CN103849295B - A kind of phthalocyanine base sulfonic acid doped with polyaniline protective system - Google Patents
A kind of phthalocyanine base sulfonic acid doped with polyaniline protective system Download PDFInfo
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Abstract
The invention discloses a kind of phthalocyanine base sulfonic acid doped with polyaniline protective system, prepare by the following method, 1) synthesis of polyaniline in eigenstate; 2) synthesis of phthalocyanine base sulfonic acid doped with polyaniline: get polyaniline in eigenstate N, dinethylformamide fully dissolves, then phthalocyanine base sulfonic acid solutions is added, react at 60 ~ 70 DEG C after 10 ~ 15 hours, be washed with distilled water to filtrate colourless, namely solid vacuum-drying obtain phthalocyanine base sulfonic acid doped with polyaniline; 3) preparation of polyaniline anticorrosion paint: at room temperature, phthalocyanine base sulfonic acid doped with polyaniline, aqueous epoxy resins solution, flow agent and defoamer are mixed, disperse 10 minutes under 1500r/min, filtration, adds solidifying agent and thinner fully mixes the protective system namely obtaining needs.The present invention effectively can overcome dedoping phenomenon, preparation is simple, sticking power is good, antiseptic property is excellent.
Description
Technical field
The present invention relates to protective system, specifically refer to a kind of phthalocyanine base sulfonic acid doped with polyaniline anticorrosive coating, can be used in the rotproofing of iron, belong to technical field of coatings.
Background technology
DeBerry in 1985 finds that polyaniline has protective effect to ferrous metals, after polyaniline paint is coated in metallic surface, air, water and salinity can be effectively stoped to play a role, check metal rusting and corrosion, and this coating have nontoxic, consumption is low, density is little, the feature good, easy to use with the compatibility of organic resin, there is the characteristic that common coating is incomparable, as scratch resistance, anti-spot corrosion and prevent sea organism attachment etc., these excellent characteristics have opened up the anticorrosion application of polyaniline paint under rigor condition, as the field such as navigation, space flight.
The preparation of polyaniline anti-corrosive paint generally has following three kinds of methods: 1, electrochemical polymerization method, namely directly deposited the method for polyaniline coating at surface of metal electrode by electrochemical polymerization reaction, but this method is difficult to use in larger metal parts, applies limited; 2, molten method is total to, namely form molten thing altogether by polyaniline and traditional polymer solvent to apply, coating is formed after solvent evaporates, this method exists that polyaniline solubleness in usual vehicle is little, the shortcoming of poor adhesive force, and high boiling solvent N-Methyl pyrrolidone costly, and toxicity is larger; 3, blending method, polyaniline and conventional coating filmogen apply as epoxy resin, polyacrylic resin etc. are used in combination, the protective system prepared of this method not only excellent performance but also sticking power and be all better than first two method to the shielding effect of water.
The polyaniline of eigenstate, complete oxidation and complete reduction-state is nonconducting, be only incomplete oxidation state or incomplete reduction state time, just there is conductivity; On the other hand because benzene formula in polyaniline in eigenstate chemical structure and quinoid structure alternately exist with 1:1 ratio, by interactions such as hydrogen bonds between macromolecular chain, make this solubleness in Conventional solvents of polyaniline very low.In polyaniline chain, in quinoid structure, the polyaniline obtaining and have electroconductibility that adulterates is carried out in double bond nitrogen and acid, and the doping agent usually adopted is mineral acid example hydrochloric acid, sulfuric acid etc., and organic acid is as picric acid, vinylformic acid etc.Due to the polyaniline stability of small molecules acid doping and solubility all very poor, thus the organic sulfonic acid doped polyanilines such as camphorsulfonic acid, p-methyl benzenesulfonic acid, Witco 1298 Soft Acid are developed, substantially increase doped polyaniline solvability in organic solvent, but dedoping effect can be there is at N-Methyl pyrrolidone in this kind of conventional organic sulfonic acid doped polyaniline.
