CN106800880A - The preparation method of the electroactive intrinsic hydridization oligomer coating of benzoxazine polyaniline - Google Patents
The preparation method of the electroactive intrinsic hydridization oligomer coating of benzoxazine polyaniline Download PDFInfo
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- 0 C*(c1ccccc1)c(cc1)ccc1N(C/C1=C(/C2)\COCN2c(cc2)ccc2[N+]c2ccccc2)CO/C1=C(\C)/C=C Chemical compound C*(c1ccccc1)c(cc1)ccc1N(C/C1=C(/C2)\COCN2c(cc2)ccc2[N+]c2ccccc2)CO/C1=C(\C)/C=C 0.000 description 4
- KCXGEKKXLWMFAM-UHFFFAOYSA-N CCN(Cc1c(C)ccc(C2(c3ccccc3-c3ccccc23)c(cc2)cc(C3)c2OCN3c(cc2)ccc2Nc2ccccc2)c1)c(cc1)ccc1Nc1ccccc1 Chemical compound CCN(Cc1c(C)ccc(C2(c3ccccc3-c3ccccc23)c(cc2)cc(C3)c2OCN3c(cc2)ccc2Nc2ccccc2)c1)c(cc1)ccc1Nc1ccccc1 KCXGEKKXLWMFAM-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses the preparation method of the intrinsic hydridization oligomer coating of electroactive benzoxazine polyaniline, the coating is prepared using following steps：(1) by the intrinsic hydridization oligomer of the electroactive benzoxazine polyaniline of 5 50 weight portions and 50 95 weight portion benzoxazine monomers, it is dispersed in 80 120 weight parts organic solvents, obtains coating forerunner's pre-composition；(2) pre-composition is evenly applied to carbon steel, purple steel or articles made of aluminium alloy surface, is heat-treated 0.5 1.5 hours under the conditions of 180 DEG C 200 DEG C, the uniform semitransparent coating that thickness is 5 200 microns is obtained after natural cooling.The present invention introduces the electroactive benzoxazine structure of polarity by MOLECULE DESIGN in polyaniline molecule main chain, obtains the electrically active function oligomer with excellent machinability.The oligomer has flexible MOLECULE DESIGN performance, good thermal stability and excellent mechanical property and preferable processing characteristics.The coating for being provided has excellent adhesive strength, high glass-transition temperature and good chemicals-resistant corrosive nature.
Description
Technical field
It is specifically a kind of to be based on electroactive Ben Bing Evil the present invention relates to a kind of high-molecular organic material technical field
Piperazine-polyaniline hybridized oligomer, and use the coating and preparation method of its making.
Background technology
At present, in industrial circle, metallic material corrosion is a global problem, often results in serious economic damage
Lose and trigger safety problem.The method of this problem should be mainly carries out metal erosion protection using corrosion-inhibiting coating, using painting
Layer preserving method, with simple to operate, economical and practical, applied widely, the simultaneous advantage with decoration functions.
At present, the coating for using on the market is mainly Conductive Polymer Material Polypyrrole (PPy), polyaniline (PANI) and gathers
Thiophene (PTH) and their derivative coating, be the important anti-corrosive metal coating of a class (Hou Jian, Guo Weimin, Wang Juntao,《It is a kind of
The preparation method of heteropoly acid modified polypyrrole anti-corrosive coating, 201110191911.3；Zheng Chunqiu,《A kind of high adhesion force polyaniline
Anticorrosive paint and preparation method thereof》, application number 201510932417.6；Zhang Wenzhi, huge Wen Xing, Wu Xinming,《It is a kind of to be total to ITO
The preparation method of the electrochromic polythiophenes derivative film that valence link connects》, application number 201510218450.2).
In above-mentioned coating material, relative to polypyrrole and polythiophene coating, polyaniline coating has cheap, conduction
Property good, charge density it is high and the advantages of be easy to doping, a kind of electroactive polymer anti-corrosion as potential use value high is applied
Layer (Pan Taijun, Wang Tao, Xue Wenlong,《A kind of preparation method of novel conductive composite coating》, application number 201210186354.0).
