CN100363445C - Phosphoric acid doped polyphenylamine phosphate priming paint and preparing process thereof - Google Patents
Phosphoric acid doped polyphenylamine phosphate priming paint and preparing process thereof Download PDFInfo
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- CN100363445C CN100363445C CNB2005100195157A CN200510019515A CN100363445C CN 100363445 C CN100363445 C CN 100363445C CN B2005100195157 A CNB2005100195157 A CN B2005100195157A CN 200510019515 A CN200510019515 A CN 200510019515A CN 100363445 C CN100363445 C CN 100363445C
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Abstract
The present invention relates to the phosphoric acid doped polyphenylamine phosphorizing priming paint and the preparing process thereof, which comprises a component A and a component B. Novel phosphorizing priming paint is prepared from electrically conductive high molecule (phosphoric acid doped polyphenylamine) to match with aluminum tripolyphosphate and various antirust phosphate pigments instead of the traditional zinc tetrahydroxychromate and polyvinyl butyral resin. Or the phosphoric acid doped polyphenylamine phosphorizing priming paint with in-situ polymerization is directly prepared from small molecule aniline to replace polyaniline. The novel phosphorizing priming paint and the phosphoric acid doped polyphenylamine phosphorizing priming paint with in-situ polymerization have good paint film adhesive force and antirust performance in thin coating pre-painting priming paint. The phosphoric acid doped polyphenylamine phosphorizing priming paint provided by the present invention as a thin coating has good paint film adhesive force and antirust performance. Therefore, the phosphoric acid doped polyphenylamine phosphorizing priming paint can be matched with various kinds of anticorrosive paint to further enhance the corrosion prevention protective capability of paint film. In addition, the phosphoric acid doped polyphenylamine phosphorizing priming paint provided by the present invention has the advantages of easy preparation and easy popularization and is suitable for industrial production.
Description
Technical field
The present invention relates to material field, particularly a kind of phosphoric acid doped polyphenylamine phosphate priming paint and preparation method thereof.
Background technology
As everyone knows, the eigenstate electroconductibility of polyaniline (PANI) is lower, acid doping attitude electroconductibility is fine, it is a kind of novel conductive macromolecular material, acid doping attitude is called polyaniline salt again, the exploitation polyaniline anticorrosion paint has become the new Application Areas of macromolecule conducting material, also is a new focus of coating development research field in recent years.
Electrically conductive polyaniline in the coating helps forming stable metal oxide passive film at steel surface; give the anodic protection effect; also impel simultaneously cathodic reaction (reduction of oxygen) to take place on the surface of polyaniline prime coat; make and separate with cathodic reaction in the anodic reaction of steel surface; stoped the rising of steel surface pH, and made coating be difficult for taking place cathodic disbonding.
At present, polyaniline is used doping agents such as hydrochloric acid, Witco 1298 Soft Acid always, and joins anticorrosive coating with these doped polyanilines and general coating resin, always has too early big area corrosion phenomena, and doped hydrochloride agent meeting is volatilized gradually and lost; If formulate thin coating shop primer can produce more serious big area corrosion.
CN1243852A has introduced " preparation method of non-solvent anticorrosion conducting paint of polyphenylamine ", this method mixed curing agent of polyaniline in eigenstate/aliphatic polyamine solution as Resins, epoxy, obtain a kind of novel solvent-free, free of contamination protective system, be suitable for the protective system of making boats and ships.
CN1358812A has introduced " a kind of preparation technology of polyaniline anti-corrosive paint ", and it is with Resins, epoxy and polyaniline, mixing diluents, with phenolic aldehyde amine, polymeric amide self-vulcanizing.The gained coating has very high hardness and excellent abrasive, can make metal avoid corrosion by generating passive film after coating is scratched.