Feng Wei etc. report and adulterate in aqueous phase and oil phase respectively to polyaniline in eigenstate with Cu sulfophthalocyanine, obtain the molecular structure with phthalocyanine function base polyaniline, this polymkeric substance has excellent solubility property and film forming ability, but its photoelectric properties mainly studied, do not do the trial of coating aspect.Huang Meirong etc. using polyaniline aqueous microemulsion and epoxy blend as priming paint, then make protective system with epoxy resin finish compound, this coating not with an organic solvent, is a kind of Environmentally friendly coatings, wherein doping agent is Witco 1298 Soft Acid, and resin is EP-618.But this coating is made up of finish paint and priming paint two portions, coating process requires higher.Chinese invention patent CN201010226027.4 provides dye adulterated polyaniline of a kind of resistance to dedoping and its preparation method and application, namely the dyestuff containing groups that can adulterate such as sulfonic groups is utilized to carry out doped polyaniline, introduce amino in doping agent, the group such as alkylamino radical and azo-group improves the resistance to dedoping ability of doped polyaniline, such dye adulterated polyaniline has good solvability or dispersiveness in N-Methyl pyrrolidone, be easy to form layer/polyaniline conductive coating, by containing sulfonic group, carboxylic acid group or metal-complexing base can carry out doping vario-property by dopant dye p-poly-phenyl amine, prepare dye adulterated conducting polyaniline material, be applied to anti-corrosion of metal, environmental protection treatment, catalytic material, photoelectric material, the fields such as conductive plastics.The dye adulterated polyaniline of this patent application protection mainly adopts molten legal system altogether for polyaniline anti-corrosive paint, to there is the shortcoming that solubleness is little, poor adhesive force, cost are high.
Can be found out by above-mentioned background introduction, existing polyaniline adopts the large class doping agent of mineral acid and organic sulfonic acid two to adulterate usually, although mineral acid doping can obtain the higher polyaniline of specific conductivity, its solubility property and environmental stability poor; The sulfonic acid doped polyaniline of organic molecule is both containing non-polar group, polar functionalities again, substantially increase environmental stability and the solvability in a solvent of doped polyaniline, but can there is dedoping phenomenon in a solvent in these organic sulfonic acid doped polyanilines at present, reduce electric conductivity, limit the use of polyaniline anti-corrosive paint.
Summary of the invention
Low for existing polyaniline anti-corrosive paint electric conductivity, there is the problems such as dedoping phenomenon and coating process be complicated, the invention provides and a kind ofly effectively overcome dedoping phenomenon, preparation is simple, sticking power is good, antiseptic property is excellent phthalocyanine base sulfonic acid doped with polyaniline protective system.
Technical scheme of the present invention is achieved in that
A kind of phthalocyanine base sulfonic acid doped with polyaniline protective system, prepares by the following method,
1) synthesis of polyaniline in eigenstate: first take aniline monomer in reactor, then in reactor, the hydrochloric acid that concentration is 1mol/l is added, dimethylbenzene is added after stirring, stir again to form uniform milky emulsion, slowly oxygenant is dripped in system, in less than 20 DEG C isothermal reactions 5 ~ 7 hours, product is filtration under diminished pressure after breakdown of emulsion, and it is colourless to be washed with distilled water to filtrate; Product after filtering is added 8%(V/V) ammonia treatment 10 ~ 24 hours, pH value 7 ~ 8, decompression filters, and namely filtration cakes torrefaction obtains polyaniline in eigenstate; Wherein the volume ratio of aniline monomer, hydrochloric acid, oxygenant and ammoniacal liquor is 1:10 ~ 25:1.2 ~ 1.8:30 ~ 40, and the volume of dimethylbenzene is 1/4 of hydrochloric acid volume;
2) synthesis of phthalocyanine base sulfonic acid doped with polyaniline: get polyaniline in eigenstate DMF and fully dissolve, then adds a certain amount of phthalocyanine base sulfonic acid solutions, and the mass ratio of polyaniline and phthalocyanine base sulfonic acid is 1:2 ~ 5; React after 10 ~ 15 hours at 60 ~ 70 DEG C, be washed with distilled water to filtrate colourless, namely solid vacuum-drying obtain phthalocyanine base sulfonic acid doped with polyaniline;
3) preparation of polyaniline anticorrosion paint: at room temperature, phthalocyanine base sulfonic acid doped with polyaniline, aqueous epoxy resins solution, flow agent and defoamer are mixed, disperse 10 minutes under 1500r/min, filtration, adds solidifying agent and thinner fully mixes the protective system namely obtaining needs; Wherein, the viscosity 400mPas of aqueous epoxy resins solution, solid content 38-42%, pH are 7 ~ 9; The volume ratio of phthalocyanine base sulfonic acid doped with polyaniline, aqueous epoxy resins solution, flow agent, defoamer, solidifying agent and thinner is 9 ~ 18:70 ~ 90:0.25 ~ 0.45:0.5 ~ 1.5:1 ~ 2:30 ~ 50.
