CN102311703A - Aqueous polypyrrole/attapulgite electrically-conducting paint and its preparation method - Google Patents
Aqueous polypyrrole/attapulgite electrically-conducting paint and its preparation method Download PDFInfo
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Abstract
The invention relates to an electrically-conducting paint, more specifically to a two-component aqueous polyurethane electrically-conducting paint and its preparation method. The electrically-conducting paint is prepared by the following steps of: firstly, preparing a polypyrrole/attapulgite nanometer conducting composite material; then, dispersing the obtained conducting composite material into an aqueous hydroxyl acrylic emulsion; and finally adding various auxiliary agents and hydrophilic modified polyisocyanates to obtain the two-component aqueous polyurethane electrically-conducting paint. The preparation method provided by the invention has a simple process; in addition, the product has high cost performance and is environmentally friendly.
Description
Technical field
The present invention relates to electrically conducting coating, in more detail, relate to a kind of double-component waterborne polyurethane electrically conducting coating and preparation method thereof.
Background technology
Electrostatic produces and accumulation brings a lot of troubles for the modern life, production and scientific activities, or even disaster.If the static charge of gathering in a large number can not in time discharge, will destroy circuit, damage electrical equipment, even produce electrical spark; Cause accidents such as fire, blast, cause tremendous loss, therefore; In the place of a lot of accumulate static charges easily such as terrace, equipment all need carry out anti-electrostatic and handle; Electrically conducting coating is a kind of important features type coating, the market requirement that it has wide research and development prospect and increase day by day in electromagnetic shielding, field such as antistatic, at present; Most widely used is the mixed electrically conducting coating; Promptly in resin, evenly sneak into conductive filler material, be coated on body surface then, conductive filler material mainly contains metal-powder, charcoal based material and doped metal-oxide powder 3 big classes.Metal-powder generally is metal-powders such as silver, copper, nickel; Shortcoming is big, easy deposition of density and difficult the dispersion; The charcoal based material mainly contains graphitized carbon black, graphite, carbon nanotube and Graphene etc.; Shortcoming is black and difficult dispersion of color, and the doped metal-oxide powder mainly contains antimony doped tin oxide (ATO), mixes indium White tin oxide (ITO), Al-Doped ZnO (ZAO), conduction mica, conductive titanium oxide and conduction permanent white etc., and the shortcoming of this type material is that conductivity is not good enough; Generally speaking, mainly there is following deficiency in traditional electrically conducting coating technology of preparing: the one, and conductive filler material is not ideal enough, and this shows that mainly conductive effect is bad or conductivity is unstable or costs an arm and a leg; The 2nd, existing electrically conducting coating almost all is solvent with the organic solvent; Environmental pollution is serious; Chinese patent CN101220240A proposes a kind of anticorrosion paint for polyurethane electrostatic resistance preparation method; Its conductive filler material remains traditional metal-powder, graphite and conductive mica powder etc., and the solvent that uses be not environmental protection of organic solvent.
Polypyrrole (PPy) is regarded as the conducting polymer composite that is hopeful substituted metal powder and carbon dust filler most, still owing to have the simple and conductivity excellence of preparation method; Polypyrrole exists shortcomings such as insoluble molten, mechanical poor ductility, processing difficulties, is difficult to direct processed and applied, it is promoted the use be restricted; Discovered in recent years is coated to electric polypyrrole and prepares matrix material on the inorganic nano-particle, and it is synthetic convenient, and the price raw material is low; Antioxidant property is good, has solved on the one hand the processing and the formability problem of electric polypyrrole, on the other hand can be with the functional polyalkylene of the electroconductibility of polymer self and nanoparticle in one; Improved the specific conductivity of polypyrrole; Simultaneously thermostability and mechanical ductility also are improved, but also can obtain other functional character, attapulgite (ATP) be a kind of layer of chain-like structure contain Shuifu County's zeopan clay mineral; Its crystal is needle-like, fibrous agrregate; The diameter of single fiber crystalline substance is about 20nm, and length can reach several microns, is a kind of natural monodimension nanometer material.With the nano-attapulgite stone is nucleome, coats the electric polypyrrole layer in its surface in situ polymerization, makes the PPy/ATP conductive nano composites, is unusual ideal electrically conducting coating additive.Up to now, also less than report about environment-friendly type polypyrrole/attapulgite waterborne conductive coating.