CN1401718A has introduced " preparation technology of polyaniline anti-corrosive paint ", it is at first with conventional fillers, as the micro mist of silicon-dioxide, titanium dioxide, montmorillonite, aluminum oxide, polyvinyl chloride or nano powder etc., carry out surface treatment, form the organic or inorganic filler that polyaniline coats in its surface in situ polymerization again.This filler and Resins, epoxy, solvent, defoamer, softening agent etc. disperse, mix, and get the high hardness abrasive resistance bi-component polyaniline anti-corrosive paint.The content of polyaniline is very low in this filler, and building-up process is simple and needn't dissolve direct application, and is therefore easy to use and cost is extremely cheap.
CN1429258A has introduced " corrosion resistant coating ", is a kind of two-component coating, contains non-conductive polyaniline, primary amine solidifying agent, curable resin.The coating solution long-term stability of this invention is even described coating composition also has good preservative effect under extremely low polyaniline concentration.
CN1528845A has introduced " waterborne metal anti-corrosive paint ", and this coating is to carry out condensation reaction with aniline that has carboxyl on the molecular chain and aliphatic polyamine, by-CO
2Amino condensation in H and the aliphatic polyamine, aliphatic polyamine is grafted on the polyaniline molecule chain, make the water-soluble polyaniline of a kind of energy/aliphatic polyamine condenses type epoxy curing agent, this solidifying agent and aqueous epoxy resins is composite, thus obtain a kind of low solidification value and satisfy the metal anti-corrosive paint that Green Chemistry requires.It can be applicable to the anticorrosion of fields such as boats and ships, freight container, offshore platform, Nuclear power plants.
CN1385486A has introduced " polyaniline paint compositions ", and contained polyaniline particle has polymer core that contains strong acid group and the polyaniline shell that adheres to, and can give the metal substrate erosion resistance with the coating of its preparation.And provide a kind of polyaniline particulate method and a kind of product that comprises by the coating of this coating composition preparation of preparing.
CN1215744A has introduced " preparation method of conductive antifouling corrosion-resistant poly-aniline paint ", this invention is a medium with organic solvent or water, adopting functionalized protonic acid is that doping agent has prepared the electrically conductive polyaniline dispersion liquid, with blend such as multipolymers such as Resins, epoxy, urethane, chlorinated rubber or water-soluble silicate, pure dissolubility partial hydrolysis tetraethoxy, Red copper oxide after prepare electrically conducting coating.Coating electricity under ocean environment is led and is kept stable above 1 year.The antifouling paint that can be used for boats and ships, but and double as boats and ships protective system.
Summary of the invention
Technical problem to be solved by this invention is: a kind of phosphoric acid doped polyphenylamine phosphate priming paint and preparation method thereof is provided, and this shop primer shallow layer has good film adhesive and rustless property.
The technical solution adopted for the present invention to solve the technical problems is as follows:
Phosphoric acid doped polyphenylamine phosphate priming paint provided by the invention, its composition comprise A, B two components.
The A component is ground and is made into by 10% polyvinyl butyral acetal solution, aluminium triphosphate, phosphate-doped polyaniline, phosphoric acid salt rust-stabilising pigment, talcum powder, alcohol solvent, its quality proportioning is by 10% polyvinyl butyral acetal solution, phosphate-doped polyaniline 0.1%～5.0%, aluminium triphosphate 1.5%～6.5%, phosphoric acid salt rust-stabilising pigment 2.0%～4.5%, talcum powder 0.5%～2.5%, alcohol solvent surplus.
The B component is made into by 85% phosphoric acid, distilled water and alcoholic solvent.Alcoholic solvent is 3: 1 ethanol and a butanols mixed solvent.
Phosphate-doped polyaniline in the A component, its constitutional features is as follows:
A
-: be H
2PO
4 -, HPO
4 2-Or PO
4 3-
Above-mentioned phosphoric acid doped polyphenylamine phosphate priming paint provided by the invention, its preparation method has following several:
A kind of is to form phosphate-doped polyaniline with phosphate-doped polyaniline, utilizes the electroconductive polymer of phosphate-doped polyaniline to cooperate with aluminium triphosphate, phosphoric acid salt rust-stabilising pigment again, is made into polyvinyl butyral resin then.
