyaniline is alkylated processing, alkylated polyphenyls amine is to improve polyaniline in aqueous alcoholic in the introducing of alkyl
Dispersibility in acid resin, to improve the stability of anticorrosive paint, compatibility, rigidity and adhesion strength；Pass through alkyd
Resin with alkylated polyphenyls amine is compound prepares composite anticorrosion coating, while enhancing the water resistance of coating, further improve gold
The antiseptic property of metal surface.Product of the present invention can realize the unification of anticorrosive paint compatibility, rigidity and adhesion strength, solve
The industries common technologies such as polyaniline/aqueous alkide resin composite anticorrosion coating stability is poor, water resistance is low, adhesive force is bad are asked
Topic is used for Metal surface anti-corrosion, can greatly improve anti-corrosion capability, water resistance of metal etc..
Specific embodiment
A kind of preparation method of alkylated polyphenyls amine/aqueous alkide resin composite anticorrosion coating of the present invention, including walk as follows
It is rapid:
1) in parts by mass, by 5 parts of aniline, 5~10 portions of high molecular surfactants are dissolved in 50~100 parts of 1M/L hydrochloric acid
Obtain mixed liquor A；
2) 5~10 parts of water soluble starters are dissolved in 50~100 parts of 1M/L hydrochloric acid and obtain mixed liquid B；
3) 0.2~0.4 part of p-phenylenediamine is dissolved in 5~10 parts of dehydrated alcohols and obtains mixed liquor C；
4) mixed liquor A is cooled to 0~5 DEG C, mixed liquid B is added, reacted 1-2 hours.Then mixed liquor C is added again anti-
It answers in liquid, the reaction was continued 4 hours obtains mixed liquor D；
5) mixed liquor D is filtered by vacuum and is washed to neutrality, suction filtration obtains filter residue, obtains polyphenyl after vacuum drying
Amine；
6) 0.5~1 part of sodium hydride is dissolved in 5~10 parts of anhydrous dimethyl sulphoxides and obtains mixed liquor E；
7) mixed liquor E is warming up to 60 DEG C, 1 part of polyaniline is added, reaction was cooled to 35~45 DEG C after 4 hours.Then plus
Enter 1-3 parts of brominated alkanes the reaction was continued 14~18 hours to obtain mixed liquor F；
8) mixed liquor F be filtered by vacuum and alternately be cleaned respectively three times with methanol, deionized water and acetone, filtered
To filter residue, alkylated polyphenyls amine is obtained after vacuum drying；
9) 15 parts of vinyl monomers and 1 part of oil-soluble initiator are mixed to get mixed liquor G；
10) 15 parts of alkyd resins, 0.1 part of oil-soluble initiator are dissolved in 20 parts of organic solvents at 65-85 DEG C, so
After start that mixed liquor G is added dropwise, drip off within about 2-3 hour, drip off subsequent continuation of insurance temperature 3-4 hours, add into system 2-4 parts of organic bases with
Then 0.015~0.15 part of alkylated polyphenyls amine is added in 0.5-1.5 parts of drier, finally dispersed with 80-90 DEG C of deionized water
It is 45-50% to system effective mass score, obtains alkylated polyphenyls amine/aqueous alkide resin composite anticorrosion coating.
Wherein, it is between 150-190 based on oleic acid that the alkyd resin acid value, which is by iodine number, and acid value is in 15-20, admittedly contain
Value is one of alkyd resin of 97.5%-99.7% or a variety of mixtures arbitrarily matched.
The high molecular surfactant be polyoxethylene octylphenyl phenol ether -10, alkylol polyoxyethylene (3) ammonium sulfate,
Allyloxy Nonyl pheno (10) one of ether ammonium sulfate and disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate is a variety of any
The mixture of proportion.
The water soluble starter is one of potassium peroxydisulfate, sodium peroxydisulfate, ammonium persulfate or a variety of any proportions
Mixture.
The brominated alkanes are bis- bromooctane of 1,8-, bis- bromo certain herbaceous plants with big flowers alkane of 1,10-, bis- bromododecane of 1,12- and 1,14-
One of two bromotetradecanes or a variety of mixtures arbitrarily matched.
The organic solvent is that one or both of N,N-dimethylformamide or N-Methyl pyrrolidone are arbitrarily matched
The mixture of ratio.