Summary of the invention
The object of the invention is to provide excellent waterborne conductive coating of a kind of good conductivity, stability and preparation method thereof, and this method has the simple and product of technology and has advantages such as high performance-price ratio, environmental protection.
It is the preparation method of the double-component waterborne polyurethane electrically conducting coating of conductive filler material with polypyrrole/attapulgite matrix material that the present invention provides a kind of.This electrically conducting coating prepares by following step: at first; Preparation polypyrrole/palygorskite nano conducing composite material; Then; The composite conducting material of gained is distributed in the water-based hydroxyl ACRYLIC EMULSION, adds the POLYMETHYLENE POLYPHENYLISOCYANATE of various auxiliary agents and hydrophilic modifying again, promptly obtain the double-component waterborne polyurethane electrically conducting coating.
This double-component waterborne polyurethane electrically conducting coating is made up of A, B component: the A component: water-based hydroxyl ACRYLIC EMULSION 50 ~ 80 weight parts; Skimmer 0.5 ~ 1.5 weight part; Flow agent 1 ~ 3 weight part; Thickening material 1 ~ 4 weight part is as polypyrrole/attapulgite matrix material slurry 8 ~ 30 weight parts of conductive filler material, deionized water 5 ~ 20 weight parts; The B component: the POLYMETHYLENE POLYPHENYLISOCYANATE of hydrophilic modifying is as solidifying agent.
Concrete technical scheme of the present invention is following:
(1) preparation of polypyrrole/attapulgite matrix material filter cake: to mass concentration is to add amino silicane coupling agent in 10 ~ 200 grams per liter attapulgite slurries, is warming up to 60 ~ 90 ℃, insulated and stirred reaction 2 ~ 20 hours; Be cooled to 0 ~ 30 ℃, add pyrrole monomer and doping agent successively, continue to stir; Add oxygenant, insulation reaction 1 ~ 6 hour, suction filtration; Washing to filtrating is neutral, promptly obtains polypyrrole/attapulgite matrix material filter cake;
(2) preparation of polypyrrole/attapulgite matrix material slurry: in the polypyrrole/attapulgite matrix material filter cake of step (1) preparation, add deionized water, dispersion agent; Disperseed 10 ~ 30 minutes; Obtain polypyrrole/attapulgite matrix material slurry, the mass ratio of polypyrrole in the slurry/attapulgite matrix material and deionized water is 0.05 ~ 0.5:1; The quality that the quality of polypyrrole in the said slurry/attapulgite matrix material equals polypyrrole/attapulgite matrix material filter cake multiply by its solid content;
(3) coating A component preparation: add polypyrrole/attapulgite matrix material slurry, deionized water, skimmer, flow agent, the thickening material of step (2) preparation in hydrotropisms's hydroxyl acrylic emulsion, mix, obtain the A component;
(4) preparation of double-component waterborne polyurethane electrically conducting coating: according to [OH]: the mixed in molar ratio A of [NCO]=1:0.8 ~ 2, B component; Stir; Promptly be mixed with the double-component waterborne polyurethane electrically conducting coating, wherein, the B component is the POLYMETHYLENE POLYPHENYLISOCYANATE of hydrophilic modifying; [NCO] comes from POLYMETHYLENE POLYPHENYLISOCYANATE, and [OH] is from the water-based hydroxyl ACRYLIC EMULSION.