A kind of is the wash primer of directly preparing phosphate-doped polyaniline with aniline, its method is: directly simultaneously form doped polyaniline by situ aggregation method in film forming with small molecules aniline, make on the spot the electroconductive polymer of the phosphate-doped polyaniline that generates and aluminium triphosphate, phosphoric acid salt rust-stabilising pigment and 10% polyvinyl butyral acetal solution form good rust-preventing characteristic and film.
A kind of is to be mixed with phosphoric acid doped polyphenylamine phosphate priming paint by polyaniline composite zinc phosphate and aluminium triphosphate and 10% polyvinyl butyral acetal solution.
Wherein, the synthetic method of polyaniline composite zinc phosphate is: by the mol ratio of aniline and phosphoric acid be 1: 1.5～4, the mol ratio of aniline and dichromate is 1: 0.2～0.4, the mass ratio of aniline and industrial phosphoric acid zinc is 1: 1～4 ratio, aniline, distilled water are mixed, add industrial phosphoric acid zinc rust-stabilising pigment, under continuously stirring, be warming up to 60 ℃ of heating 3 hours, be cooled to room temperature, add phosphoric acid and distilled water, stir down, slowly drip dichromate oxidation liquid, room temperature reaction 3 hours, suction filtration, with distilled water filter wash 3 times, 60 ℃ of vacuum-drying 24 hours.
Shop primer provided by the invention as shallow layer, has good film adhesive and rustless property.Therefore, can be used, further strengthen the anti-corrosion protection ability of filming with all kinds of anticorrosive coatings.In addition, priming paint provided by the invention prepares easily, is suitable for suitability for industrialized production, is easy to promote.
Embodiment
The invention relates to a kind of phosphoric acid doped polyphenylamine phosphate priming paint and preparation method thereof.
One. phosphoric acid doped polyphenylamine phosphate priming paint
Its composition comprises A, B two components,
The A component is ground and is made into by 10% polyvinyl butyral acetal solution, aluminium triphosphate, phosphate-doped polyaniline, phosphoric acid salt rust-stabilising pigment, talcum powder, alcohol solvent, its quality proportioning is by 10% polyvinyl butyral acetal solution, phosphate-doped polyaniline 0.1%～5.0%, aluminium triphosphate 1.5%～6.5%, phosphoric acid salt rust-stabilising pigment 2.0%～4.5%, talcum powder 0.5%～2.5%, alcohol solvent is an amount of.
The B component is made into by 85% phosphoric acid, distilled water and alcoholic solvent.Alcoholic solvent is 3: 1 ethanol and a butanols mixed solvent.
Phosphate-doped polyaniline in the A component, its constitutional features is as follows:
A
-: be H
2PO
4 -, HPO
4 2-Or PO
4 3-
Above-mentioned phosphoric acid salt rust-stabilising pigment can adopt a kind of in industrial phosphoric acid zinc, modified zinc phosphate, alkaline phosphatase zinc, modified alkaline zinc phosphate, strontium phosphate, modified phosphate strontium, alkaline zinc phosphite, calcium modified alkaline zinc phosphite and the aluminium triphosphate, perhaps two kinds, perhaps two or more mixtures.
Two. the preparation of phosphoric acid doped polyphenylamine phosphate priming paint
The composition of phosphoric acid doped polyphenylamine phosphate priming paint sees before and states, and the preparation of this priming paint has following method.
The method of the phosphate-doped polyaniline preparation of example 1. usefulness:
(1) forms phosphate-doped polyaniline with phosphate-doped polyaniline earlier, utilize the electroconductive polymer of phosphate-doped polyaniline to cooperate again, be made into 10% polyvinyl butyral acetal solution then, promptly get described priming paint with aluminium triphosphate, phosphoric acid salt rust-stabilising pigment.
