CN101824264B - Nuclear shell conductive polyaniline aqueous antistatic coating and preparation method thereof - Google Patents
Nuclear shell conductive polyaniline aqueous antistatic coating and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a nuclear shell conductive polyaniline aqueous antistatic coating. The nuclear shell conductive polyaniline aqueous antistatic coating comprises the following components: micron-sized conductive polymer nuclear shell composite particles, nanoscale conductive polymer nuclear shell composite particles, and an aqueous coating resin emulsion, wherein the micron-sized conductive polymer nuclear shell composite particles account for 0.5 to 20 mass percent of the aqueous coating resin emulsion; and the nanoscale conductive polymer nuclear shell composite particles account for0.125 to 5 mass percent of the aqueous coating resin emulsion. A preparation method comprises the following steps of: adding the micron-size conductive polymer nuclear shell composite particles and the nanoscale conductive polymer nuclear shell composite particles into the aqueous coating resin emulsion at the same time with stirring and dispersing uniformly to obtain the nuclear shell conductive polyaniline aqueous antistatic coating. Nuclear shell conductive polyaniline is added into the coating as a conductive additive, so that the coating has the advantages of light specific gravity, low cost, adjustable conductivity, high bonding capacity with a film-forming resin and the like.
Description
Technical field
The present invention relates to a kind of nuclear shell conductive polyaniline aqueous antistatic coating and preparation method thereof.
Background technology
The today of improve constantly in science and technology, society constantly developing, particularly along with the fast development of digital machine and large-scale integrated circuit technology, static brings about great losses for people's productive life.In the recent period u. s. published relate to the damage survey result who causes because of static of more than 10 industry, direct economic loss every year on average is up to more than 200 hundred million dollars, the loss that only electronics industry every year damages electronic component because of static hazard is just up to more than 100 hundred million dollars.And use antistatic coating be eliminate static hazard the most succinctly, effective means.
Present antistatic coating mainly is in coating, to introduce anti static additive.Existing anti static additive mainly contains following several kinds: one, carbon system (carbon black, graphite etc.); Two, metal powder or silk; Three, compound system (metallized glass silk, mica etc.).Though first kind price comparison is cheap, there are defectives such as color is dark, dull coloring, difficult dispersion, electrical property instability; Second type: plain metal powder or silk are prone to oxidized in the resin treatment process, and precious metal that performance is good such as gold and silver etc. are again because expensive is difficult to large-scale application; The 3rd type adds and has spoilage problems man-hour.And the affinity between above-mentioned materials and the organic resin is all limited, and the last film forming performance of coating is caused disadvantageous effect.
Electrically conductive polyaniline is that a kind of synthetic convenience, cost of material are low, asepsis environment-protecting, antioxidant property is good, specific conductivity is higher and adjustable macromolecular material; Be one type and have the density of plastics, the electroconductibility of metal; The chemistry that possesses metal and plastics again and be short of and the special type function material of chemical property are unusual ideal antistatic coating additives.Polyaniline antistatic coating mainly is solvent type at present, contains a large amount of organic solvents in the coating, and the use of these solvents has not only increased cost, and solvent evaporate into the healthy of contaminate environment in the atmosphere, infringement workmen in construction process.The aqueous polyanion antistatic coating of environment-friendly type then can be avoided the defective of above solvent-borne type product.The aqueous polyanion antistatic coating has wide practical use in the fields such as transportation storage of telecommunications industry, national defense safety, starting material (like coal, oil) and inflammable and explosive dangerous goods.Add the report of the aqueous antistatic coating of micron order nuclear shell conductive polyaniline and nano level nuclear shell conductive polyaniline when at present, not having in the prior art about environment-friendly type.
Summary of the invention
To above-mentioned prior art, the invention provides a kind ofly has excellent conductive capability, and has the nuclear shell conductive polyaniline aqueous antistatic coating of environmental protection simultaneously concurrently, and its preparation method is provided.