The described amino silicane coupling agent of step (1) is: γ-An Bingjisanyiyangjiguiwan, γ-An Bingjisanjiayangjiguiwan, N-β (aminoethyl)-γ-An Bingjisanjiayangjiguiwan, N-β (aminoethyl)-γ-aminopropyl methyl dimethoxysilane, N-β (aminoethyl)-γ-aminopropyl methyldiethoxysilane, phenylamino Union carbide A-162, phenylamino methyltrimethoxy silane, N-β (aminoethyl)-γ-An Bingjisanyiyangjiguiwan or aminoethyl aminoethyl aminopropyl trimethoxysilane; Wherein, the mass ratio of coupling agent and attapulgite is: 0.05 ~ 0.4:1.
The mass ratio of described pyrrole monomer of step (1) and attapulgite is: 0.1 ~ 0.5:1.
The described doping agent of step (1) is in Supragil GN, tosic acid, naphthene sulfonic acid, sodium laurylsulfonate or the X 2073, and the add-on of doping agent and the mol ratio of pyrrole monomer are: 0.14 ~ 0.68:1.
The described oxygenant of step (1) is in ammonium persulphate, Potassium Persulphate or the Sodium Persulfate, and the add-on of oxygenant and the mol ratio of pyrrole monomer are: 0.5 ~ 1.5:1.
The described dispersing method of step (2) is a kind of during ultra-sonic dispersion, dispersed with stirring and sand milling disperse.
The described dispersion agent of step (2) is the polyamine amides, and the mass ratio of the add-on of dispersion agent and polypyrrole/attapulgite matrix material is: 0.01 ~ 0.04:1.
The described flow agent of step (3) is N-BUTYL ACETATE Mierocrystalline cellulose or silicone based flow agent.
The described thickening material of step (3) is an organobentonite.
The described skimmer of step (3) is silicone based skimmer.
In the described A component of step (3), 50 ~ 80 parts of water-based hydroxyl ACRYLIC EMULSIONs, 8 ~ 30 parts of polypyrroles/attapulgite conductive filler material, 5 ~ 20 parts of deionized waters, 0.5 ~ 1.5 part of skimmer, 1 ~ 3 part of flow agent, 1 ~ 4 part of organobentonite.
The described solidifying agent of step (4) is the POLYMETHYLENE POLYPHENYLISOCYANATE of hydrophilic modifying: be specially hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), tolylene diisocyanate (TDI), ditan-4,4 '-a kind of in vulcabond (MDI) and the Methylcyclohexyl diisocyanate (HTDI).
Electrically conducting coating of the present invention is formed and preparation method for coating has the following advantages:
1, the present invention selects for use be polypyrrole/attapulgite matrix material slurry as conductive filler material, the preparation method is simple for this filler, attapulgite clay abundant raw material and low price have reduced the cost of coating, make this coating have high cost performance;
2, be coated on polypyrrole with on the attapulgite behind the aminosilane coupling agent modifying; Improved the coating integrity of polypyrrole to attapulgite; Attapulgite is the rod-like fibre structure, forms fine and close conductive network easily, obtains the more excellent matrix material of conductivity;
3, the waterborne conductive coating conductivity of preparing is excellent and have good conductive stability, and coating is placed electroconductibility no change half a year;
4, become slurry to improve its degree of scatter in emulsion polypyrrole/attapulgite Composite Preparation, avoided the agglomeration of matrix material in emulsion;
5, this electrically conducting coating does not add or trace interpolation organic solvent, does not add any heavy metal, can not pollute environment, and polypyrrole also has very high heat and chemicalstability, is a kind of environment-friendly type coating.
Embodiment
The present invention will be elaborated to technical scheme of the present invention through following specific embodiment, but never be confined to the embodiment of following proposition.