Concrete steps are as follows:
Polyvinyl butyral resin is dissolved into 10% polyvinyl butyral acetal solution with 3: 1 ethanol and butanols mixed solvent;
Get 10% polyvinyl butyral acetal solution 130g, aluminium triphosphate 1.95～8.45g, phosphate-doped polyaniline 0.13～6.5g, phosphoric acid salt rust-stabilising pigment 2.6～5.9g, talcum powder 0.6～3.3g, alcohol solvent 150ml, grind and be made into the A component;
Get 85% phosphatase 11 0g, distilled water 8g, 3: 1 ethanol and butanols mixed solvent 120ml, be made into the B component.
During use, the A component is mixed with the B component, be applied to surface of steel plate, form the dry film of 8～10 μ m.
(2) phosphate-doped polyaniline is synthetic:
Phosphate-doped polyaniline be with phosphoric acid make doping agent, ammonium persulphate is made oxygenant, chemical method is directly synthetic, concrete grammar is: by the mol ratio of aniline and phosphoric acid be 1: 1.5～4, the mol ratio of aniline and ammonium persulphate is 1: 0.55～1.1 ratio, aniline with the dissolving of 0.1～1mol/L phosphoric acid solution, is stirred down, slowly drip ammonium persulfate solution, 10～25 ℃ were reacted 3～10 hours, suction filtration, with 0.1～1mol/L phosphoric acid solution filter wash 3 times, 60～80 ℃ of vacuum-drying 24 hours.
Record phosphate-doped polyaniline volume specific resistance 2 * 10 with two-point method
3Ω cm.
The method that example 2. usefulness aniline are directly prepared:
Directly form doped polyaniline by situ aggregation method simultaneously in film forming with small molecules aniline, make the electroconductive polymer of the phosphate-doped polyaniline that generates on the spot and the coating that aluminium triphosphate, phosphoric acid salt rust-stabilising pigment and 10% polyvinyl butyral acetal solution form phosphoric acid doped polyphenylamine phosphate priming paint, this coating has good anti-rust properties.
With the difference of example 1 be: replace phosphate-doped polyaniline in the A component with aniline, the B component adds a certain amount of chromic acid class oxygenant.Described chromic acid class oxygenant comprises: chromic acid, chromic anhydride, sodium dichromate 99, ammonium dichromate, potassium bichromate etc.
The method of example 3. usefulness polyaniline composite zinc phosphates preparation:
Its method is: polyaniline composite zinc phosphate and aluminium triphosphate and 10% polyvinyl butyral acetal solution are formulated.
Wherein, the synthetic method of polyaniline composite zinc phosphate is: by the mol ratio of aniline and phosphoric acid be 1: 1.5～4, the mol ratio of aniline and dichromate is 1: 0.2～0.4, the mass ratio of aniline and industrial phosphoric acid zinc is 1: 1～4 ratio, aniline, distilled water are mixed, add industrial phosphoric acid zinc rust-stabilising pigment, under continuously stirring, be warming up to 60 ℃ of heating 3 hours, be cooled to room temperature, add phosphoric acid and distilled water, stir down, slowly drip dichromate oxidation liquid, room temperature reaction 3 hours, suction filtration, with distilled water filter wash 3 times, 60 ℃ of vacuum-drying 24 hours.
Above-mentioned dichromate can adopt a kind of in sodium dichromate 99, ammonium dichromate, the potassium bichromate, and perhaps two kinds, perhaps two or more mixtures.