The vinyl monomer is acrylic acid, butyl acrylate, methyl methacrylate, ethyl acrylate, methyl-prop
One of olefin(e) acid ethyl ester, styrene, α-methylstyrene or a variety of mixtures arbitrarily matched.
The oil-soluble initiator is azodiisobutyronitrile, azobisisoheptonitrile, azo-bis-iso-dimethyl, peroxidating
Benzoyl, one of tert-butyl hydroperoxide or a variety of mixtures arbitrarily matched.
The organic base are as follows: ethylenediamine, triethylamine, dimethylethanolamine, triethanolamine, diethanol amine, in ethanol amine
One or more mixtures arbitrarily matched.
The drier is one of cobalt naphthenate, manganese naphthenate, cobalt iso-octoate, manganese iso-octoate or a variety of arbitrarily matches
The mixture of ratio.
The present invention will be further described in detail below with reference to the embodiments, this implementation column does not constitute restriction to the present invention.
Embodiment 1:
1) in parts by mass, by 5 parts of aniline, 5 parts of polyoxethylene octylphenyl phenol ethers -10, which are dissolved in 50 parts of 1M/L hydrochloric acid, to be obtained
Mixed liquor A；
2) 5 parts of potassium peroxydisulfates are dissolved in 50 parts of 1M/L hydrochloric acid and obtain mixed liquid B；
3) 0.2 part of p-phenylenediamine is dissolved in 5 parts of dehydrated alcohols and obtains mixed liquor C；
4) mixed liquor A is cooled to 0 DEG C, mixed liquid B is added, reacted 1 hour.Then reaction solution is added in mixed liquor C again
In, the reaction was continued 4 hours obtains mixed liquor D；
5) mixed liquor D is filtered by vacuum and is washed to neutrality, suction filtration obtains filter residue, obtains polyphenyl after vacuum drying
Amine；
6) 0.5 part of sodium hydride is dissolved in 5 parts of anhydrous dimethyl sulphoxides and obtains mixed liquor E；
7) mixed liquor E is warming up to 60 DEG C, 1 part of polyaniline is added, reaction was cooled to 35 DEG C after 4 hours.Then it is added 1 part
The reaction was continued 11 hours obtains mixed liquor F for bis- bromooctane of 1,8-；
8) mixed liquor F be filtered by vacuum and alternately be cleaned respectively three times with methanol, deionized water and acetone, filtered
To filter residue, alkylated polyphenyls amine is obtained after vacuum drying；
9) 1 part of acrylic acid, 10 parts of methyl methacrylates, 2 parts of styrene, 2 parts of butyl acrylates and 1 part of azo two is different
Heptonitrile is mixed to get mixed liquor G；
10) by 15 parts of alkyd resins (oleic acid iodine number 155, acid value 18, mass fraction 98%), 0.1 part of azo at 65 DEG C
Two different heptonitriles are dissolved in 20 parts of n,N-Dimethylformamide, are then started that mixed liquor G is added dropwise, are dripped off within about 2 hours, drip off subsequent
Continuation of insurance temperature 3 hours, 2 parts of dimethylethanolamines and 0.5 part of manganese naphthenate are added into system, and it is poly- that 0.015 part of alkylation is then added
Aniline, being finally dispersed to system effective mass score with 80 DEG C of deionized water is 45%, obtains alkylated polyphenyls amine/aqueous alcoholic
Acid resin composite anticorrosion coating.