Embodiment 1
(1) is to add 12 gram γ-An Bingjisanyiyangjiguiwans in the 60 grams per liter attapulgite matrix material slurries to 1 mass per liter concentration, is warming up to 80 ℃, insulated and stirred reaction 8 hours; Be cooled to 10 ℃, add 24.35 gram sodium laurylsulfonates (0.089mol), 18 gram pyrrole monomers (0.27mol) successively, continue to stir; Add 61.38 gram ammonium persulphates (0.27mol), insulation reaction 4 hours, suction filtration; Washing to filtrating is neutral; Promptly obtain polypyrrole/attapulgite matrix material filter cake, recording the filter cake solid content is 25% (mass percent, down together);
(2) get in the polypyrrole/attapulgite matrix material filter cake of 60 gram steps (1) preparations and add 105 gram deionized waters, 0.45 gram BKY-161, ultra-sonic dispersion 25 minutes obtains polypyrrole/attapulgite matrix material slurry;
(3) (spinning the auxiliary reagent factory in Taixing City, Jiangsu Province produces to 80 gram water-based hydroxyl ACRYLIC EMULSIONs; Solid content is 45%; Hydroxyl value is 39.6mgKOH/g; Be that [OH] content is 0.000706 mole in every gram emulsion; The conduction slurry that contains 12 gram polypyrrole/attapulgite matrix materials, 10 that adds step (2) preparation down together) restrains deionized waters, 0.8 gram, 201 methyl-silicone oils, 1.6 gram N-BUTYL ACETATE Mierocrystalline celluloses (CAB381-0.1), 2.4 gram organobentonites (Claytone 34), and ultra-sonic dispersion is 20 minutes then, obtains the A component;
(4) according to [OH]: (content of [NCO] is 0.005 mole of every gram to hexamethylene diisocyanate (HDI) 13.56 grams of the ratio of [NCO]=1:1.2 adding hydrophilic modifying in the A component of step (3) preparation; Down together); Stir, promptly be mixed with the double-component waterborne polyurethane electrically conducting coating.
Embodiment 2
(1) is to add 4 gram γ-An Bingjisanjiayangjiguiwans in the 10 grams per liter attapulgite slurries to the 1L mass concentration, is warming up to 60 ℃, insulated and stirred reaction 2 hours; Be cooled to 0 ℃, add 0.73 gram X 2073 (0.0021mol), 1 gram pyrrole monomer (0.015mol) successively, continue to stir; Add 1.71 gram ammonium persulphates (0.0075mol); Insulation reaction 1 hour, suction filtration, washing to filtrating is neutral; Promptly obtain polypyrrole/attapulgite matrix material filter cake, recording the filter cake solid content is 25%;
(2) get in the polypyrrole/attapulgite matrix material filter cake of 60 gram steps (1) preparations and add 255 gram deionized waters, 0.15 gram BKY-163, ultra-sonic dispersion 30 minutes obtains polypyrrole/attapulgite matrix material slurry;
(3) in 50g water-based hydroxyl ACRYLIC EMULSION, add the conduction slurry that contains 8 gram polypyrrole/attapulgite matrix materials, 5 gram deionized waters, 0.5 gram, 201 methyl-silicone oils, 1 gram N-BUTYL ACETATE Mierocrystalline cellulose (CAB551-0.01), the 1 gram organobentonite (Claytone 34) of step (2) preparation; Sand milling disperseed 20 minutes then, obtained the A component;
(4) according to [OH]: the ratio of [NCO]=1:0.8 adds hexamethylene diisocyanate (HDI) 5.65 grams of hydrophilic modifying in the A component of step (3) preparation, stir, and promptly is mixed with the double-component waterborne polyurethane electrically conducting coating.