Three. the specific examples of preparation phosphoric acid doped polyphenylamine phosphate priming paint (hereinafter to be referred as wash primer)
Example 1: the wash primer preparation of phosphoric acid doped polyaniline
Comprise A, B component, it is formulated as follows:
The A component: (the polyvinyl butyral acetal trade mark is BH-45 to get 130 grams, 10% polyvinyl butyral acetal; butyryl radicals 43%～48%) solution, 2.5 gram aluminium triphosphates (APW-1, the south of the River, Nanning Fine Chemical Works), the phosphate-doped polyaniline of 5.5 grams, 4 gram industrial phosphoric acid zinc rust-stabilising pigments (Xin Dong chemical plant, Xinyue City, Hebei), 2 gram talcum powder and 150ml ethanol are ground to fineness and reach 40～50 μ m.
B component: get 85% phosphatase 11,0 gram, distilled water 8 grams, 90ml ethanol, the mixing of 30ml butanols.
Synthesizing of phosphate-doped polyaniline in the A component: get 40.2 gram (NH
4)
2S
2O
8Dissolve stand-by.14.9 gram aniline are added to the 0.8mol/L H of 640ml
3PO
4Dissolve in the solution, under agitation, room temperature drips (NH
4)
2S
2O
8Solution, control reaction temperature is below 25 ℃, about 1 hour of dropping time, and dropwise and continued stirring reaction 3.5 hours, static back suction filtration is used 0.8mol/LH
3PO
4Solution washing, filtering and washing triplicate, 80 ℃ of vacuum-drying 24 hours.
Example 2: the wash primer preparation of phosphoric acid doped polyaniline
With the industrial phosphoric acid zinc rust-stabilising pigment in the alkaline phosphatase zinc replacement example 1.
Example 3: the wash primer preparation of phosphoric acid doped polyaniline
With the industrial phosphoric acid zinc rust-stabilising pigment in the strontium phosphate replacement example 1.
Example 4: the wash primer preparation of phosphoric acid doped polyaniline
With the industrial phosphoric acid zinc rust-stabilising pigment in the alkaline zinc phosphite replacement example 1.
Example 5: the wash primer preparation of phosphoric acid doped polyaniline
With the industrial phosphoric acid zinc rust-stabilising pigment in the modified alkaline zinc phosphite replacement example 1.
Example 6: contain the wash primer preparation of PANI composite zinc phosphate
Get 5 gram aniline, the mixing of 100ml distilled water, add 10 gram industrial phosphoric acid zinc, under continuously stirring, be warming up to 60 ℃, heated 3 hours, be cooled to room temperature again.
26 grams, 85% phosphoric acid is mixed with 100ml distilled water, get 40ml phosphoric acid solution adding 8.04 restrain six water sodium dichromate 99s dissolve oxidation liquid.Remaining phosphoric acid solution mixes with aniline-zinc phosphate solution, under continuously stirring, slowly drips sodium dichromate 99 oxidation liquid, and temperature control dripped 30 minutes below 25 ℃, reacts 3 hours again, and suction filtration is with distilled water washing 3 times.Getting 1/5 of this product replaces phosphate-doped polyaniline and industrial phosphoric acid zinc rust-stabilising pigment in the example 1 to join lacquer.
Example 7: contain the wash primer preparation of aniline
A component: get 130 grams, 10% polyvinyl butyral acetal solution, 8 gram aluminium triphosphates, 2 gram aniline, 4 gram industrial phosphoric acid zinc rust-stabilising pigments, 2 gram talcum powder and 150ml ethanol and be ground to fineness and reach 40～50 μ m.
B component: get 85% phosphatase 11,0 gram, 3g sodium dichromate 99, distilled water 8 grams, 90ml ethanol, the mixing of 30ml butanols.
A, B two components are mixed japanning, and in film forming simultaneously, in-situ polymerization forms doped polyaniline.
Compare below by Comparative Examples and subordinate list rust-preventing characteristic and sticking power wash primer of the present invention.