The present invention realizes through following technical scheme:
A kind of nuclear shell conductive polyaniline aqueous antistatic coating; Form by the component of following weight part: micron order conductive polymers nucleocapsid composite particles; Nano-level conducting polyalcohol nucleocapsid composite particles, the water-borne coatings resin emulsion, wherein; The quality of micron order conductive polymers nucleocapsid composite particles accounts for 0.5～20% of water-borne coatings resin emulsion quality, and the quality of nano-level conducting polyalcohol nucleocapsid composite particles accounts for 0.125～5% of water-borne coatings resin emulsion quality.
The kernel of said micron order conductive polymers nucleocapsid composite particles is (vinylbenzene-SSS) multipolymer; The kernel of nano-level conducting polyalcohol nucleocapsid composite particles is (methyl methacrylate-butyl acrylate-vinylformic acid) terpolymer resin; The conductive polymers shell is an electrically conductive polyaniline.
Said water-borne coatings resin emulsion is that solid content is that 30～80% aqueous epoxy resin emulsion or solid content are that 30～80% water-borne acrylic resin emulsion or solid content are 30～80% aqueous polyurethane resin emulsion.
The preparation method of said nuclear shell conductive polyaniline aqueous antistatic coating may further comprise the steps (the following stated umber is weight part):
(1) preparation micron order conductive polymers nucleocapsid composite particles: 1.5～3 parts of Vinylpyrrolidone polymers, 5～20 parts of zero(ppm) water, 8～15 parts of vinylbenzene, 80～150 parts of ethanol and 0.1～0.15 part of Diisopropyl azodicarboxylate are joined stirring and dissolving in the there-necked flask, and reaction is 4～8 hours when being warming up to 70 ℃; Add 0.5～2.5 part of SSS, 1.5～4 parts of water, 0.001 part of Potassium Persulphate and 20～30 parts of solution (being controlled at 10～30min adds) that ethanol is formed again, continue reaction 3～5 hours, gathered (vinylbenzene-SSS) microballoon; Gather (vinylbenzene-SSS) microballoon, 0.25 part of hydrochloric acid (wt=36%), 0.3～1 part of aniline monomer of getting 1 part of purge drying then join in 50～100 parts of water; After fully disperseing; Join in 50 parts of aqueous solution that are dissolved with 0.3～2 part of ammonium persulphate reaction 18～24h, centrifugation; Gathered (vinylbenzene-SSS)/polyaniline nucleocapsid micron particle after the drying, that is: (PS-PSS/PANI) composite particles;
(2) preparation nano-level conducting polyalcohol nucleocapsid composite particles: 0.3～0.5 part of sodium lauryl sulphate is dissolved in 86 parts of zero(ppm) water obtains the aqueous solution earlier; Again 8～12 parts of TEB 3Ks, 4～2 parts of Bing Xisuandingzhis, 0.5～1 part of vinylformic acid and 0.3～0.6 part of n-hexadecane are mixed and oil solution be added to and stir in the aqueous solution, put in the ultrasonic cleaner that fills frozen water ultrasonic 30 minutes into; Be warmed up to 70 ℃ then, add 0.2～0.4 part of Potassium Persulphate, react and obtained the terpolymer resin miniemulsion in 4～6 hours; 2 parts of these terpolymer resin miniemulsions, 0.1～0.5 part of aniline and 0.1～0.5 part of hydrochloric acid (wt=36%) joined in 100～150 parts of water stir; Join again in 30 parts of aqueous solution that are dissolved with 0.1～1 part of ammonium persulphate (being controlled at 15～45min drips); Reaction is 18～24 hours under ice bath, nitrogen protection; The product that obtains is purified; Gathered (methyl methacrylate-butyl acrylate-vinylformic acid)/polyaniline core-shell nano, that is: P (MMA-BA-AA)/PANI composite particles;
(3) composite: micron order conductive polymers nucleocapsid composite particles and nano-level conducting polyalcohol nucleocapsid composite particles are joined in the water-borne coatings resin emulsion simultaneously, and dispersed with stirring is even, has both got nuclear shell conductive polyaniline aqueous antistatic coating; Wherein, the quality of micron order conductive polymers nucleocapsid composite particles accounts for 0.5～20% of water-borne coatings resin emulsion quality, and the quality of nano-level conducting polyalcohol nucleocapsid composite particles accounts for 0.125～5% of water-borne coatings resin emulsion quality.