But, polyaniline is regular rigid structure so that its is insoluble not to melt, and processing characteristics is poor, in actual applications by the very day of one's doom
System.Regarding to the issue above, document points out polyaniline oligomer segment can be incorporated into polyarylether or poly- by MOLECULE DESIGN
Urea side chain, you can prepare with certain solubility property electroactive new material, have to metal good antisepsis (Chao Danming,
Jia Xiaoteng, Liu Hongtao, He Libing, Lu Xiaofeng, Wang Ce,《Side chain type electroactive polyarylether polymer and preparation method thereof》, application
Numbers 201010293748.7；Chao Danming, Chi Maoqiang, Liang Yuan, Liu Xincai, Wang Ce,《Side chain type electroactive polyurea polymer, preparation
Method and its application in terms of anti-corrosion》, application number 201410010359.7).It is to solve that chemical modification is carried out to molecular structure
The key of Polyaniline Processability energy.Therefore, designing and synthesizing the polyaniline derivative material containing Oligoanilines has important answering
With value and practical significance.
It is contemplated that by molecular modification, preparing polyaniline intrinsic hydridization oligomer of the main chain containing benzoxazine structure and preventing
Rotten coating.Benzoxazine monomer (Ba) is to be reacted to prepare through Mannich by phenols, aminated compounds and paraformaldehyde or formaldehyde
Containing N and O 6-membered heterocyclic compounds (when sturdy pines, Wang Kemin, Chen Penghui etc., a kind of synthesis of self-initiating self-crosslinking benzoxazine and
Thermal performance analysis [J] polymer material sciences and engineering, 2014,30 (11):35-39,44.).Benzoxazine monomer molecule sets
Meter is flexible, by changing the structure of primary amine and phenol, can prepare benzoxazine monomer (Huang Jie, Bai Fan, Tang An of different structure
Refined, Li Jianxue,《Phosphonitrile type benzoxazine colophony of ring three and preparation method thereof and the phosphonitrile type benzoxazine colophony composition of ring three》,
Application number 201510662292.X).Benzoxazine monomer is formed the polyphenyl with network size structure simultaneously by after thermal-ring-opening polymerization
Oxazine resin (PBa).Polybenzoxazine resin has good thermally-stabilised and chemical resistance.Polybenzoxazine resin and phenol
Urea formaldehyde, epoxy resin and bismaleimide resin be respectively provided with good compatibility (Yu Lijiao, Dan Ruijun, Chen Shuaijin, fourth go out,《Ben Bing Evil
Piperazine prepreg composition and preparation method》, application number 201510438489.5), composite can be prepared with these resin copolymerization
Or coating.Based on the good hot property of Polybenzoxazine resin and excellent mechanical strength, benzoxazine monomer, Polybenzoxazine
Resin and its composite cause increasing concern.C-N and C-O isopolarities structure makes it more readily soluble in benzoxazine structure
In various organic solvents, therefore, benzoxazine structure is incorporated into polyaniline structure, Polyaniline Processability can be effectively improved
Can, expand polyaniline application field.But at present, not yet there is the product for meeting above-mentioned requirements to occur on the market, also it is not carried out
Corresponding technical flow design, therefore, develop corresponding product and grope optimal preparation method, for improving metal material
Antiseptic effect have great meaning.
The content of the invention
The purpose of the present invention is the problem existed according to prior art, there is provided a kind of electroactive benzoxazine-polyaniline sheet
Levy hydridization oligomer and its coating.By MOLECULE DESIGN, the electroactive benzoxazine knot of polarity is introduced in polyaniline molecule main chain
Structure, obtains the electrically active function oligomer with excellent machinability.The oligomer has flexible MOLECULE DESIGN performance, good
Thermal stability, excellent mechanical property and processing characteristics；Electroactive benzoxazine-the polyaniline provided using the present invention
The coating that intrinsic hydridization oligomer makes has excellent adhesive strength, high glass-transition temperature and good chemicals-resistant
Corrosive nature, can be used for seawater, salt solution and Acidic water condition medium carbon steel, the anti-corrosion of the purple metal material such as steel and aluminium alloy
Field.