Contrast 1:
The polyaniline salt hydrochlorate is synthetic: get 100.5 gram (NH
4)
2S
2O
8Be dissolved among the 240ml 1mol/L HCl stand-by.37.3 gram aniline are added in the 560ml 1mol/L HCl solution and dissolve, and under agitation, room temperature drips (NH
4)
2S
2O
8Solution, control reaction temperature is below 25 ℃, about 1 hour of dropping time, dropwise and continued stirring reaction 3.5 hours, static back suction filtration, with the 1mol/LHCl solution washing to there not being SO
4 2-(use BaCl
2Check), 80 ℃ of vacuum-drying is 24 hours.
Contain the wash primer preparation of polyaniline salt hydrochlorate:
The A component: (the polyvinyl butyral acetal trade mark is BH-45 to get 130 grams, 10% polyvinyl butyral acetal; butyryl radicals 43%～48%) solution, 2.5 gram aluminium triphosphates (APW-1, the south of the River, Nanning Fine Chemical Works), 5.5 gram polyaniline salt hydrochlorates, 4 gram industrial phosphoric acid zinc rust-stabilising pigments (Xin Dong chemical plant, Xinyue City, Hebei), 2 gram talcum powder and 150ml ethanol are ground to fineness and reach 40～50 μ m.
B component: get 85% phosphatase 11,0 gram, distilled water 8 grams, 90ml ethanol, the mixing of 30ml butanols.
Contrast 2:
Prepare wash primer with the industrial phosphoric acid zinc rust-stabilising pigment that alkaline phosphatase zinc substitutes in the contrast 1.
Contrast 3:
Substitute industrial phosphoric acid zinc rust-stabilising pigment preparation wash primer in the contrast 1 with calcium modified alkaline zinc phosphite.
The subordinate list explanation
Rust-preventing characteristic is estimated: with the sand papering of 5 * 12cmA3 cold-rolled steel sheet, all wash primers apply together after A, B two components are mixed, build 8～10 μ m, do the back with the limit of sealing with wax, in 3% sodium chloride aqueous solution, soak 24h, show rust-preventing characteristic with corrosion area percentage table.
Sticking power is estimated: wash primer is applied on the tinplate sheet, applies the green alkyd resin enamel of one deck after doing again, dry back is surveyed with drawing the circle method. sticking power, 1 grade best, 7 grades the poorest.
The result shows: the new phosphide priming paint of preparing with phosphate-doped polyaniline among the present invention, or directly replace polyaniline to be made into having the wash primer that in-situ polymerization forms phosphate-doped polyaniline with small molecules aniline, owing to utilized the doping effect of phosphoric acid and the phosphorization in priming paint thereof dexterously, therefore, wash primer of the present invention has good film adhesive and rustless property in the shallow layer shop primer.Please see attached list, aspect rust-preventing characteristic and sticking power, wash primer of the present invention is better than existing polyaniline salt hydrochlorate priming paint technology.
Subordinate list
The comparison of rust-preventing characteristic and sticking power
| Example | The rust-stabilising pigment feature | Corrosion area/% | Sticking power/level |
| 1 | Phosphate-doped polyaniline, industrial phosphoric acid zinc | 50 | 3 |
| 2 | Phosphate-doped polyaniline, alkaline phosphatase zinc | 1 | 1～2 |
| 3 | Phosphate-doped polyaniline, strontium phosphate | 10 | 2 |
| 4 | Phosphate-doped polyaniline, alkaline zinc phosphite | 1 | 1 |
| 5 | Phosphate-doped polyaniline, calcium modified alkaline zinc phosphite | 0 | 1 |
| 6 | The PANI composite zinc phosphate | 30 | 2 |
| 7 | The aniline in-situ polymerization | 0～1 | 1 |
| Contrast 1 | The polyaniline salt hydrochlorate, industrial phosphoric acid zinc | 60 | 4 |
| Contrast 2 | The polyaniline salt hydrochlorate, alkaline phosphatase zinc | 30 | 3 |
| Contrast 3 | The polyaniline salt hydrochlorate, calcium modified alkaline zinc phosphite | 40 | 3 |
Claims (8)
1. priming paint, its composition comprises A, B two components, and the B component is made into by 85% phosphoric acid, distilled water and alcoholic solvent, and alcoholic solvent is 3: 1 ethanol and a butanols mixed solvent, it is characterized in that described priming paint is a kind of phosphoric acid doped polyphenylamine phosphate priming paint,
The A component is ground by 10% polyvinyl butyral acetal solution, aluminium triphosphate, phosphate-doped polyaniline, phosphoric acid salt rust-stabilising pigment, talcum powder and alcohol solvent and is made into, its quality proportioning is by 10% polyvinyl butyral acetal solution, phosphate-doped polyaniline 0.1%～5.0%, aluminium triphosphate 1.5%～6.5%, phosphoric acid salt rust-stabilising pigment 2.0%～4.5%, talcum powder 0.5%～2.5%, alcohol solvent surplus.