Embodiment 3
(1) is to add 0.5 gram N-β (aminoethyl)-γ-An Bingjisanjiayangjiguiwan in the 10 grams per liter attapulgite slurries to the 1L mass concentration, is warming up to 90 ℃, insulated and stirred reaction 20 hours.Be cooled to 30 ℃, add 9.14 gram Supragil GNs (0.051mol), 5 gram pyrrole monomers (0.075mol) successively, continue to stir; Add 8.55 gram ammonium persulphates (0.0375mol); Insulation reaction 6 hours, suction filtration, washing to filtrating is neutral; Promptly obtain polypyrrole/attapulgite matrix material filter cake, recording the filter cake solid content is 25%;
(2) get in the polypyrrole/attapulgite matrix material filter cake of 60 gram steps (1) preparations and add 30 gram deionized waters, 0.6 gram BKY-164, ultra-sonic dispersion 30 minutes obtains polypyrrole/attapulgite matrix material slurry;
(3) restrain the conduction slurry that contains 30 gram polypyrrole/attapulgite matrix materials, 20 gram deionized waters, the 1.5 gram BYK-141,3 that add step (2) preparation in the water-based hydroxyl ACRYLIC EMULSIONs to 80 and restrain N-BUTYL ACETATE Mierocrystalline celluloses (CAB381-20), 4 gram organobentonites (Claytone 34); Dispersed with stirring is 20 minutes then, obtains the A component;
(4) according to [OH]: the ratio of [NCO]=1:2 adds isophorone diisocyanate (IPDI) 22.59 grams of hydrophilic modifying in the A component of step (3) preparation, stir, and promptly is mixed with the double-component waterborne polyurethane electrically conducting coating.
Embodiment 4
(1) is to add 80 gram N-β (aminoethyl)-γ-aminopropyl methyl dimethoxysilanes in the 200 grams per liter attapulgite slurries to the 1L mass concentration, is warming up to 90 ℃, insulated and stirred reaction 20 hours.Be cooled to 30 ℃, add 35.9 gram tosic acid (0.2087mol), 100 gram pyrrole monomers (1.493mol) successively, continue to stir; Add 510.9 gram ammonium persulphates (2.239mol); Insulation reaction 1 hour, suction filtration, washing to filtrating is neutral; Promptly obtain polypyrrole/attapulgite matrix material filter cake, recording the filter cake solid content is 25%;
(2) get in the polypyrrole/attapulgite matrix material filter cake of 60 gram steps (1) preparations and add 105 gram deionized waters, 0.3 gram BKY-151, high-speed stirring was disperseed 10 minutes, obtained polypyrrole/attapulgite matrix material slurry;
(3) restrain the conduction slurry that contains 30 gram polypyrrole/attapulgite matrix materials, 20 gram deionized waters, the 0.5 gram BYK-141,1 that add step (2) preparation in the water-based hydroxyl ACRYLIC EMULSIONs to 60 and restrain BYK-301,1 gram organobentonite (Claytone HT); Ultra-sonic dispersion is 20 minutes then, obtains the A component;
(4) according to [OH]: the ratio of [NCO]=1:1.4 adds tolylene diisocyanate (TDI) 11.86 grams of hydrophilic modifying in the A component of step (3) preparation, stir, and promptly is mixed with the double-component waterborne polyurethane electrically conducting coating.
Embodiment 5
(1) is to add 10 gram phenylamino Union carbide A-162s in the 200 grams per liter attapulgite slurries to the 1L mass concentration, is warming up to 70 ℃, insulated and stirred reaction 8 hours.Be cooled to 10 ℃, add 42.27 gram naphthene sulfonic acid (0.203mol), 20 gram pyrrole monomers (0.298mol) successively, continue to stir; Add 73.43 gram Sodium Persulfates (0.308mol); Insulation reaction 3 hours, suction filtration, washing to filtrating is neutral; Promptly obtain polypyrrole/attapulgite matrix material filter cake, recording the filter cake solid content is 25%;
(2) get in the polypyrrole/attapulgite matrix material filter cake of 60 gram steps (1) preparations and add 30 gram deionized waters, 0.6 gram BKY-154, high-speed stirring was disperseed 30 minutes, obtained polypyrrole/attapulgite matrix material slurry;
(3) restrain the conduction slurry that contains 20 gram polypyrrole/attapulgite matrix materials, 10 gram deionized waters, the 1 gram BYK-065,2 that add step (2) preparation in the water-based hydroxyl ACRYLIC EMULSIONs to 80 and restrain BYK-302,3 gram organobentonites (Claytone HT); Dispersed with stirring is 20 minutes then, obtains the A component;
(4) according to [OH]: the ditan-4,4 of the ratio of [NCO]=1:1.7 adding hydrophilic modifying in the A component of step (3) preparation '-vulcabond (MDI) 19.20 grams, stir, promptly be mixed with the double-component waterborne polyurethane electrically conducting coating.