Embodiment 2:
1) in parts by mass, by 5 parts of aniline, 10 parts of disodium 4-dodecyl-2,4 '-oxydibenzenesulfonates are dissolved in 100 parts of 1M/L hydrochloric acid
Obtain mixed liquor A；
2) 10 parts of ammonium persulfates are dissolved in 100 parts of 1M/L hydrochloric acid and obtain mixed liquid B；
3) 0.4 part of p-phenylenediamine is dissolved in 5~10 parts of dehydrated alcohols and obtains mixed liquor C；
4) mixed liquor A is cooled to 5 DEG C, mixed liquid B is added, reacted 2 hours.Then reaction solution is added in mixed liquor C again
In, the reaction was continued 4 hours obtains mixed liquor D；
5) mixed liquor D is filtered by vacuum and is washed to neutrality, suction filtration obtains filter residue, obtains polyphenyl after vacuum drying
Amine；
6) 1 part of sodium hydride is dissolved in 10 parts of anhydrous dimethyl sulphoxides and obtains mixed liquor E；
7) mixed liquor E is warming up to 60 DEG C, 1 part of polyaniline is added, reaction was cooled to 45 DEG C after 4 hours.Then 2 parts are added
The reaction was continued 18 hours obtains mixed liquor F for bis- bromododecane of 1,12-；
8) mixed liquor F be filtered by vacuum and alternately be cleaned respectively three times with methanol, deionized water and acetone, filtered
To filter residue, alkylated polyphenyls amine is obtained after vacuum drying；
9) by 1.5 parts of acrylic acid, 11.5 parts of methyl methacrylates, 1 part of styrene, 1 part of butyl acrylate and 1 part of azo
Two isobutyl dimethyl phthalates are mixed to get mixed liquor G；
10) by 15 parts of alkyd resins (oleic acid iodine number 190, acid value 15, mass fraction 99.5%), 0.1 part of idol at 85 DEG C
Two isobutyl dimethyl phthalate of nitrogen is dissolved in 20 parts of N-Methyl pyrrolidones, is then started that mixed liquor G is added dropwise, is dripped off within about 3 hours, drips
Complete subsequent continuation of insurance temperature 4 hours, into system plus 4 parts of diethanol amine and 1.5 parts of cobalt iso-octoates, then 0.15 part of alkylation of addition gathered
Aniline, being finally dispersed to system effective mass score with 90 DEG C of deionized water is 50%, obtains alkylated polyphenyls amine/aqueous alcoholic
Acid resin composite anticorrosion coating.
Embodiment 3:
1) in parts by mass, by 5 parts of aniline, 7 parts of allyloxy Nonyl pheno (10) ether ammonium sulfates are dissolved in 75 parts
Mixed liquor A is obtained in 1M/L hydrochloric acid；
2) 7 parts of potassium peroxydisulfates are dissolved in 75 parts of 1M/L hydrochloric acid and obtain mixed liquid B；
3) 0.3 part of p-phenylenediamine is dissolved in 8 parts of dehydrated alcohols and obtains mixed liquor C；
4) mixed liquor A is cooled to 3 DEG C, mixed liquid B is added, reacted 1.5 hours.Then mixed liquor C is added again and is reacted
In liquid, the reaction was continued 4 hours obtains mixed liquor D；
5) mixed liquor D is filtered by vacuum and is washed to neutrality, suction filtration obtains filter residue, obtains polyphenyl after vacuum drying
Amine；
6) 0.7 part of sodium hydride is dissolved in 7 parts of anhydrous dimethyl sulphoxides and obtains mixed liquor E；
7) mixed liquor E is warming up to 60 DEG C, 1 part of polyaniline is added, reaction was cooled to 40 DEG C after 4 hours.Then it is added 1 part
The reaction was continued 15 hours obtains mixed liquor F for bis- bromotetradecane of 1,14-；
8) mixed liquor F be filtered by vacuum and alternately be cleaned respectively three times with methanol, deionized water and acetone, filtered
To filter residue, alkylated polyphenyls amine is obtained after vacuum drying；
9) 1 part of acrylic acid, 12 parts of styrene, 2 parts of butyl acrylates and 1 part of tert-butyl hydroperoxide are mixed to get mixing
Liquid G；
10) by 15 parts of alkyd resins (oleic acid iodine number 175, acid value 17, mass fraction 98%), 0.1 part of tertiary fourth at 75 DEG C
Base hydrogen peroxide is dissolved in 20 parts of n,N-Dimethylformamide, is then started that mixed liquor G is added dropwise, is dripped off within about 2.5 hours, drip off
Subsequent continuation of insurance temperature 3.5 hours, 2.5 parts of ethylenediamines and 1 part of cobalt iso-octoate are added into system, 0.03 part of alkylated polyphenyls is then added
Amine, being finally dispersed to system effective mass score with 85 DEG C of deionized water is 47%, obtains alkylated polyphenyls amine/water alcohol acid
Resin compounded anticorrosive paint.