2. priming paint according to claim 1, it is characterized in that: the phosphoric acid salt rust-stabilising pigment adopts a kind of in industrial phosphoric acid zinc, modified zinc phosphate, alkaline phosphatase zinc, modified alkaline zinc phosphate, strontium phosphate, modified phosphate strontium, alkaline zinc phosphite, calcium modified alkaline zinc phosphite and the aluminium triphosphate, perhaps two kinds, perhaps two or more mixtures.
3. the preparation method of a priming paint, its composition comprises A, B two components, the B component is by 85% phosphoric acid, distilled water and alcoholic solvent are made into, alcoholic solvent is 3: 1 ethanol and a butanols mixed solvent, it is characterized in that the A component is by 10% polyvinyl butyral acetal solution, aluminium triphosphate, phosphate-doped polyaniline, the phosphoric acid salt rust-stabilising pigment, talcum powder, alcohol solvent grinds and is made into, its quality proportioning is by 10% polyvinyl butyral acetal solution, phosphate-doped polyaniline 0.1%～5.0%, aluminium triphosphate 1.5%～6.5%, phosphoric acid salt rust-stabilising pigment 2.0%～4.5%, talcum powder 0.5%～2.5%, the alcohol solvent surplus
The preparation method of A component is: form phosphate-doped polyaniline with phosphate-doped polyaniline, utilize the electroconductive polymer of phosphate-doped polyaniline to cooperate again, be made into the A component of phosphoric acid doped polyphenylamine phosphate priming paint then with 10% polyvinyl butyral acetal solution with aluminium triphosphate, phosphoric acid salt rust-stabilising pigment, talcum powder, alcohol solvent.
4. the preparation method of a priming paint, its composition comprises A, B two components, the B component comprises 85% phosphoric acid, distilled water and alcoholic solvent, it is characterized in that directly preparing phosphoric acid doped polyphenylamine phosphate priming paint with aniline, its method is: directly simultaneously form phosphate-doped polyaniline by situ aggregation method in film forming with small molecules aniline, make the electroconductive polymer of the phosphate-doped polyaniline that generates on the spot and the coating that other component forms phosphoric acid doped polyphenylamine phosphate priming paint
The A component is ground and is made into by 10% polyvinyl butyral acetal solution, aluminium triphosphate, aniline, phosphoric acid salt rust-stabilising pigment, talcum powder, alcohol solvent, its quality proportioning is by 10% polyvinyl butyral acetal solution, aniline 0.1%～3.0%, aluminium triphosphate 1.5%～6.5%, phosphoric acid salt rust-stabilising pigment 2.0%～4.5%, talcum powder 0.5%～2.5%
The B component also comprises chromic acid class oxygenant, and the mol ratio of itself and aniline is 0.2～0.6: 1; Alcoholic solvent is 75: 25～50: 50 ethanol and a butanols mixed solvent.
5. according to the preparation method of the described priming paint of claim 4, it is characterized in that chromic acid class oxygenant is selected from: a kind of in chromic acid, chromic anhydride, sodium dichromate 99, ammonium dichromate, the potassium bichromate, perhaps two kinds, perhaps two or more mixtures.