Step 1) described in aniline monomer through second distillation purify obtain, oxygenant is the one of ammonium persulphate, Potassium Persulphate or iron trichloride.
Step 2) described in phthalocyanine base sulfonic acid be the one of copper phthalocyanine disulfonic acid, cobalt phthalocyanine disulfonic acid, copper phthalocyanine tetrasulfonic acid or cobalt phthalocyanine tetrasulfonic acid.
Step 3) in flow agent be Bi Ke chemical company produce BYK-3xx series in one, solidifying agent is methyl-etherified terpolycyantoamino-formaldehyde resin, defoamer is dimethyl silicone oil or BYK-020, BYK-028, and thinner is the one in ethylene glycol monomethyl ether, ethylene glycol ethyl ether or butyl glycol ether.
Compared to existing technology, the present invention has the following advantages:
Phthalocyanine base sulfonic acid has molecular structure stabilized, good water solubility, feature that hydrogen ion ionizing ability is strong, can be introduced into easily on polyaniline chain, significantly improve the specific conductivity of polyaniline; On the other hand, adopt the protective system of epoxy resin and the blended preparation of phthalocyanine base sulfonic acid doped with polyaniline, not only there is excellent Corrosion Protection, and there is simple, the cheap advantage of preparation, can be used in the protection against corrosion application of iron.
Embodiment
Phthalocyanine base sulfonic acid doped with polyaniline protective system of the present invention, adopts phthalocyanine base sulfonic acid doped with polyaniline to make filler, adopts blending method to prepare with epoxy resin.Concrete preparation process is as follows:
1) synthesis of polyaniline in eigenstate: first take aniline monomer in reactor, then in reactor, the hydrochloric acid that concentration is 1mol/l is added, dimethylbenzene is added after stirring, stir again to form uniform milky emulsion, slowly oxygenant is dripped in system, in less than 20 DEG C isothermal reactions 5 ~ 7 hours, product is filtration under diminished pressure after breakdown of emulsion, and it is colourless to be washed with distilled water to filtrate; Product after filtering is added 8%(V/V) ammonia treatment 10 ~ 24 hours, pH value 7 ~ 8, decompression filters, and namely filtration cakes torrefaction obtains polyaniline in eigenstate; Wherein aniline monomer is purified through second distillation and is obtained, and oxygenant is the one of ammonium persulphate, Potassium Persulphate or iron trichloride; The volume ratio of aniline monomer, hydrochloric acid, oxygenant and ammoniacal liquor is 1:10 ~ 25:1.2 ~ 1.8:30 ~ 40, and the volume of dimethylbenzene is 1/4 of hydrochloric acid volume;
2) synthesis of phthalocyanine base sulfonic acid doped with polyaniline: get polyaniline in eigenstate N, dinethylformamide (DMF) fully dissolves, then add a certain amount of phthalocyanine base sulfonic acid solutions, the mass ratio of polyaniline in eigenstate and the phthalocyanine base sulfonic acid mass ratio of solute (in the ie in solution) is 1:2 ~ 5; React after 10 ~ 15 hours at 60 ~ 70 DEG C, be washed with distilled water to filtrate colourless, namely solid vacuum-drying obtain phthalocyanine base sulfonic acid doped with polyaniline; Wherein phthalocyanine base sulfonic acid is the one of copper phthalocyanine disulfonic acid, cobalt phthalocyanine disulfonic acid, copper phthalocyanine tetrasulfonic acid or cobalt phthalocyanine tetrasulfonic acid.