Embodiment 4:
1) in parts by mass, by 5 parts of aniline, 8 parts of allyloxy Nonyl pheno (10) ether ammonium sulfates are dissolved in 50 parts
Mixed liquor A is obtained in 1M/L hydrochloric acid；
2) 6 parts of sodium peroxydisulfates are dissolved in 80 parts of 1M/L hydrochloric acid and obtain mixed liquid B；
3) 0.25 part of p-phenylenediamine is dissolved in 5 parts of dehydrated alcohols and obtains mixed liquor C；
4) mixed liquor A is cooled to 0 DEG C, mixed liquid B is added, reacted 1.5 hours.Then mixed liquor C is added again and is reacted
In liquid, the reaction was continued 4 hours obtains mixed liquor D；
5) mixed liquor D is filtered by vacuum and is washed to neutrality, suction filtration obtains filter residue, obtains polyphenyl after vacuum drying
Amine；
6) 0.6 part of sodium hydride is dissolved in 10 parts of anhydrous dimethyl sulphoxides and obtains mixed liquor E；
7) mixed liquor E is warming up to 60 DEG C, 1 part of polyaniline is added, reaction was cooled to 35 DEG C after 4 hours.Then 3 parts are added
The reaction was continued 15 hours obtains mixed liquor F for bis- bromo certain herbaceous plants with big flowers alkane of 1,10-；
8) mixed liquor F be filtered by vacuum and alternately be cleaned respectively three times with methanol, deionized water and acetone, filtered
To filter residue, alkylated polyphenyls amine is obtained after vacuum drying；
9) 2 parts of acrylic acid, 10 parts of styrene, 3 parts of methyl methacrylates and 1 part of azobisisoheptonitrile are mixed to get mixed
Close liquid G；
10) by 15 parts of alkyd resins (oleic acid iodine number 170, acid value 18, mass fraction 99%), 0.1 part of azo at 70 DEG C
Two different heptonitriles are dissolved in 20 parts of N-Methyl pyrrolidones, are then started that mixed liquor G is added dropwise, are dripped off within about 2 hours, continue after dripping off
Heat preservation 3 hours adds 3 parts of triethanolamines and 0.5 part of manganese iso-octoate into system, 0.05 part of alkylated polyphenyls amine is then added, most
Being dispersed to system effective mass score with 90 DEG C of deionized water afterwards is 48%, obtains alkylated polyphenyls amine/aqueous alkide resin
Composite anticorrosion coating.
Embodiment 5:
1) in parts by mass, by 5 parts of aniline, 10 parts of polyoxethylene octylphenyl phenol ethers -10, which are dissolved in 85 parts of 1M/L hydrochloric acid, to be obtained
To mixed liquor A；
2) 5 parts of ammonium persulfates are dissolved in 75 parts of 1M/L hydrochloric acid and obtain mixed liquid B；
3) 0.4 part of p-phenylenediamine is dissolved in 10 parts of dehydrated alcohols and obtains mixed liquor C；
4) mixed liquor A is cooled to 5 DEG C, mixed liquid B is added, reacted 2 hours.Then reaction solution is added in mixed liquor C again
In, the reaction was continued 4 hours obtains mixed liquor D；
5) mixed liquor D is filtered by vacuum and is washed to neutrality, suction filtration obtains filter residue, obtains polyphenyl after vacuum drying
Amine；
6) 1 part of sodium hydride is dissolved in 5 parts of anhydrous dimethyl sulphoxides and obtains mixed liquor E；
7) mixed liquor E is warming up to 60 DEG C, 1 part of polyaniline is added, reaction was cooled to 40 DEG C after 4 hours.Then it is added 1 part
The reaction was continued 16 hours obtains mixed liquor F for bis- bromooctane of 1,8- and 1 part of bis- bromododecane of 1,12-；
8) mixed liquor F be filtered by vacuum and alternately be cleaned respectively three times with methanol, deionized water and acetone, filtered
To filter residue, alkylated polyphenyls amine is obtained after vacuum drying；
9) by 1 part of acrylic acid, 5 parts of methyl acrylates, 5 parts of methyl methacrylates, 4 parts of styrene and 1 part of benzoyl peroxide
Formyl is mixed to get mixed liquor G；
10) by 15 parts of alkyd resins (oleic acid iodine number 170, acid value 18, mass fraction 97.8%), 0.1 part of mistake at 70 DEG C
Benzoyl Oxide is dissolved in 20 parts of n,N-Dimethylformamide, is then started that mixed liquor G is added dropwise, is dripped off within about 2 hours, after dripping off
Continue heat preservation 4 hours, 2 parts of ethanol amines and 1 part of cobalt naphthenate are added into system, 0.1 part of alkylated polyphenyls amine is then added, finally
Being dispersed to system effective mass score with 90 DEG C of deionized water is 49.5%, obtains alkylated polyphenyls amine/aqueous alkide resin
Composite anticorrosion coating.