6. according to the preparation method of claim 3 or 4 described priming paint, it is characterized in that the phosphoric acid salt rust-stabilising pigment adopts a kind of in industrial phosphoric acid zinc, modified zinc phosphate, alkaline phosphatase zinc, modified alkaline zinc phosphate, strontium phosphate, modified phosphate strontium, alkaline zinc phosphite, calcium modified alkaline zinc phosphite and the aluminium triphosphate, perhaps two kinds, perhaps two or more mixtures.
7. the preparation method of a priming paint is characterized in that being mixed with phosphoric acid doped polyphenylamine phosphate priming paint by polyaniline composite zinc phosphate and aluminium triphosphate and 10% polyvinyl butyral acetal solution,
Wherein, the synthetic method of polyaniline composite zinc phosphate is: by the mol ratio of aniline and phosphoric acid be 1: 1.5～4, the mol ratio of aniline and dichromate is 1: 0.2～0.4, the mass ratio of aniline and industrial phosphoric acid zinc is 1: 1～4 ratio, aniline, distilled water are mixed, add industrial phosphoric acid zinc rust-stabilising pigment, under continuously stirring, be warming up to 60 ℃ of heating 3 hours, be cooled to room temperature, add phosphoric acid and distilled water, stir down, slowly drip dichromate oxidation liquid, room temperature reaction 3 hours, suction filtration, with distilled water filter wash 3 times, 60 ℃ of vacuum-drying 24 hours.
8. according to the preparation method of the described priming paint of claim 7, it is characterized in that dichromate adopts a kind of in sodium dichromate 99, ammonium dichromate, the potassium bichromate, perhaps two kinds, perhaps two or more mixtures.
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| CN102924716B (en) * | 2012-11-26 | 2014-07-02 | 广西大学 | Preparation method for polyphosphoric acid doped polyaniline |
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| CN1186091A (en) * | 1996-12-25 | 1998-07-01 | 中国科学院长春应用化学研究所 | Preparation of mixed polyaniline aqueous solution and dispersant liquid |
| CN1215744A (en) * | 1997-10-25 | 1999-05-05 | 中国科学院长春应用化学研究所 | Method for preparing conductive antifouling corrosion-resistant poly-aniline paint |
| CN1401718A (en) * | 2002-09-20 | 2003-03-12 | 西安交通大学 | Process for preparing corrosion-resistant polyaniline paint |
| CN1631939A (en) * | 2004-11-09 | 2005-06-29 | 武汉理工大学 | Process for preparing doped conductive polyaniline |
-
2005
- 2005-09-29 CN CNB2005100195157A patent/CN100363445C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1186091A (en) * | 1996-12-25 | 1998-07-01 | 中国科学院长春应用化学研究所 | Preparation of mixed polyaniline aqueous solution and dispersant liquid |
| CN1215744A (en) * | 1997-10-25 | 1999-05-05 | 中国科学院长春应用化学研究所 | Method for preparing conductive antifouling corrosion-resistant poly-aniline paint |
| CN1401718A (en) * | 2002-09-20 | 2003-03-12 | 西安交通大学 | Process for preparing corrosion-resistant polyaniline paint |
| CN1631939A (en) * | 2004-11-09 | 2005-06-29 | 武汉理工大学 | Process for preparing doped conductive polyaniline |
Non-Patent Citations (3)
| Title |
|---|
| 磷酸掺杂对聚苯胺电导率及微观结构的影响. 唐晓萍.西南民族学院学报·自然科学版，第29卷第2期. 2003 * |
| 磷酸掺杂对聚苯胺电导率及微观结构的影响. 甘孟瑜等.重庆大学学报，第26卷第10期. 2003 * |
| 质子酸掺杂聚苯胺导电材料的合成. 汪水平等：.纤维复合材料，第1期. 2005 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1752160A (en) | 2006-03-29 |
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