Embodiment 6
(1) is to add 80 gram phenylamino methyltrimethoxy silanes in the 200 grams per liter attapulgite slurries to the 1L mass concentration, is warming up to 80 ℃, insulated and stirred reaction 15 hours.Be cooled to 15 ℃, add 14.56 gram sodium laurylsulfonates (0.0535mol), 20 gram pyrrole monomers (0.298mol) successively, continue to stir; Add 80.56 gram Potassium Persulphates (0.298mol); Insulation reaction 5 hours, suction filtration, washing to filtrating is neutral; Promptly obtain polypyrrole/attapulgite matrix material filter cake, recording the filter cake solid content is 25%;
(2) get in the polypyrrole/attapulgite matrix material filter cake of 60 gram steps (1) preparations and add 55 gram deionized waters, 0.15 gram BKY-170, high-speed stirring was disperseed 20 minutes, obtained polypyrrole/attapulgite matrix material slurry;
(3) restrain the conduction slurry that contains 20 gram polypyrrole/attapulgite matrix materials, 5 gram deionized waters, the 1 gram BYK-066,2 that add step (2) preparation in the water-based hydroxyl ACRYLIC EMULSIONs to 50 and restrain BYK-346,2 gram organobentonites (Claytone HT); Sand milling disperseed 20 minutes then, obtained the A component;
(4) according to [OH]: the ratio of [NCO]=1:1.8 adds Methylcyclohexyl diisocyanate (HTDI) 12.71 grams of hydrophilic modifying in the A component of step (3) preparation, stir, and promptly is mixed with the double-component waterborne polyurethane electrically conducting coating.
Comparative example 1
(1) be to add 24.35 gram sodium laurylsulfonates (0.089mol), 18 gram pyrrole monomers (0.027mol) in the 60 grams per liter attapulgite matrix material slurries to the 1L mass concentration; Continue to stir, add 61.38 gram ammonium persulphates (0.27mol), insulation reaction 4 hours; Suction filtration; Washing to filtrating is neutral, promptly obtains polypyrrole/attapulgite matrix material filter cake, and recording the filter cake solid content is 25%;
Other operation is all identical with embodiment 1.
Comparative example 2
In embodiment 1, using volume specific resistance is polypyrrole filter cake replacement polypyrrole/attapulgite matrix material filter cake of 2 Ω cm, and other operation is all identical with embodiment 1.
Comparative example 3
(1) preparation manipulation of polypyrrole/attapulgite matrix material filter cake is identical with embodiment 1;
(2) restrain the conduction filter cake that contains 12 gram polypyrrole/attapulgite matrix materials, 4 gram deionized waters, 0.8 gram, 201 methyl-silicone oils, 1.6 that add step (1) preparation in the water-based hydroxyl ACRYLIC EMULSIONs to 80 and restrain N-BUTYL ACETATE Mierocrystalline celluloses (CAB381-0.1), 2.4 gram organobentonites (Claytone 34); Ultra-sonic dispersion is 20 minutes then, obtains the A component;
(3) according to [OH]: the ratio of [NCO]=1:1.2 adds the hexamethylene diisocyanate (HDI) of hydrophilic modifying in the A component, stir, and promptly is mixed with the double-component waterborne polyurethane electrically conducting coating.