3) preparation of polyaniline anticorrosion paint: at room temperature, phthalocyanine base sulfonic acid doped with polyaniline, aqueous epoxy resins solution, flow agent and defoamer are mixed, disperse 10 minutes under 1500r/min, filtration, adds solidifying agent and thinner fully mixes the protective system namely obtaining needs; Wherein, the viscosity 400mPas of aqueous epoxy resins solution, solid content 38-42%, pH are 7 ~ 9; The volume ratio of phthalocyanine base sulfonic acid doped with polyaniline, aqueous epoxy resins solution, flow agent, defoamer, solidifying agent and thinner is 9 ~ 18:70 ~ 90:0.25 ~ 0.45:0.5 ~ 1.5:1 ~ 2:30 ~ 50.
Wherein flow agent is the one in the BYK-3xx series of Bi Ke chemical company production, solidifying agent is methyl-etherified terpolycyantoamino-formaldehyde resin, defoamer is dimethyl silicone oil or BYK-020, BYK-028, and thinner is the one in ethylene glycol monomethyl ether, ethylene glycol ethyl ether or butyl glycol ether; Room temperature is 25 ± 2 DEG C.
Because phthalocyanine base sulfonic acid molecules size is comparatively large, be not easy to be diffused near molecular chain, thus adopt polyaniline in eigenstate and phthalocyanine base sulfonic acid to carry out reacting and will make it excessive in DMF solution, carry out to guarantee to react completely; On the other hand owing to being bonded to the phthalocyanine base Sulfonic acid structures relative complex of polyaniline chain, easily surface tension gradient is formed in local area during coating film forming, and show as the appearance of permanent shrinkage cavity, therefore select when film forming using the flow agent of the Organo-modified siloxanes BYK-3xx series that is main component and containing organosilyl defoamer as coatings additive(s), the surface tension of coating system can not only be reduced, and wettability, the generation resistance to bond of ground can be improved, increase surface slip and glossiness.
Below in conjunction with embodiment, the present invention is described in further detail.
EXAMPLE l
1) synthesis of polyaniline in eigenstate
Take aniline monomer 10ml in three-necked flask, then add 1mol/l hydrochloric acid 200ml, stir and add 50ml dimethylbenzene after 5 minutes, stir about, after 30 minutes, forms uniform milky emulsion; In system, slowly drip the aqueous solution 30ml containing 12g ammonium persulphate, 15 DEG C are reacted after 5 hours, filtration under diminished pressure after breakdown of emulsion, and it is colourless to be washed with distilled water to filtrate.Product after filtering is added 350ml8% ammonia treatment 16 hours, and pH value is 8, and decompression filters, and filter cake, in 45 DEG C of vacuum-dryings to constant weight, obtains blue polyaniline in eigenstate.
2) synthesis of copper phthalocyanine sulfonic acid doped with polyaniline
Get 10g polyaniline in eigenstate 50mlN, dinethylformamide (DMF) dissolves, then the aqueous solution 130ml containing 20g copper phthalocyanine disulfonic acid is added, 65 DEG C are heated in three-necked flask, stirring reaction is after 12 hours, filter, it is colourless that filter cake is washed with distilled water to filtrate, and namely solid vacuum-drying obtain the copper phthalocyanine sulfonic acid doped with polyaniline of purple.
3) preparation of polyaniline anticorrosion paint
At room temperature, by 9g copper phthalocyanine sulfonic acid doped with polyaniline, 65g aqueous epoxy resins solution, the mixing of 0.25gBYK-300 and 0.68g Simethicone, 10 minutes are disperseed in order to 1500r/min, filter, add 1.1g methyl-etherified terpolycyantoamino-formaldehyde resin and 32g butyl glycol ether is uniformly mixed, i.e. the copper phthalocyanine sulfonic acid doped with polyaniline protective system of obtained moderate viscosity.
Embodiment 2
1) synthesis of polyaniline in eigenstate
Take aniline monomer 10ml in three-necked flask, then add 1mol/l hydrochloric acid 220ml, stir and add 55ml dimethylbenzene after 5 minutes, stir about, after 30 minutes, forms uniform milky emulsion; In system, slowly drip the aqueous solution 30ml containing 13.5g ammonium persulphate, 14 DEG C are reacted after 5 hours, filtration under diminished pressure after breakdown of emulsion, and it is colourless to be washed with distilled water to filtrate.Product after filtering is added 350ml8% ammonia treatment 16 hours, and pH value is 8, and decompression filters, and filter cake, in 45 DEG C of vacuum-dryings to constant weight, obtains blue polyaniline in eigenstate.