The transmission electron microscope picture of micron order that the present invention obtains and nano level nuclear shell conductive polyaniline composite particles is as shown in Figure 4.
Coating of the present invention has added nuclear shell conductive polyaniline as conductive additive, has light specific gravity, cost is low, electric conductivity is adjustable, the advantage good etc. with the bonding force of film-forming resin.The contriver is according to the notion of " particle design ", and through design dexterously, meticulous design, on purpose the conductive polyaniline composite particle of preparation with nucleocapsid structure comes p-poly-phenyl amine to carry out modification, and nucleocapsid structure can be given composite particles with the excellent comprehensive performance.It is the nucleocapsid structure composite particles of the good plasticity insulating polymer of shell, mechanical property for nuclear that the present invention has prepared electrically conductive polyaniline; This composite particles had both had electroconductibility, the static resistance of conductive polymers; The thermoplasticity, the snappiness that have superpolymer again; It is added in the resin emulsion, and the antistatic coating over-all properties that obtains is superior to common product.
It is emphasized that the present invention has added micron order nuclear shell conductive polyaniline and nano level nuclear shell conductive polyaniline simultaneously; The particle of two kinds of different sizes can be realized orderly arrangement after the coating film forming, forms complete conductive network and helps realizing high electric conductivity.As shown in Figure 1: Fig. 1 is the arrangement synoptic diagram that coating of the present invention becomes electrically conductive polyaniline nucleocapsid composite particles in the paint film; After micron order electrically conductive polyaniline nucleocapsid composite particles is tightly packed; Nano-level conducting polyaniline nucleocapsid composite particles forms ordered arrangement again in its " space "; So just can more perfect conductive network be arranged, thereby obtain higher electric conductivity than the coating paint film (as shown in Figure 2) that adds single micron order nuclear shell conductive polyaniline.Coating of the present invention is realized ordered arrangement owing to the mutual extrusion effect between two kinds of different size nuclear shell conductive polyaniline particles than adding single nano level nuclear shell conductive polyaniline (as shown in Figure 3) more easily simultaneously.The preparation technology of preparation ratio nano level nuclear shell conductive polyaniline who considers the micron order nuclear shell conductive polyaniline again is simple, adds the nucleocapsid composite particles of two kinds of different sizes simultaneously and can more effectively control cost than adding single nano level nucleocapsid composite particles.
The one-tenth membrane matrix that the present invention uses is a water-base resin, does not contain or only contain a small amount of organic solvent, compares the advantage with environmental protection with the solvent-borne type product, and the water consumption substitution organic solvent can reduce production costs simultaneously.
To sum up, antistatic coating of the present invention have present conventional antistatic coating incomparable advantage, be a kind of product of high performance-price ratio of real environmental protection, compared with prior art, possess outstanding substantive distinguishing features and obvious improvement.
Description of drawings
Fig. 1 by coating of the present invention the arrangement synoptic diagram of electrically conductive polyaniline nucleocapsid composite particles in the one-tenth paint film;
Fig. 2 by the coating of the single micron order nuclear shell conductive polyaniline of interpolation the arrangement synoptic diagram of electrically conductive polyaniline nucleocapsid composite particles in the one-tenth paint film;
Fig. 3 by the coating of the single nano level nuclear shell conductive polyaniline of interpolation the arrangement synoptic diagram of electrically conductive polyaniline nucleocapsid composite particles in the one-tenth paint film;
Fig. 4 is transmission electron microscope (TEM) figure of nucleocapsid polyaniline particle, wherein, (A) is micron order nucleocapsid polyaniline, (B) is nano level nucleocapsid polyaniline.