Technical scheme is as follows：
The preparation method of the electroactive intrinsic hydridization oligomer coating of benzoxazine-polyaniline, comprises the following steps：
(1) by the intrinsic hydridization oligomer of the electroactive benzoxazine-polyaniline of 5-50 weight portions and 50-95 weight portion Ben Bing Evil
Piperazine monomer, is dispersed in 80-120 weight parts organic solvents, obtains coating forerunner's pre-composition；
(2) pre-composition is evenly applied to carbon steel, purple steel or articles made of aluminium alloy surface, the heat under the conditions of 180 DEG C -200 DEG C
Treatment 0.5-1.5 hours, obtains the uniform semitransparent coating that thickness is 5-200 microns after natural cooling.
Further, in the step of prepares coating (1), the benzoxazine monomer is Pyrogentisinic Acid's aniline type benzoxazine list
Body, bisphenol-A aniline type benzoxazine monomer, Bisphenol F aniline type benzoxazine monomer, phenolphthalein aniline type benzoxazine monomer and sulphur
For any one in biphenol aniline type benzoxazine monomer.
Further, in the step of prepares coating (1), the organic solvent is by acetone, chloroform, dioxane, tetrahydrochysene furan
Mutter, one or more compositions in butanone and isopropanol low boiling-point and polarity organic solvent.
Further, in the step of prepares coating (1), the electroactive intrinsic hydridization oligomer of benzoxazine-polyaniline,
By the one kind in structure a, structure b, structure c, structure d, structure e this several electroactive benzoxazines-polyaniline hybridized oligomer
Or several compositions, the structure a, structure b, structure c, structure d, the structural formula of structure e are respectively：
Structure a：
Structure b:
Structure c:
Structure d:
Structure e:
Wherein, R isN=5-50.
Further, above-mentioned electroactive benzoxazine-polyaniline hybridized oligomer, is prepared by following steps：
(1) the electroactive benzoxazine monomer of 500-800 weight portions, 100-200 weight portions p-phenylenediamine or biphenyl two are weighed
Amine and 1000-1500 weight portion decentralized media are added in reactor, are passed through nitrogen, and 200-600 revs/min of speed mechanical is stirred
Mix, 20-40 DEG C of control system temperature；
(2) during 5-40 parts of catalyst dissolution of weighing is the hydrochloric acid-aqueous solution of 0.2-1.0 mol/Ls to 10-80 parts of concentration,
After catalyst dissolution is complete, catalyst solution 0.5-2 hours is added drop-wise in step (1) dispersion liquid；
(3) after catalyst solution is dripped, 20-40 DEG C of constant reaction temperature continues stirring reaction 6-12 hours, filters,
Obtain dark gray powder；
(4) dark gray powder water, acetone and absolute ethyl alcohol are respectively washed 3-6 times successively, 70-110 DEG C of vacuum drying 8-16
After hour, the electroactive benzoxazine of black-polyaniline hybridized oligomer granular solids are obtained.
Further, in the step of making electroactive benzoxazine-polyaniline hybridized oligomer (1), the electroactive benzene
Bing oxazine monomers, by the one kind or several in structure I, structure II, structure III, structure IV and the electroactive benzoxazine monomer of structure V
Plant composition.Structure I, structure II, structure III, structure IV and the chemical formula of structure V are respectively：
Structure I：
Structure II
Structure III：
Structure IV：
Structure V：
Further, in the step of making electroactive benzoxazine-polyaniline hybridized oligomer (1), the decentralized medium
It is N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, 1-METHYLPYRROLIDONE, dimethyl sulfoxide (DMSO), dioxane, tetrahydrochysene furan
One or more compositions in muttering.
Further, in the step of making electroactive benzoxazine-polyaniline hybridized oligomer (1), the catalyst is
One kind or ammonium persulfate and potassium peroxydisulfate or ammonium persulfate and sodium peroxydisulfate group in ammonium persulfate, potassium peroxydisulfate or sodium peroxydisulfate
Into ammonium persulfate is 1 with the part by weight of potassium peroxydisulfate, ammonium persulfate and sodium peroxydisulfate:9-9:1.
By coating obtained in above-mentioned steps, can be used for seawater, salt solution and Acidic water condition medium carbon steel, purple steel and
The corrosion-resistant field of aluminum alloy materials.