(4) according to [OH]: (content of [NCO] is 0.005 mole of every gram to hexamethylene diisocyanate (HDI) 13.56 grams of the ratio of [NCO]=1:1.2 adding hydrophilic modifying in the A component of step (3) preparation; Down together); Stir, promptly be mixed with the double-component waterborne polyurethane electrically conducting coating.
The coating that obtains is brushed the tinplate tin surface after polishing uniformly; Coat-thickness 35 ~ 50 μ m; Drying is 24 hours under 40 ℃, obtains conductive coating, and the coating test result of above-mentioned six embodiment and three comparative example gained is as shown in table 1 below; Visible by table 1, electrically conducting coating of the present invention has excellent conduction and mechanical property.
Sticking power is measured the regulation of pressing GB/T 1720 and is carried out.
Resistance to impact shock is measured the regulation of pressing GB/T 1732 and is carried out.
Measurement of hardness is pressed the regulation of GB/T 6739 and is carried out.
The coating test result of above-mentioned six embodiment of table 1 and three comparative example gained
Claims (9)
1. water-based polypyrrole/attapulgite electrically conducting coating; It is characterized in that: said electrically conducting coating is to be mixed and formed by A, B component: the A component: water-based hydroxyl ACRYLIC EMULSION 50 ~ 80 weight parts; Skimmer 0.5 ~ 1.5 weight part, flow agent 1 ~ 3 weight part, thickening material 1 ~ 4 weight part; As polypyrrole/attapulgite matrix material slurry 8 ~ 30 weight parts of conductive filler material, deionized water 5 ~ 20 weight parts; The B component: the POLYMETHYLENE POLYPHENYLISOCYANATE of hydrophilic modifying is as solidifying agent.
2. a kind of water-based polypyrrole as claimed in claim 1/attapulgite electrically conducting coating is characterized in that: described flow agent is N-BUTYL ACETATE Mierocrystalline cellulose or silicone based flow agent.
3. a kind of water-based polypyrrole as claimed in claim 1/attapulgite electrically conducting coating is characterized in that: described thickening material is an organobentonite.
4. a kind of water-based polypyrrole as claimed in claim 1/attapulgite electrically conducting coating is characterized in that: described skimmer is silicone based skimmer.
5. a kind of water-based polypyrrole as claimed in claim 1/attapulgite electrically conducting coating; It is characterized in that: described solidifying agent be hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), tolylene diisocyanate (TDI), ditan-4,4 '-a kind of in vulcabond (MDI) and the Methylcyclohexyl diisocyanate (HTDI).
6. a kind of water-based polypyrrole as claimed in claim 1/attapulgite electrically conducting coating is characterized in that: the preparation method of said polypyrrole/attapulgite matrix material slurry is following:
(1) preparation of polypyrrole/attapulgite matrix material filter cake: to mass concentration is to add amino silicane coupling agent in 10 ~ 200 grams per liter attapulgite slurries, is warming up to 60 ~ 90 ℃, insulated and stirred reaction 2 ~ 20 hours; Be cooled to 0 ~ 30 ℃, add pyrrole monomer and doping agent successively, continue to stir; Add oxygenant, insulation reaction 1 ~ 6 hour, suction filtration; Washing to filtrating is neutral, promptly obtains polypyrrole/attapulgite matrix material filter cake;
(2) preparation of polypyrrole/attapulgite matrix material slurry: in the polypyrrole/attapulgite matrix material filter cake of step (1) preparation, add deionized water, dispersion agent; Disperseed 10 ~ 30 minutes; Obtain polypyrrole/attapulgite matrix material slurry, the mass ratio of polypyrrole in the slurry/attapulgite matrix material and deionized water is 0.05 ~ 0.5:1; The quality that the quality of polypyrrole in the said slurry/attapulgite matrix material equals polypyrrole/attapulgite matrix material filter cake multiply by its solid content.