2) synthesis of copper phthalocyanine base sulfonic acid doped with polyaniline
Get 10g polyaniline in eigenstate 50mlDMF to dissolve, then the aqueous solution 150ml containing 25g copper phthalocyanine disulfonic acid is added, 65 DEG C are heated in three-necked flask, stirring reaction is after 12 hours, filter, it is colourless that filter cake is washed with distilled water to filtrate, and namely solid vacuum-drying obtain the copper phthalocyanine sulfonic acid doped with polyaniline of purple.
3) preparation of polyaniline anticorrosion paint
At room temperature, by 12g copper phthalocyanine sulfonic acid doped with polyaniline, 80g aqueous epoxy resins solution, the mixing of 0.30gBYK-300 and 0.77g Simethicone, 10 minutes are disperseed in order to 1500r/min, filter, add 1.5g methyl-etherified terpolycyantoamino-formaldehyde resin and 39g butyl glycol ether is uniformly mixed, i.e. the copper phthalocyanine sulfonic acid doped with polyaniline protective system of obtained moderate viscosity.
Embodiment 3
1) synthesis of polyaniline in eigenstate
Take aniline monomer 10ml in three-necked flask, then add 1mol/l hydrochloric acid 250ml, stir and add 63ml dimethylbenzene after 5 minutes, stir about, after 30 minutes, forms uniform milky emulsion; In system, slowly drip the aqueous solution 35ml containing 15.2g Potassium Persulphate, 17 DEG C are reacted after 5 hours, filtration under diminished pressure after breakdown of emulsion, and it is colourless to be washed with distilled water to filtrate.Product after filtering is added 370ml8% ammonia treatment 16 hours, and pH value is 8, and decompression filters, and filter cake, in 45 DEG C of vacuum-dryings to constant weight, obtains blue polyaniline in eigenstate.
2) synthesis of cobalt phthalocyanine base sulfonic acid doped with polyaniline
Get 10g polyaniline in eigenstate 50mlDMF to dissolve, then the aqueous solution 150ml containing 24.5g cobalt phthalocyanine disulfonic acid is added, 65 DEG C are heated in three-necked flask, stirring reaction is after 12 hours, filter, it is colourless that filter cake is washed with distilled water to filtrate, and namely solid vacuum-drying obtain the cobalt phthalocyanine sulfonic acids doped polyaniline of purple.
3) preparation of polyaniline anticorrosion paint
At room temperature, by 11g cobalt phthalocyanine sulfonic acids doped polyaniline, 80g aqueous epoxy resins solution, 0.30gBYK-333 and 0.82gBYK-020 mixing, 10 minutes are disperseed in order to 1500r/min, filter, add 1.5g methyl-etherified terpolycyantoamino-formaldehyde resin and 40g butyl glycol ether is uniformly mixed, i.e. the cobalt phthalocyanine sulfonic acids doped polyaniline protective system of obtained moderate viscosity.
Embodiment 4
1) synthesis of polyaniline in eigenstate
Take aniline monomer 10ml in three-necked flask, then add 1mol/l hydrochloric acid 250ml, stir and add 63ml dimethylbenzene after 5 minutes, stir about, after 30 minutes, forms uniform milky emulsion; In system, slowly drip the aqueous solution 35ml containing 15.2g Potassium Persulphate, 15 DEG C are reacted after 5 hours, filtration under diminished pressure after breakdown of emulsion, and it is colourless to be washed with distilled water to filtrate.Product after filtering is added 370ml8% ammonia treatment 16 hours, and pH value is 8, and decompression filters, and filter cake, in 45 DEG C of vacuum-dryings to constant weight, obtains blue polyaniline in eigenstate.
2) synthesis of cobalt phthalocyanine base sulfonic acid doped with polyaniline
Get 10g polyaniline in eigenstate 50mlDMF to dissolve, then the aqueous solution 160ml containing 28g cobalt phthalocyanine disulfonic acid is added, 65 DEG C are heated in three-necked flask, stirring reaction is after 12 hours, filter, it is colourless that filter cake is washed with distilled water to filtrate, and namely solid vacuum-drying obtain the cobalt phthalocyanine sulfonic acids doped polyaniline of purple.