The method have the benefit that：
(1) be incorporated into electroactive benzoxazine structure in polyaniline backbone from the angle of MOLECULE DESIGN by the present invention,
Design and prepare the intrinsic hydridization oligomer of electroactive benzoxazine-polyaniline with New function；Such electroactive Ben Bing Evil
The intrinsic hydridization oligomer of piperazine-polyaniline had both had the Flexible molecules design of benzoxazine, and the application characteristic of polyaniline is retained again,
So that this kind of novel polyphenyl amine derivative has fabulous application prospect；
(2) the intrinsic hydridization oligomer of electroactive benzoxazine-polyaniline that the present invention is provided, contains polarized in backbone structure
Benzoxazine structure, can preferably be dissolved in acetone, chloroform, N, N- dimethyl acyls methylamine, DMA, N- first
In the dissolving of base pyrrolidones isopolarity, assign such electroactive intrinsic hydridization oligomer of benzoxazine-polyaniline good film forming
Property and workability energy；The intrinsic hydridization oligomer of electroactive benzoxazine-polyaniline that the present invention is provided, possesses benzoxazine good
Good processing characteristics simultaneously, solves the problems, such as that electrically conductive polyaniline poor processability, filming performance are poor；
(3) present invention is provided and is based on the intrinsic hydridization oligomer coating of electroactive benzoxazine-polyaniline, in heat treatment process
In the intrinsic hydridization oligomer backbone structure Zhong oxazine rings of electroactive-benzoxazines-polyaniline can open loop, participate in benzoxazine list
Body cross-linking reaction, formation chemical bond is strong to be connect, and can improve coated adhesive intensity, heat resistance and chemicals-resistant corrosive nature；
(4) present invention provide based on the intrinsic hydridization oligomer coating of electroactive benzoxazine-polyaniline, preparation process letter
It is single, it is easy to industrialized production and application；The intrinsic hydridization oligomer coating of electroactive benzoxazine-polyaniline that the present invention is provided can
For the corrosion-resistant field of seawater, salt solution and Acidic water condition medium carbon steel, purple steel and aluminum alloy materials, can solve well
The metal protection problem in above-mentioned perishable region.
Brief description of the drawings
Fig. 1 is coating intrinsic hydridization oligomer (structure a) coatings containing electroactive benzoxazine-polyaniline described in embodiment 1
Charcoal steel and comparative example 1 described in only coat bisphenol-A aniline type benzoxazine coating charcoal steel polarization curve；
Fig. 2 is the electroactive intrinsic hydridization oligomer of benzoxazine-polyaniline (structure b) cyclic voltammetries described in embodiment 2
Electroactive curve.
Specific embodiment
The present invention is further detailed with reference to the accompanying drawings and examples.
The performance test being related in the embodiment of the present invention is carried out by the following method：
1st, cyclic voltammetry
Lead to AUTOLAB electrochemical workstations using Switzerland ten thousand and be circulated volt-ampere test, with Ag/AgCl as reference electrode,
Platinum filament is that, to electrode, ITO electro-conductive glass is working electrode, and the sulfuric acid solution of 1mol/L is electrolyte.Test parameter is set：1. it is electric
Pressure window：- 0.2~1.0V；2. sweep speed：80mV/s；3. the number of turns is scanned:3.
2nd, polarization curve test
Lead to the enterprising action potential polarization test of Autolab potentiostat 302N electrochemical workstations in Switzerland ten thousand.
With Ag/AgCl as reference electrode, platinum filament is that, to electrode, sample is working electrode (test area~1cm2), all tests exist
Carried out in the NaCl solution of 3.5wt% and operated at room temperature.Before test, electrode is soaked into 30min so that electrode potential reaches
Stable state simultaneously is at least repeated 3 times to ensure the reliability of result.During curved measurement, sweep limits be rotten candle current potential Ecorr ±
100mV vs Ag/AgCl, sweep speed 2Mv/s.