Performance data of the anti-corrosion paint prepared under the conditions of different embodiments on iron plate:
Note: the preparation method is the same as that of Example 1 for comparative sample, and alkylated polyphenyls amine is only replaced with polyaniline；Iron plate is 400 mesh sand
Tinplate after paper polishing, 3.5% NaCl solution is as corrosive medium；Electro-chemical test is electricity with 3.5%NaCl solution
Liquid is solved, saturated calomel electrode is reference electrode, and platinum electrode is to electrode, and working electrode is composite anti-corrosive coating.
Embodiment 6:
1) in parts by mass, by 5 parts of aniline, 5 portions of high molecular surfactants, which are dissolved in 50 parts of 1M/L hydrochloric acid, to be mixed
Liquid A；
2) 5 parts of water soluble starters are dissolved in 50 parts of 1M/L hydrochloric acid and obtain mixed liquid B；
3) 0.2 part of p-phenylenediamine is dissolved in 5 parts of dehydrated alcohols and obtains mixed liquor C；
4) mixed liquor A is cooled to 0 DEG C, mixed liquid B is added, reacted 1 hour.Then reaction solution is added in mixed liquor C again
In, the reaction was continued 4 hours obtains mixed liquor D；
5) mixed liquor D is filtered by vacuum and is washed to neutrality, suction filtration obtains filter residue, obtains polyphenyl after vacuum drying
Amine；
6) 0.5 part of sodium hydride is dissolved in 5 parts of anhydrous dimethyl sulphoxides and obtains mixed liquor E；
7) mixed liquor E is warming up to 60 DEG C, 1 part of polyaniline is added, reaction was cooled to 35 DEG C after 4 hours.Then it is added 1 part
The reaction was continued 14 hours obtains mixed liquor F for brominated alkanes；
8) mixed liquor F be filtered by vacuum and alternately be cleaned respectively three times with methanol, deionized water and acetone, filtered
To filter residue, alkylated polyphenyls amine is obtained after vacuum drying；
9) 15 parts of vinyl monomers and 1 part of oil-soluble initiator are mixed to get mixed liquor G；
10) 15 parts of alkyd resins, 0.1 part of oil-soluble initiator are dissolved in 20 parts of organic solvents at 65 DEG C, then
Start that mixed liquor G is added dropwise, drip off within about 3 hours, drip off subsequent continuation of insurance temperature 4 hours, adds 4 parts of organic bases into system and 1.5 parts are urged
Dry agent, is then added 0.15 part of alkylated polyphenyls amine, being finally dispersed to system effective mass score with 90 DEG C of deionized water is
50%, obtain alkylated polyphenyls amine/aqueous alkide resin composite anticorrosion coating.
Embodiment 7:
1) in parts by mass, by 5 parts of aniline, 10 portions of high molecular surfactants, which are dissolved in 100 parts of 1M/L hydrochloric acid, to be mixed
Close liquid A；
2) 10 parts of water soluble starters are dissolved in 100 parts of 1M/L hydrochloric acid and obtain mixed liquid B；
3) 0.4 part of p-phenylenediamine is dissolved in 10 parts of dehydrated alcohols and obtains mixed liquor C；
4) mixed liquor A is cooled to 5 DEG C, mixed liquid B is added, reacted 2 hours.Then reaction solution is added in mixed liquor C again
In, the reaction was continued 4 hours obtains mixed liquor D；
5) mixed liquor D is filtered by vacuum and is washed to neutrality, suction filtration obtains filter residue, obtains polyphenyl after vacuum drying
Amine；
6) 1 part of sodium hydride is dissolved in 10 parts of anhydrous dimethyl sulphoxides and obtains mixed liquor E；
7) mixed liquor E is warming up to 60 DEG C, 1 part of polyaniline is added, reaction was cooled to 45 DEG C after 4 hours.Then 3 parts are added
The reaction was continued 18 hours obtains mixed liquor F for brominated alkanes；
8) mixed liquor F be filtered by vacuum and alternately be cleaned respectively three times with methanol, deionized water and acetone, filtered
To filter residue, alkylated polyphenyls amine is obtained after vacuum drying；
9) 15 parts of vinyl monomers and 1 part of oil-soluble initiator are mixed to get mixed liquor G；
10) 15 parts of alkyd resins, 0.1 part of oil-soluble initiator are dissolved in 20 parts of organic solvents at 65 DEG C, then
Start that mixed liquor G is added dropwise, drip off within about 2 hours, drip off subsequent continuation of insurance temperature 3 hours, adds 2 parts of organic bases into system and 0.5 part is urged
Dry agent, is then added 0.015 part of alkylated polyphenyls amine, being finally dispersed to system effective mass score with 80 DEG C of deionized water is
45%, obtain alkylated polyphenyls amine/aqueous alkide resin composite anticorrosion coating.
