CN1752160A - 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 PDF

Info

Publication number
CN1752160A
CN1752160A CN 200510019515 CN200510019515A CN1752160A CN 1752160 A CN1752160 A CN 1752160A CN 200510019515 CN200510019515 CN 200510019515 CN 200510019515 A CN200510019515 A CN 200510019515A CN 1752160 A CN1752160 A CN 1752160A
Authority
CN
China
Prior art keywords
phosphoric acid
phosphate
priming paint
aniline
zinc
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN 200510019515
Other languages
Chinese (zh)
Other versions
CN100363445C (en
Inventor
张学敏
郑化
陈在红
马定桂
陈纪纲
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wuhan University of Technology WUT
Original Assignee
Wuhan University of Technology WUT
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Wuhan University of Technology WUT filed Critical Wuhan University of Technology WUT
Priority to CNB2005100195157A priority Critical patent/CN100363445C/en
Publication of CN1752160A publication Critical patent/CN1752160A/en
Application granted granted Critical
Publication of CN100363445C publication Critical patent/CN100363445C/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Landscapes

  • Paints Or Removers (AREA)

Abstract

A phosphorizing priming paint of phosphoric acid doped polyphenylamine is composed of components A and B, and is prepared from the electrically conductive high-molecular material (phosphoric acid doped polyphenylamine), antirust phosphate pigments, and polyvinyl butyral resin. Its advantages are high adhesion and high antirust effect.

Description

A kind of phosphoric acid doped polyphenylamine phosphate priming paint and preparation method thereof
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%.
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 polyvinyl butyral resin 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 polyvinyl butyral resin.
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:
Figure A20051001951500061
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 polyvinyl butyral resin 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% resin 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 polyvinyl butyral resin 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 polyvinyl butyral resin are mixed with.
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 O.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 1mol/L HCl 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 (9)

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 a kind of phosphoric acid doped polyphenylamine phosphate priming paint,
The A component is ground by 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%
The constitutional features of phosphate-doped polyaniline is as follows:
Figure A2005100195150002C1
A -: be H 2PO 4 -, HPO 4 2-Or PO 4 3-
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 made into by 85% phosphoric acid, distilled water and alcoholic solvent, alcoholic solvent is 3: 1 ethanol and a butanols mixed solvent, it is characterized in that the A component forms phosphate-doped polyaniline with phosphate-doped polyaniline, utilize the electroconductive polymer of phosphate-doped polyaniline to cooperate again, be made into phosphoric acid doped polyphenylamine phosphate priming paint with polyvinyl butyral resin then with aluminium triphosphate, phosphoric acid salt rust-stabilising pigment
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%.
4. according to the preparation method of the described priming paint of claim 3, it is characterized in that phosphate-doped polyaniline is made by following chemical synthesis process:
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 is dissolved with 0.1~1mol/L phosphoric acid solution, stir down, slowly drip ammonium persulfate solution, 10~25 ℃ of reactions 3~10 hours, suction filtration is with 0.1~1mol/L phosphoric acid solution filter wash 3 times, 60~80 ℃ of vacuum-drying 24 hours
The constitutional features of phosphate-doped polyaniline is as follows:
Figure A2005100195150002C2
A -: be H 2PO 4 -, HPO 42 -Or PO 43 -
5. 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 doped polyaniline by situ aggregation method in film forming with small molecules aniline, make the electroconductive polymer and the aluminium triphosphate of the phosphate-doped polyaniline that generates on the spot, phosphoric acid salt rust-stabilising pigment and polyvinyl butyral resin form the coating of 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.
6. according to the preparation method of the described priming paint of claim 5, it is characterized in that chromic acid class oxygenant comprises: a kind of in chromic acid, chromic anhydride, sodium dichromate 99, ammonium dichromate, the potassium bichromate, perhaps two kinds, perhaps two or more mixtures.
7. according to the preparation method of claim 3 or 5 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.
8. 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 polyvinyl butyral resin,
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.
9. the preparation method of described priming paint according to Claim 8 is characterized in that dichromate adopts a kind of in sodium dichromate 99, ammonium dichromate, the potassium bichromate, perhaps two kinds, and perhaps two or more mixtures.
CNB2005100195157A 2005-09-29 2005-09-29 Phosphoric acid doped polyphenylamine phosphate priming paint and preparing process thereof Expired - Fee Related CN100363445C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CNB2005100195157A CN100363445C (en) 2005-09-29 2005-09-29 Phosphoric acid doped polyphenylamine phosphate priming paint and preparing process thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CNB2005100195157A CN100363445C (en) 2005-09-29 2005-09-29 Phosphoric acid doped polyphenylamine phosphate priming paint and preparing process thereof

Publications (2)

Publication Number Publication Date
CN1752160A true CN1752160A (en) 2006-03-29
CN100363445C CN100363445C (en) 2008-01-23

Family

ID=36679167

Family Applications (1)

Application Number Title Priority Date Filing Date
CNB2005100195157A Expired - Fee Related CN100363445C (en) 2005-09-29 2005-09-29 Phosphoric acid doped polyphenylamine phosphate priming paint and preparing process thereof

Country Status (1)