Embodiment 1
Weigh the electroactive benzoxazine monomer of the type of 550 weight portion structure I, 110 weight portion p-phenylenediamine and 1000 weight portions
1-METHYLPYRROLIDONE is added in reactor, is passed through nitrogen, 300 revs/min of mechanical agitations, 30 DEG C of control system temperature.Claim
(ammonium persulfate is 1 with potassium peroxydisulfate part by weight to 6 parts of ammonium persulfates of amount with potassium peroxydisulfate mixed catalyst:9).By mixed catalytic
Agent is added to during 10 parts of concentration are the hydrochloric acid-aqueous solution of 0.8 mol/L, after catalyst is completely dissolved, catalyst solution is existed
It is added drop-wise in 1 hour in reactor dispersion liquid.After catalyst solution is dripped, keep reaction temperature constant at 30 DEG C, persistently stir
Reaction 10 hours is mixed, dark gray powder is then filtrated to get.Dark gray powder water, acetone and absolute ethyl alcohol are respectively washed 3 successively
It is secondary, it is subsequently placed in after 70 DEG C of vacuum environments are dried 14 hours and obtains the black intrinsic hydridization oligomerisation of electroactive benzoxazine-polyaniline
Thing (structure a) granular solids.
By taking the electroactive benzoxazine monomer of type of structure I as an example, the intrinsic hydridization oligomerisation of electroactive benzoxazine-polyaniline is illustrated
(the specific preparation process of structure a), its reaction equation is shown below thing：
5 weight portions are passed through into electroactive intrinsic hydridization oligomer (the structure a) of benzoxazine-polyaniline obtained in the above method
With 95 parts by weight of bisphenol A aniline type benzoxazine monomers, after being dispersed in 80 pbw acetones and stirring, smearing is covered in
Carbon steel surface, is heat-treated 0.5 hour under 180 DEG C of environment, then heats to be heat-treated 0.5 hour under 200 DEG C of environment, obtains thickness
It is 100 ± 3 microns of uniform semitransparent coatings to spend.
Comparative example 1
By 100 parts by weight of bisphenol A aniline type benzoxazine monomers, after being dispersed in 80 pbw acetones, it is coated in
Carbon steel surface, 180 DEG C are heat-treated 0.5 hour, and 200 DEG C are heat-treated 0.5 hour, obtain thickness for 100 ± 3 microns uniform translucent
Coating
Fig. 1 is that the intrinsic hydridization oligomer (structure a) coatings containing electroactive benzoxazine-polyaniline are coated described in embodiment 1
Charcoal steel and comparative example 1 described in only coat bisphenol-A aniline type benzoxazine coating charcoal steel polarization curve.Can be with from Fig. 1
See, the critical passivation corrosion potential of charcoal steel described in comparative example 1 is -0.92V, and the critical passivation of charcoal steel described in embodiment 1 is corroded
Current potential is -0.75V.The critical passivation corrosion electric current density of comparative example 1 and charcoal steel described in embodiment 1 is respectively 10-7.0MA and 10-8.2The critical passivation corrosion potentials of mA are more whole, and the antiseptic property of material is better；Critical passivation corrosion current is smaller, corrodes slower.From
Fig. 1 is it is recognised that the intrinsic hydridization oligomer of electroactive benzoxazine-polyaniline has good antiseptic property, and energy to charcoal steel
Effectively delay charcoal steel corrosion.
Embodiment 2
Weigh the electroactive benzoxazine monomer of the type of 590 weight portion structure II, 190 weight portion benzidines and 1200 weight portions
N-N- dimethylformamides are added in reactor, are passed through nitrogen, 200 revs/min of mechanical agitations, and control system temperature is 40
℃.Weigh 40 parts of ammonium persulfate catalyst.Mixed catalyst is added to hydrochloric acid-aqueous solution that 60 parts of concentration is 0.5 mol/L
In, after catalyst is completely dissolved, catalyst solution was added drop-wise in reactor dispersion liquid in 2 hours.Catalyst solution drips
After adding, 40 DEG C of constant reaction temperature continues stirring reaction 6 hours, and filtering obtains dark gray powder.Dark gray powder is used
Water, acetone and absolute ethyl alcohol are respectively washed 6 times successively, and the electroactive benzo of black is obtained after being vacuum dried 12 hours under 100 DEG C of environment
Oxazine-polyaniline intrinsic hydridization oligomer (structure b) granular solids.