3) preparation of polyaniline anticorrosion paint
At room temperature, by 12g cobalt phthalocyanine sulfonic acids doped polyaniline, 80g aqueous epoxy resins solution, 0.30gBYK-300 and 0.87gBYK-028 mixing, 10 minutes are disperseed in order to 1500r/min, filter, add 1.4g methyl-etherified terpolycyantoamino-formaldehyde resin and 42g butyl glycol ether is uniformly mixed, i.e. the cobalt phthalocyanine sulfonic acids doped polyaniline protective system of obtained moderate viscosity.
Embodiment 5
1) synthesis of polyaniline in eigenstate
Take aniline 10ml in three-necked flask, then add 1mol/l hydrochloric acid 220ml, stir and add 55ml dimethylbenzene after 5 minutes, stir about, after 30 minutes, forms uniform milky emulsion; In system, slowly drip the aqueous solution 30ml containing 10g iron trichloride, 16 DEG C are reacted after 5 hours, filtration under diminished pressure after breakdown of emulsion, and it is colourless to be washed with distilled water to filtrate.Product after filtering is added 440ml8% ammonia treatment 16 hours, and pH value is 8, and decompression filters, and filter cake, in 45 DEG C of vacuum-dryings to constant weight, obtains blue polyaniline in eigenstate.
2) synthesis of copper phthalocyanine base sulfonic acid doped with polyaniline
Get 10g polyaniline in eigenstate 50mlDMF to dissolve, then the aqueous solution 120ml containing 32g copper phthalocyanine tetrasulfonic acid is added, 65 DEG C are heated in three-necked flask, stirring reaction is after 12 hours, filter, it is colourless that filter cake is washed with distilled water to filtrate, and namely solid vacuum-drying obtain the copper phthalocyanine sulfonic acid doped with polyaniline of purple.
3) preparation of polyaniline anticorrosion paint
Under room temperature part, by 17g copper phthalocyanine sulfonic acid doped with polyaniline, 85g aqueous epoxy resins solution, the mixing of 0.37gBYK-310 and 1.2g Simethicone, 10 minutes are disperseed in order to 1500r/min, filter, add 1.4g methyl-etherified terpolycyantoamino-formaldehyde resin and 45g butyl glycol ether is uniformly mixed, i.e. the copper phthalocyanine sulfonic acid doped with polyaniline protective system of obtained moderate viscosity.
Embodiment 6
1) synthesis of polyaniline in eigenstate
Take aniline 10ml in three-necked flask, then add 1mol/l hydrochloric acid 220ml, stir and add 55ml dimethylbenzene after 5 minutes, stir about, after 30 minutes, forms uniform milky emulsion; In system, slowly drip the aqueous solution 30ml containing 10.5g iron trichloride, 15 ± 2 DEG C are reacted after 5 hours, filtration under diminished pressure after breakdown of emulsion, and it is colourless to be washed with distilled water to filtrate.Product after filtering is added 350ml8% ammonia treatment 16 hours, and pH value is 8, and decompression filters, and filter cake, in 45 DEG C of vacuum-dryings to constant weight, obtains blue polyaniline in eigenstate.
2) synthesis of copper phthalocyanine base sulfonic acid doped with polyaniline
Get 10g polyaniline in eigenstate 50mlDMF to dissolve, then the aqueous solution 150ml containing 31g cobalt phthalocyanine tetrasulfonic acid is added, 65 DEG C are heated in three-necked flask, stirring reaction is after 12 hours, filter, it is colourless that filter cake is washed with distilled water to filtrate, and namely solid vacuum-drying obtain the cobalt phthalocyanine sulfonic acids doped polyaniline of purple.
3) preparation of polyaniline anticorrosion paint
At room temperature, by 18g copper phthalocyanine sulfonic acid doped with polyaniline, 90g aqueous epoxy resins solution, the mixing of 0.44gBYK-300 and 1.3g Simethicone, 10 minutes are disperseed in order to 1500r/min, filter, add 1.7g methyl-etherified terpolycyantoamino-formaldehyde resin and 48g butyl glycol ether is uniformly mixed, i.e. the cobalt phthalocyanine sulfonic acids doped polyaniline protective system of obtained moderate viscosity.