It is multiple that the present invention uses dibromoalkane hydrocarbon modified polyaniline to be used to prepare alkylated polyphenyls amine/aqueous alkide resin for the first time
Close anticorrosive paint.When products made thereby is used for Metal surface anti-corrosion, alkylated polyphenyls amine is dispersed in aqueous alkide resin
Raising has been arrived, to improve the stability of anticorrosive paint, compatibility, rigidity and adhesion strength, while having enhanced coating
Water resistance further improves the antiseptic property of metal surface.Product of the present invention can realize anticorrosive paint compatibility, rigidity and
The unification of adhesion strength, solves that polyaniline/aqueous alkide resin composite anticorrosion coating stability is poor, water resistance is low, adhesive force
The industries common technology problem such as bad is used for Metal surface anti-corrosion, can greatly improve anti-corrosion capability, water resistance of metal etc..
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, is not taking off
Under the premise of from present inventive concept, several simple deduction or replace can also be made, all shall be regarded as belonging to the present invention by institute
Claims of submission determine scope of patent protection.
Claims (10)
1. a kind of preparation method of alkylated polyphenyls amine/aqueous alkide resin composite anticorrosion coating, which is characterized in that including as follows
Step:
Aniline and high molecular surfactant are dissolved in hydrochloric acid, the salt containing water soluble starter is sequentially added under condition of ice bath
Acid, p-phenylenediamine ethanol solution are reacted；After reaction solution is filtered and washed, filter residue and drying obtains polyaniline；
Polyaniline is added in the dimethyl sulfoxide of dissolution sodium hydride and is reacted, brominated alkanes are then added, and the reaction was continued；It will
Solution after reaction filters, and filter residue and drying after cleaning obtains alkylated polyphenyls amine；
Alkyd resin is dissolved in the organic solvent that oil-soluble initiator is added, the second of dissolution oil-soluble initiator is slowly added dropwise
Alkenyl monomer is reacted, and is sequentially added organic base and is neutralized, and drier is added and contains the organic molten of alkylated polyphenyls amine
Agent；Water dispersion is added to obtain alkylated polyphenyls amine/aqueous alkide resin composite anticorrosion coating.
2. the preparation method of alkylated polyphenyls amine/aqueous alkide resin composite anticorrosion coating according to claim 1, special
Sign is, in the preparation process of the polyaniline, the additional proportion of raw material are as follows:
In parts by mass, every 5 parts of aniline be added 5~10 portions of high molecular surfactants, 5~10 parts of water soluble starters, 0.2~
0.4 part of p-phenylenediamine.
3. the preparation method of alkylated polyphenyls amine/aqueous alkide resin composite anticorrosion coating according to claim 1, special
Sign is, after the hydrochloric acid containing water soluble starter is added, 0~5 DEG C reaction 1-2 hours, then add p-phenylenediamine second
Alcoholic solution, the reaction was continued 4 hours.
4. the preparation method of alkylated polyphenyls amine/aqueous alkide resin composite anticorrosion coating according to claim 1, special
Sign is, in the preparation process of the alkylated polyphenyls amine, the additional proportion of raw material are as follows:
In parts by mass, 5~10 parts of anhydrous dimethyl sulphoxides, 1 part of polyaniline and 1-3 parts of bromos are added in every 0.5~1 part of sodium hydride
Alkane.
5. the preparation method of alkylated polyphenyls amine/aqueous alkide resin composite anticorrosion coating according to claim 1, special
Sign is that polyaniline is added in the dimethyl sulfoxide of dissolution sodium hydride and is warming up to 60 DEG C, is added after polyaniline reacts 4 hours and cools down
To 35~45 DEG C, brominated alkanes are then added, and the reaction was continued 14~18 hours.