7. a kind of water-based polypyrrole as claimed in claim 6/attapulgite electrically conducting coating; It is characterized in that: described amino silicane coupling agent is: γ-An Bingjisanyiyangjiguiwan, γ-An Bingjisanjiayangjiguiwan, N-β (aminoethyl)-γ-An Bingjisanjiayangjiguiwan, N-β (aminoethyl)-γ-aminopropyl methyl dimethoxysilane, N-β (aminoethyl)-γ-aminopropyl methyldiethoxysilane, phenylamino Union carbide A-162, phenylamino methyltrimethoxy silane, N-β (aminoethyl)-γ-An Bingjisanyiyangjiguiwan or aminoethyl aminoethyl aminopropyl trimethoxysilane; Wherein, the mass ratio of coupling agent and attapulgite is: 0.05 ~ 0.4:1; The mass ratio of described pyrrole monomer and attapulgite is: 0.1 ~ 0.5:1; Described doping agent is in Supragil GN, tosic acid, naphthene sulfonic acid, sodium laurylsulfonate or the X 2073, and the add-on of doping agent and the mol ratio of pyrrole monomer are: 0.14 ~ 0.68:1; Described oxygenant is in ammonium persulphate, Potassium Persulphate or the Sodium Persulfate, and the add-on of oxygenant and the mol ratio of pyrrole monomer are: 0.5 ~ 1.5:1.
8. a kind of water-based polypyrrole as claimed in claim 6/attapulgite electrically conducting coating; It is characterized in that: described dispersing method is a kind of during ultra-sonic dispersion, dispersed with stirring and sand milling disperse; Described dispersion agent is the polyamine amides, and the mass ratio of the add-on of dispersion agent and polypyrrole/attapulgite matrix material is: 0.01 ~ 0.04:1.
9. the preparation method of a kind of water-based polypyrrole as claimed in claim 1/attapulgite electrically conducting coating may further comprise the steps:
(1) preparation of polypyrrole/attapulgite matrix material filter cake: to mass concentration is to add amino silicane coupling agent in 10 ~ 200 grams per liter attapulgite slurries, is warming up to 60 ~ 90 ℃, insulated and stirred reaction 2 ~ 20 hours; Be cooled to 0 ~ 30 ℃, add pyrrole monomer and doping agent successively, continue to stir; Add oxygenant, insulation reaction 1 ~ 6 hour, suction filtration; Washing to filtrating is neutral, promptly obtains polypyrrole/attapulgite matrix material filter cake;
(2) preparation of polypyrrole/attapulgite matrix material slurry: in the polypyrrole/attapulgite matrix material filter cake of step (1) preparation, add deionized water, dispersion agent; Disperseed 10 ~ 30 minutes; Obtain polypyrrole/attapulgite matrix material slurry, the mass ratio of polypyrrole in the slurry/attapulgite matrix material and deionized water is 0.05 ~ 0.5:1; The quality that the quality of polypyrrole in the said slurry/attapulgite matrix material equals polypyrrole/attapulgite matrix material filter cake multiply by its solid content;
(3) coating A component preparation: add polypyrrole/attapulgite matrix material slurry, deionized water, skimmer, flow agent, the thickening material of step (2) preparation in hydrotropisms's hydroxyl acrylic emulsion, mix, obtain the A component;
(4) preparation of double-component waterborne polyurethane electrically conducting coating: according to [OH]: the mixed in molar ratio A of [NCO]=1:0.8 ~ 2, B component; Stir; Promptly be mixed with the double-component waterborne polyurethane electrically conducting coating, wherein, the B component is the POLYMETHYLENE POLYPHENYLISOCYANATE of hydrophilic modifying; [NCO] comes from POLYMETHYLENE POLYPHENYLISOCYANATE, and [OH] is from the water-based hydroxyl ACRYLIC EMULSION.
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