As shown in Fig. 2 the electroactive intrinsic hydridization oligomer of benzoxazine-polyaniline (structure b) cyclic voltammetries test song
Obvious redox peaks are occurred in that on line, and oxidation peak and reduction peak are relatively more symmetrical (Ia/Ic=1), peak shape is not enclosed with scanning
Several change and change, therefore understand to there occurs the reversible redox reaction of stabilization on the working electrode (s.
By the above-mentioned electroactive intrinsic hydridization oligomer of benzoxazine-polyaniline of 10 weight portions, (structure b) is double with 50 weight portions
Phenol A aniline type benzoxazine monomers, are dispersed in the mixing of the weight portion chloroform of -5 parts by weight of isopropyl alcohol of 90 pbw acetone -5 molten
After in agent, smearing is covered in purple steel surface, is heat-treated 0.5 hour under 200 DEG C of environment, and it is 6 ± 1 microns uniform half to obtain thickness
Clear coat.
Embodiment 3
Weigh the electroactive benzoxazine monomer of the type of 610 weight portion structure III, 160 weight portion benzidines and 1400 weight portions
Dimethyl sulfoxide (DMSO) is added in reactor, is passed through nitrogen, 600 revs/min of mechanical agitations, 20 DEG C of control system temperature.Weigh 20
(ammonium persulfate is 5 with sodium peroxydisulfate part by weight to part ammonium persulfate with sodium peroxydisulfate mixed catalyst:5).By mixed catalyst
It is added to during 40 parts of concentration are the hydrochloric acid-aqueous solution of 0.8 mol/L, after after the complete solvent of catalyst, by catalyst solution 1.5
Hour is added drop-wise in reactor dispersion liquid.After catalyst solution is dripped, 20 DEG C of constant reaction temperature continues stirring reaction 12 small
When, filtering obtains dark gray powder.Dark gray powder water, acetone and absolute ethyl alcohol are respectively washed 4 times successively, 90 DEG C of vacuum are done
Electroactive benzoxazine-the polyaniline of black intrinsic hydridization oligomer (structure c) granular solids are obtained after dry 12 hours.
By the above-mentioned electroactive intrinsic hydridization oligomer of benzoxazine-polyaniline of 50 weight portions, (structure c) is double with 80 weight portions
Phenol F aniline type benzoxazine monomers, after being dispersed in the weight portion butanone of 60 weight portion tetrahydrofuran -20, are coated in 5052
Type aluminum alloy material surface, 190 DEG C are heat-treated 0.5 hour, obtain thickness for 195 ± 2 microns of uniform semitransparent coatings.
Embodiment 4
Weigh the electroactive benzoxazine monomer of the type of 800 weight portion structure IV, 200 weight portion benzidines and 1200 weight portions
The weight portion dioxane mixing decentralized medium of 1-METHYLPYRROLIDONE -300 is added in reactor, is passed through nitrogen, 600 revs/min
Clock mechanical agitation, 40 DEG C of control system temperature.Weigh 30 parts of ammonium persulfates and potassium peroxydisulfate mixed catalyst (ammonium persulfate and mistake
Potassium sulfate part by weight is 1:4).Mixed catalyst is added to during 80 parts of concentration are the hydrochloric acid-aqueous solution of 0.2 mol/L, is treated
After the complete solvent of catalyst, catalyst solution is added drop-wise in reactor dispersion liquid in 2 hours.After catalyst solution is dripped,
40 DEG C of constant reaction temperature, continues stirring reaction 6 hours, and filtering obtains dark gray powder.By dark gray powder water, acetone
6 times are respectively washed successively with absolute ethyl alcohol, it is intrinsic that 110 DEG C of vacuum drying obtain the electroactive benzoxazine-polyaniline of black after 16 hours
Hydridization oligomer (structure d) granular solids.