The above embodiment of the present invention is only for example of the present invention is described, and is not the restriction to embodiments of the present invention.For those of ordinary skill in the field, other multi-form change and variations can also be made on the basis of the above description.Here cannot give exhaustive to all embodiments.Every belong to technical scheme of the present invention the apparent change of amplifying out or variation be still in the row of protection scope of the present invention.
Claims (3)
1. a phthalocyanine base sulfonic acid doped with polyaniline protective system, is characterized in that, prepare by the following method,
1) synthesis of polyaniline in eigenstate: first take aniline monomer in reactor, then in reactor, the hydrochloric acid that concentration is 1mol/L is added, dimethylbenzene is added after stirring, stir again to form uniform milky emulsion, slowly oxygenant is dripped in system, in less than 20 DEG C isothermal reactions 5 ~ 7 hours, product is filtration under diminished pressure after breakdown of emulsion, and it is colourless to be washed with distilled water to filtrate; Product after filtering is added 8%(V/V) ammonia treatment 10 ~ 24 hours, pH value 7 ~ 8, decompress filter, namely filtration cakes torrefaction obtains polyaniline in eigenstate; Wherein the volume ratio of aniline monomer, hydrochloric acid, oxygenant and ammoniacal liquor is 1:10 ~ 25:1.2 ~ 1.8:30 ~ 40, and the volume of dimethylbenzene is 1/4 of hydrochloric acid volume;
2) synthesis of phthalocyanine base sulfonic acid doped with polyaniline: get polyaniline in eigenstate DMF and fully dissolve, then adds a certain amount of phthalocyanine base sulfonic acid solutions, and the mass ratio of polyaniline and phthalocyanine base sulfonic acid is 1:2 ~ 5; React after 10 ~ 15 hours at 60 ~ 70 DEG C, be washed with distilled water to filtrate colourless, namely solid vacuum-drying obtain phthalocyanine base sulfonic acid doped with polyaniline;
3) preparation of polyaniline anticorrosion paint: at room temperature, phthalocyanine base sulfonic acid doped with polyaniline, aqueous epoxy resins solution, flow agent and defoamer are mixed, disperse 10 minutes under 1500r/min, filtration, adds solidifying agent and thinner fully mixes the protective system namely obtaining needs; Wherein, the viscosity 400mPas of aqueous epoxy resins solution, solid content 38-42%, pH are 7 ~ 9; The volume ratio of phthalocyanine base sulfonic acid doped with polyaniline, aqueous epoxy resins solution, flow agent, defoamer, solidifying agent and thinner is 9 ~ 18:70 ~ 90:0.25 ~ 0.45:0.5 ~ 1.5:1 ~ 2:30 ~ 50;
Step 3) described in flow agent be Bi Ke chemical company produce BYK-3xx series in one, solidifying agent is methyl-etherified terpolycyantoamino-formaldehyde resin, defoamer is dimethyl silicone oil or BYK-020, BYK-028, and thinner is the one in ethylene glycol monomethyl ether, ethylene glycol ethyl ether or butyl glycol ether.
2. phthalocyanine base sulfonic acid doped with polyaniline protective system according to claim 1, is characterized in that: step 1) described in aniline monomer through second distillation purify obtain, oxygenant is the one of ammonium persulphate, Potassium Persulphate or iron trichloride.
3. phthalocyanine base sulfonic acid doped with polyaniline protective system according to claim 1, is characterized in that: step 2) described in phthalocyanine base sulfonic acid be the one of copper phthalocyanine disulfonic acid, cobalt phthalocyanine disulfonic acid, copper phthalocyanine tetrasulfonic acid or cobalt phthalocyanine tetrasulfonic acid.
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| CN106590191A (en) * | 2016-11-17 | 2017-04-26 | 闻承岳 | Modified polyaniline-doped non-corrosibility-improved chlorosulfonated polyethylene anticorrosive coating |
| CN108752927A (en) * | 2018-04-27 | 2018-11-06 | 同济大学 | A kind of preparation method of cysteine/polyaniline anticorrosion functional material |
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