Embodiment
Below in conjunction with embodiment the present invention is further described:
Embodiment 1: prepare a kind of nuclear shell conductive polyaniline aqueous antistatic coating
Step is following:
1. prepare micron order conductive polymers nucleocapsid composite particles earlier: 1.5g Vinylpyrrolidone polymer, 5g zero(ppm) water, 8g vinylbenzene, 80g ethanol, 0.1g Diisopropyl azodicarboxylate are joined stirring and dissolving in the there-necked flask, and reaction is 4 hours when being warming up to 70 ℃; Add the solution (being controlled at 10min adds) that 0.5g SSS, 1.5g water, 0.001g Potassium Persulphate and 20g ethanol are formed again, reaction continues to be gathered in 3 hours (vinylbenzene-SSS) microballoon.The 1g exsiccant is gathered (vinylbenzene-SSS) microballoon, 0.25g hydrochloric acid (wt=36%), 0.3g aniline monomer to join in the 50g water; Fully disperse the back to add the aqueous solution that 50g is dissolved with the 0.3g ammonium persulphate; Reaction 18h; Centrifugation is gathered (vinylbenzene-SSS)/polyaniline nucleocapsid micron particle, that is: (PS-PSS/PANI) composite particles after the drying.
2. refabrication nano-level conducting polyalcohol nucleocapsid composite particles: earlier the 0.3g sodium lauryl sulphate is dissolved in 86g zero(ppm) water and obtains the aqueous solution; Again 8g TEB 3K, 4g Bing Xisuandingzhi, 0.5g vinylformic acid, 0.3g n-hexadecane blended oil solution are added in the aqueous solution and stir, put in the ultrasonic cleaner that fills frozen water ultrasonic 30 minutes into.Be warmed up to 70 ℃, add Potassium Persulphate 0.2g, react and obtained the terpolymer resin miniemulsion in 4 hours; This terpolymer resin miniemulsion of 2g, 0.1g aniline and 0.1g hydrochloric acid (wt=36%) joined in the 100g water stir; Add the aqueous solution (30g) (being controlled at 15min drips) that is dissolved with the 0.1g ammonium persulphate, be reflected at and carry out 18h under ice bath, the nitrogen protection.The product purification is gathered (methyl methacrylate-butyl acrylate-vinylformic acid)/polyaniline core-shell nano, that is: P (MMA-BA-AA)/PANI composite particles.
3. composite: it is that dispersed with stirring evenly gets final product in 30% aqueous epoxy resin emulsion that nanometer P (the MMA-BA-AA)/PANI particle of micron PS-PSS/PANI particle and the aqueous epoxy resin emulsion quality 0.125% of aqueous epoxy resin emulsion quality 0.5% is joined solid content simultaneously.
Embodiment 2: prepare a kind of nuclear shell conductive polyaniline aqueous antistatic coating
Step is following:
1. prepare micron order conductive polymers nucleocapsid composite particles earlier: 3g Vinylpyrrolidone polymer, 20g zero(ppm) water, 15g vinylbenzene, 150g ethanol, 0.15g Diisopropyl azodicarboxylate are joined stirring and dissolving in the there-necked flask, and reaction is 8 hours when being warming up to 70 ℃; Add the solution (being controlled at 30min adds) that 2.5g SSS, 4g water, 0.001g Potassium Persulphate and 30g ethanol are formed again, reaction continues to be gathered in 5 hours (vinylbenzene-SSS) microballoon.The 1g exsiccant is gathered (vinylbenzene-SSS) microballoon, 0.25g hydrochloric acid (wt=36%), 1g aniline monomer to join in the 100g water; Fully disperse the back to add the aqueous solution that 50g is dissolved with the 2g ammonium persulphate; Reaction 24h; Centrifugation is gathered (vinylbenzene-SSS)/polyaniline nucleocapsid micron particle, that is: (PS-PSS/PANI) composite particles after the drying.