By 30 the weight portions above-mentioned electroactive intrinsic hydridization oligomer of benzoxazine-polyaniline (structure d) and 70 weight portion phenol
Phthalein aniline type benzoxazine monomer monomer, is dispersed in the mixing of -10 parts of dioxane of -10 parts of 60 pbw acetone tetrahydrofuran
After in solvent, smearing is covered in carbon steel surface, is heat-treated 1.5 hours under 180 DEG C of environment, obtains thickness for 150 ± 2 microns equal
Even semitransparent coating.
Embodiment 5
Weigh the electroactive benzoxazine monomer of the type of 760 weight portion structure V, 110 weight portion p-phenylenediamine and 1000 weight portions
- 100 parts of tetrahydrofuran mixing decentralized media of 1-METHYLPYRROLIDONE are added in reactor, are passed through nitrogen, 500 revs/min of machines
Tool is stirred, 25 DEG C of control system temperature.Weigh 25 parts of ammonium persulfates and sodium peroxydisulfate mixed catalyst (ammonium persulfate and persulfuric acid
Sodium part by weight is 9:1).Mixed catalyst is added to during 50 parts of concentration are the hydrochloric acid-aqueous solution of 0.5 mol/L, waits to be catalyzed
After the complete solvent of agent, catalyst solution is added drop-wise in reactor dispersion liquid in 1 hour.It is constant after catalyst solution is dripped
25 DEG C of reaction temperature, continues stirring reaction 8 hours, and filtering obtains dark gray powder.By dark gray powder water, acetone and nothing
Water-ethanol is respectively washed 4 times successively, after being vacuum dried 12 hours under 80 DEG C of environment, obtains the electroactive benzoxazine-polyaniline of black
Intrinsic hydridization oligomer (structure e) granular solids.
By 35 the weight portions above-mentioned electroactive intrinsic hydridization oligomer of benzoxazine-polyaniline (structure e) and 85 weight portion sulphur
For biphenol aniline type benzoxazine monomer, after being dispersed in 80 parts of -5 parts of acetone -5 parts of chloroform isopropyl alcohol mixed solvents,
Smearing is covered in purple steel surface, and 200 DEG C are heat-treated 0.5 hour, obtains thickness for 55 ± 3 microns of uniform semitransparent coatings.
The above, is only presently preferred embodiments of the present invention, and any formal limitation is not made to the present invention, though
So the present invention is disclosed above with preferred embodiment, but is not limited to the present invention, any to be familiar with this professional technology people
Member, without departing from the scope of the present invention, when making a little change or modification using the technology contents of the disclosure above
It is the Equivalent embodiments of equivalent variations, as long as being the content without departing from technical solution of the present invention, according to technical spirit of the invention
Any simple modification, equivalent variations and the modification made to above example, still fall within the range of technical solution of the present invention.
Claims (9)
1. the preparation method of the intrinsic hydridization oligomer coating of electroactive benzoxazine-polyaniline, it is characterised in that including following step
Suddenly：
(1) the electroactive intrinsic hydridization oligomer of benzoxazine-polyaniline, the electroactive benzo that 5-50 weight portions are configured are prepared
The intrinsic hydridization oligomer of oxazine-polyaniline and 50-95 weight portion benzoxazine monomers, are dispersed in 80-120 weight parts organic solvents
In, obtain coating forerunner's pre-composition；
(2) pre-composition is evenly applied to carbon steel, purple steel or articles made of aluminium alloy surface, is heat-treated under the conditions of 180 DEG C -200 DEG C
0.5-1.5 hours, the uniform semitransparent coating that thickness is 5-200 microns is obtained after natural cooling；
By coating obtained in above-mentioned steps, can be used for seawater, salt solution and Acidic water condition medium carbon steel, purple steel and aluminium and close
The corrosion-resistant field of golden material.
2. the preparation method of the intrinsic hydridization oligomer coating of electroactive benzoxazine-polyaniline according to claim 1, its
It is characterised by, the step of prepares coating in (1), the benzoxazine monomer is Pyrogentisinic Acid's aniline type benzoxazine monomer, bisphenol-A
Aniline type benzoxazine monomer, Bisphenol F aniline type benzoxazine monomer, phenolphthalein aniline type benzoxazine monomer and thiodiphenol
Any one in aniline type benzoxazine monomer.