6. the preparation method of alkylated polyphenyls amine/aqueous alkide resin composite anticorrosion coating according to claim 1, special
Sign is, during obtaining alkylated polyphenyls amine/aqueous alkide resin composite anticorrosion coating, the additional proportion of raw material are as follows:
In parts by mass, every 15 parts of vinyl monomers are added 1 part of oil-soluble initiator, 15 parts of alkyd resins, 0.1 part of oil-soluble and draw
Send out agent, 2-4 parts of organic bases, 0.5-1.5 parts of drier and 0.015~0.15 part of alkylated polyphenyls amine.
7. the preparation method of alkylated polyphenyls amine/aqueous alkide resin composite anticorrosion coating according to claim 1, special
Sign is, alkyd resin, oil-soluble initiator are dissolved in organic solvent at 65-85 DEG C, then starts that dissolved oil is added dropwise
The vinyl monomer of soluble initiator drips off for 2-3 hours, drips off subsequent continuation of insurance temperature 3-4 hours.
8. the preparation method of alkylated polyphenyls amine/aqueous alkide resin composite anticorrosion coating according to claim 1, special
Sign is, adds water dispersion that 80-90 DEG C of deionized water is used to be dispersed to system effective mass score as 45-50%.
9. the preparation method of alkylated polyphenyls amine/aqueous alkide resin composite anticorrosion coating according to claim 1, special
Sign is: the high molecular surfactant is polyoxethylene octylphenyl phenol ether -10, alkylol polyoxyethylene (3) ammonium sulfate, alkene
Propoxyl group Nonyl pheno (10) one of ether ammonium sulfate and disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate a variety of is arbitrarily matched
The mixture of ratio；
The water soluble starter be one of potassium peroxydisulfate, sodium peroxydisulfate, ammonium persulfate or it is a variety of arbitrarily match it is mixed
Close object；
The brominated alkanes are bis- bromooctane of 1,8-, bis- bromo certain herbaceous plants with big flowers alkane of 1,10-, bis- bromododecane of 1,12- and 1,14- dibromo
For one of tetradecane or a variety of mixtures arbitrarily matched.
10. special according to the preparation method of alkylated polyphenyls amine/aqueous alkide resin composite anticorrosion coating described in claim 1
Sign is: the organic solvent is that one or both of N,N-dimethylformamide or N-Methyl pyrrolidone arbitrarily match
Mixture；
The vinyl monomer is acrylic acid, butyl acrylate, methyl methacrylate, ethyl acrylate, methacrylic acid
One of ethyl ester, styrene, α-methylstyrene or a variety of mixtures arbitrarily matched；
The oil-soluble initiator is azodiisobutyronitrile, azobisisoheptonitrile, azo-bis-iso-dimethyl, benzoyl peroxide first
Acyl, one of tert-butyl hydroperoxide or a variety of mixtures arbitrarily matched；
The organic base are as follows: ethylenediamine, triethylamine, dimethylethanolamine, triethanolamine, diethanol amine, one in ethanol amine
Kind or a variety of mixtures arbitrarily matched；
The drier is one of cobalt naphthenate, manganese naphthenate, cobalt iso-octoate, manganese iso-octoate or a variety of arbitrarily matches
Mixture.
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| CN111378362A (en) * | 2020-04-24 | 2020-07-07 | 张杨全 | Alkyl polyaniline grafted SiO2Hydrophobic anticorrosive material of epoxy resin and its preparation method |
| CN116554573A (en) * | 2023-04-27 | 2023-08-08 | 山东金沅金新材料科技有限公司 | Composite conductive plastic and preparation method thereof |
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| CN108517173A (en) * | 2018-04-11 | 2018-09-11 | 陕西科技大学 | A kind of preparation method of ultra-hydrophobic property polyaniline composite anticorrosion coating |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111378362A (en) * | 2020-04-24 | 2020-07-07 | 张杨全 | Alkyl polyaniline grafted SiO2Hydrophobic anticorrosive material of epoxy resin and its preparation method |
| CN116554573A (en) * | 2023-04-27 | 2023-08-08 | 山东金沅金新材料科技有限公司 | Composite conductive plastic and preparation method thereof |
| CN116554573B (en) * | 2023-04-27 | 2024-04-26 | 河南海瑞祥科技有限公司 | Composite conductive plastic and preparation method thereof |
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