2. refabrication nano-level conducting polymer core shell particles: earlier the 0.5g sodium lauryl sulphate is dissolved in 86g zero(ppm) water and obtains the aqueous solution; Again 12g TEB 3K, 2g Bing Xisuandingzhi, 1g vinylformic acid, 0.6g n-hexadecane blended oil solution are added in the aqueous solution and stir, put in the ultrasonic cleaner that fills frozen water ultrasonic 30 minutes into.Be warmed up to 70 ℃, add Potassium Persulphate 0.4g, react and obtained the terpolymer resin miniemulsion in 6 hours; This terpolymer resin miniemulsion of 2g, 0.5g aniline and 0.5g hydrochloric acid (wt=36%) joined in the 150g water stir, add the aqueous solution (30g) (being controlled at 45min drips) that is dissolved with the 1g ammonium persulphate, be reflected at and carry out 24h under ice bath, the nitrogen protection.The product purification is gathered (methyl methacrylate-butyl acrylate-vinylformic acid)/polyaniline core-shell nano, that is: P (MMA-BA-AA)/PANI composite particles.
3. composite: it is to mix to be uniformly dispersed in 40% the water-borne acrylic resin emulsion to get final product that nanometer P (the MMA-BA-AA)/PANI particle of micron PS-PSS/PANI particle and the water-borne coatings resin emulsion quality 5% of water-borne coatings resin emulsion quality 20% is joined solid content simultaneously.
Embodiment 3: prepare a kind of nuclear shell conductive polyaniline aqueous antistatic coating
Step is following:
1. prepare micron order conductive polymers nucleocapsid composite particles earlier: 2g Vinylpyrrolidone polymer, 15g zero(ppm) water, 12g vinylbenzene, 120g ethanol, 0.12g Diisopropyl azodicarboxylate are joined stirring and dissolving in the there-necked flask, and reaction is 6 hours when being warming up to 70 ℃; Add the solution (being controlled at 20min adds) that 1.5g SSS, 3g water, 0.001g Potassium Persulphate and 25g ethanol are formed again, reaction continues to be gathered in 4 hours (vinylbenzene-SSS) microballoon.The 1g exsiccant is gathered (vinylbenzene-SSS) microballoon, 0.25g hydrochloric acid (wt=36%), 0.5g aniline monomer to join in the 80g water; Fully disperse the back to add the aqueous solution that 50g is dissolved with the 0.8g ammonium persulphate; Reaction 22h; Centrifugation is gathered (vinylbenzene-SSS)/polyaniline nucleocapsid micron particle, that is: (PS-PSS/PANI) composite particles after the drying.
2. refabrication nano-level conducting polymer core shell particles: earlier the 0.4g sodium lauryl sulphate is dissolved in 86g zero(ppm) water; Again 10g TEB 3K, 3g Bing Xisuandingzhi, 0.8g vinylformic acid, 0.45g n-hexadecane blended oil solution are added in the aqueous solution and stir, put in the ultrasonic cleaner that fills frozen water ultrasonic 30 minutes into.Be warmed up to 70 ℃, add Potassium Persulphate 0.3g, react and obtained the terpolymer resin miniemulsion in 5 hours; This terpolymer resin miniemulsion of 2g, 0.3g aniline and 0.2g hydrochloric acid (wt=36%) joined in the 130g water stir; Add the aqueous solution (30g) (being controlled at 25min drips) that is dissolved with the 0.7g ammonium persulphate, be reflected at and carry out 19h under ice bath, the nitrogen protection.The product purification is gathered (methyl methacrylate-butyl acrylate-vinylformic acid)/polyaniline core-shell nano, that is: P (MMA-BA-AA)/PANI composite particles.
3. composite: it is that dispersed with stirring evenly gets final product in 50% the aqueous polyurethane emulsion that nanometer P (the MMA-BA-AA)/PANI particle of micron PS-PSS/PANI particle and the aqueous polyurethane emulsion quality 0.5% of aqueous polyurethane emulsion quality 2% is joined solid content simultaneously.