Country Link
CN (1) CN100363445C (en)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102226045A (en) * 2011-04-15 2011-10-26 贵阳神迪化工有限公司 Aluminum-tripolyphosphate-doped polyaniline antirust pigment and preparation method thereof
CN102794257A (en) * 2012-08-16 2012-11-28 南车长江车辆有限公司 Water-based paint coating process for stainless steel rail wagon
CN102898910A (en) * 2012-10-24 2013-01-30 江苏纽克莱涂料有限公司 Alcohol-soluble inorganic zinc-enriched over-rush anticorrosive paint
CN102924716A (en) * 2012-11-26 2013-02-13 广西大学 Preparation method for polyphosphoric acid doped polyaniline
CN104212343A (en) * 2014-09-18 2014-12-17 江苏海晟涂料有限公司 Elastic anticorrosive paint and preparation method thereof
CN104302411A (en) * 2012-03-28 2015-01-21 杜波依斯化工股份有限公司 Pretreatment of metal surfaces prior to paint using polyaniline particles
CN104449340A (en) * 2014-11-18 2015-03-25 安徽创业机电设备有限公司 Method for preparing high-toughness anti-corrosive coating by utilizing polyaniline
CN109385154A (en) * 2018-11-26 2019-02-26 西南石油大学 A kind of new green environment protection electrochemical protection film layer and its preparation process
CN115873478A (en) * 2022-12-31 2023-03-31 湖南亚大丰晖新材料有限公司 High-solid polyaniline epoxy anticorrosive primer and preparation method thereof

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1056165C (en) * 1996-12-25 2000-09-06 中国科学院长春应用化学研究所 Preparation of mixed polyaniline aqueous solution and dispersant liquid
CN1073608C (en) * 1997-10-25 2001-10-24 中国科学院长春应用化学研究所 Method for preparing conductive antifouling corrosion-resistant poly-aniline paint
CN1182213C (en) * 2002-09-20 2004-12-29 西安交通大学 Process for preparing corrosion-resistant polyaniline paint
CN1296410C (en) * 2004-11-09 2007-01-24 武汉理工大学 Process for preparing doped conductive polyaniline

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102226045A (en) * 2011-04-15 2011-10-26 贵阳神迪化工有限公司 Aluminum-tripolyphosphate-doped polyaniline antirust pigment and preparation method thereof
CN102226045B (en) * 2011-04-15 2014-05-07 贵阳神迪化工有限公司 Aluminum-tripolyphosphate-doped polyaniline antirust pigment and preparation method thereof
CN104302411A (en) * 2012-03-28 2015-01-21 杜波依斯化工股份有限公司 Pretreatment of metal surfaces prior to paint using polyaniline particles
CN102794257A (en) * 2012-08-16 2012-11-28 南车长江车辆有限公司 Water-based paint coating process for stainless steel rail wagon
CN102794257B (en) * 2012-08-16 2014-08-27 南车长江车辆有限公司 Water-based paint coating process for stainless steel rail wagon
CN102898910A (en) * 2012-10-24 2013-01-30 江苏纽克莱涂料有限公司 Alcohol-soluble inorganic zinc-enriched over-rush anticorrosive paint
CN102924716A (en) * 2012-11-26 2013-02-13 广西大学 Preparation method for polyphosphoric acid doped polyaniline
CN104212343A (en) * 2014-09-18 2014-12-17 江苏海晟涂料有限公司 Elastic anticorrosive paint and preparation method thereof
CN104449340A (en) * 2014-11-18 2015-03-25 安徽创业机电设备有限公司 Method for preparing high-toughness anti-corrosive coating by utilizing polyaniline
CN109385154A (en) * 2018-11-26 2019-02-26 西南石油大学 A kind of new green environment protection electrochemical protection film layer and its preparation process
CN115873478A (en) * 2022-12-31 2023-03-31 湖南亚大丰晖新材料有限公司 High-solid polyaniline epoxy anticorrosive primer and preparation method thereof

Also Published As

Publication number Publication date
CN100363445C (en) 2008-01-23

Similar Documents

Publication Publication Date Title
CN100363445C (en) Phosphoric acid doped polyphenylamine phosphate priming paint and preparing process thereof
CN1639278A (en) Anti-corrosion paint for steel with polyaniline
CN1106433C (en) Nm-class Ti polymer paint
CN111019425B (en) Water-based two-component epoxy paint and preparation method thereof
CN102358804A (en) Special binder for waterbrone inorganic zinc-rich anti-corrosion coating
CN103602220B (en) A kind of Siloxane hybrid anticorrosive paint
CN102676028A (en) Long-acting waterborne nanometer attapulgite clay/epoxy anticorrosive coating material and preparing method thereof
CN109593429A (en) A kind of preparation method and application of L-Trp modified graphene oxide aqueous epoxy resins
CN105802441A (en) Water-borne graphene composite coating, and water-borne graphene composite paint and preparation method thereof
CN1281692C (en) Anti-corrosive mixture and coating substances containing said anti-corrosive mixture
CN103232786A (en) Solvent-free nanometer epoxy anticorrosive paint and preparation method thereof
WO2015058669A1 (en) Preparation method for aqueous epoxy ester resin and use thereof
CN1075973A (en) Electvically deposited water based paint and its production and application
JP5639729B1 (en) Cationic electrodeposition coating composition
CN115044279A (en) Two-dimensional polydopamine-reinforced waterborne epoxy composite anticorrosive paint and preparation method and application thereof
CN1075102C (en) Corrosion resisting paint without need of cleaning rust
CN1528835A (en) Single-component room-temperature industrial water crosslinked coating
CN114621654A (en) Water-based epoxy zinc-rich primer and preparation method and application thereof
Ammar et al. Comparison studies on the anticorrosion and overall performance of solvent/water based epoxy-copper reinforced composite coatings
CN1147001A (en) Pigment preparation
MX2011005828A (en) Anti -corrosive paintings and coatings containing nanoparticles.
CN1526780A (en) Water soluble two-component inorganic zinc paint and its making process
CN1772823A (en) Water epoxy resin paint and its making process
CN1357028A (en) Electrodeposition baths contg. yttrium
CN1185313C (en) Polystyrene styrene-butadiene rubber anticorrosive coating

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
C17 Cessation of patent right
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20080123

Termination date: 20091029