3. the preparation method of the intrinsic hydridization oligomer coating of electroactive benzoxazine-polyaniline according to claim 1, its
Be characterised by, the step of prepares coating in (1), the organic solvent by acetone, chloroform, dioxane, tetrahydrofuran, butanone and
One or more compositions in isopropanol low boiling-point and polarity organic solvent.
4. the preparation method of the intrinsic hydridization oligomer coating of electroactive benzoxazine-polyaniline according to claim 1, its
Be characterised by, the step of prepares coating in (1), the electroactive intrinsic hydridization oligomer of benzoxazine-polyaniline, by structure a,
One or more groups in structure b, structure c, structure d, structure e this several electroactive benzoxazines-polyaniline hybridized oligomer
Into the structure a, structure b, structure c, structure d, the structural formula of structure e are respectively：
Structure a：
Structure b:
Structure c:
Structure d:
Structure e:
Wherein, R isN=5-50.
5. the preparation method of the intrinsic hydridization oligomer coating of electroactive benzoxazine-polyaniline according to claim 4, its
It is characterised by, the step of prepares coating in (1), the preparation method of the electroactive benzoxazine-polyaniline hybridized oligomer, step
It is rapid as follows：
(A) weigh 500-800 weight portions electroactive benzoxazine monomers, 100-200 weight portions p-phenylenediamine or benzidine and
1000-1500 weight portion decentralized media are added in reactor, are passed through nitrogen, 200-600 revs/min of speed mechanical stirring, control
20-40 DEG C of system temperature processed；
(B) during 5-40 parts of catalyst dissolution of weighing is the hydrochloric acid-aqueous solution of 0.2-1.0 mol/Ls to 10-80 parts of concentration, wait to urge
After agent dissolving completely, catalyst solution 0.5-2 hours is added drop-wise in step (A) dispersion liquid；
(C) after catalyst solution is dripped, keep reaction temperature constant at 20-40 DEG C, continue stirring reaction 6-12 hours, mistake
Filter, obtains dark gray powder；
(D) dark gray powder water, acetone and absolute ethyl alcohol are respectively washed 3-6 times successively, 70-110 DEG C is vacuum dried 8-16 hours
Afterwards, the electroactive benzoxazine of black-polyaniline hybridized oligomer granular solids are obtained.
6. the preparation method of the intrinsic hydridization oligomer coating of electroactive benzoxazine-polyaniline according to claim 5, its
Be characterised by, make electroactive benzoxazine-polyaniline hybridized oligomer the step of (A) in, the electroactive benzoxazine list
Body, is made up of one or more in structure I, structure II, structure III, structure IV and the electroactive benzoxazine monomer of structure V,
Structure I, structure II, structure III, structure IV and the chemical formula of structure V are respectively：
Structure I：
Structure II
Structure III：
Structure IV：
Structure V：
7. the preparation method of the intrinsic hydridization oligomer coating of electroactive benzoxazine-polyaniline according to claim 5, its
Be characterised by, make electroactive benzoxazine-polyaniline hybridized oligomer the step of (A) in, the decentralized medium be N, N- bis-
In NMF, DMAC N,N' dimethyl acetamide, 1-METHYLPYRROLIDONE, dimethyl sulfoxide (DMSO), dioxane, tetrahydrofuran one
Plant or several compositions.
8. the preparation method of the intrinsic hydridization oligomer coating of electroactive benzoxazine-polyaniline according to claim 5, makes
In the step of making electroactive benzoxazine-polyaniline hybridized oligomer (B), the catalyst uses ammonium persulfate, potassium peroxydisulfate
Or any one in sodium peroxydisulfate, or ammonium persulfate and potassium peroxydisulfate are used, or constituted with sodium peroxydisulfate using ammonium persulfate.
9. the preparation method of the intrinsic hydridization oligomer coating of electroactive benzoxazine-polyaniline according to claim 8, its
It is characterised by, the catalyst uses ammonium persulfate and potassium peroxydisulfate, or when being constituted with sodium peroxydisulfate using ammonium persulfate, over cure
Sour ammonium is 1 with the part by weight and ammonium persulfate of potassium peroxydisulfate with the part by weight of sodium peroxydisulfate:9-9:1.
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