Embodiment 4: prepare a kind of nuclear shell conductive polyaniline aqueous antistatic coating
Step is following:
1. prepare micron order conductive polymers nucleocapsid composite particles earlier: 2.8g Vinylpyrrolidone polymer, 15g zero(ppm) water, 10g vinylbenzene, 90g ethanol, 0.13g Diisopropyl azodicarboxylate are joined stirring and dissolving in the there-necked flask, and reaction is 4.5 hours when being warming up to 70 ℃; Add the solution (being controlled at 20min adds) that 1.5g SSS, 3g water, 0.001g Potassium Persulphate and 25g ethanol are formed again, reaction continues to be gathered in 4 hours (vinylbenzene-SSS) microballoon.The 1g exsiccant is gathered (vinylbenzene-SSS) microballoon, 0.25g hydrochloric acid (wt=36%), 0.8g aniline monomer to join in the 70g water; Fully disperse the back to add the aqueous solution that 50g is dissolved with the 1g ammonium persulphate; Reaction 23h; Centrifugation is gathered (vinylbenzene-SSS)/polyaniline nucleocapsid micron particle, that is: (PS-PSS/PANI) composite particles after the drying.
2. refabrication nano-level conducting polymer core shell particles: earlier the 0.35g sodium lauryl sulphate is dissolved in 86g zero(ppm) water; Again 9g TEB 3K, 4g Bing Xisuandingzhi, 1g vinylformic acid, 0.6g n-hexadecane blended oil solution are added in the aqueous solution and stir, put in the ultrasonic cleaner that fills frozen water ultrasonic 30 minutes into.Be warmed up to 70 ℃, add Potassium Persulphate 0.28g, react and obtained the terpolymer resin miniemulsion in 4.5 hours; This terpolymer resin miniemulsion of 2g, 0.2g aniline and 0.15g hydrochloric acid (wt=36%) joined in the 100g water stir; Add the aqueous solution (30g) (being controlled at 35min drips) that is dissolved with the 0.2g ammonium persulphate, be reflected at and carried out under ice bath, the nitrogen protection 19 hours.The product purification is gathered (methyl methacrylate-butyl acrylate-vinylformic acid)/polyaniline core-shell nano, that is: P (MMA-BA-AA)/PANI composite particles.
3. composite: it is that dispersed with stirring evenly gets final product in 60% the aqueous epoxy resin emulsion that nanometer P (the MMA-BA-AA)/PANI particle of micron PS-PSS/PANI particle and the aqueous epoxy resin emulsion quality 1.25% of aqueous epoxy resin emulsion quality 5% is joined solid content simultaneously.
Embodiment 5: prepare a kind of nuclear shell conductive polyaniline aqueous antistatic coating
Step is following:
1. prepare micron order conductive polymers nucleocapsid composite particles earlier: 2.4g Vinylpyrrolidone polymer, 9g zero(ppm) water, 14g vinylbenzene, 140g ethanol, 0.14g Diisopropyl azodicarboxylate are joined stirring and dissolving in the there-necked flask, and reaction is 6.5 hours when being warming up to 70 ℃; Add the solution (being controlled at 30min adds) that 0.8g SSS, 2.5g water, 0.001g Potassium Persulphate and 30g ethanol are formed again, reaction continues to be gathered in 5 hours (vinylbenzene-SSS) microballoon.The 1g exsiccant is gathered (vinylbenzene-SSS) microballoon, 0.25g hydrochloric acid (wt=36%), 0.6g aniline monomer to join in the 60g water; Fully disperse the back to add the aqueous solution that 50g is dissolved with the 0.6g ammonium persulphate; Reaction 21h; Centrifugation is gathered (vinylbenzene-SSS)/polyaniline nucleocapsid micron particle, that is: (PS-PSS/PANI) composite particles after the drying.
2. refabrication nano-level conducting polymer core shell particles: earlier the 0.3g sodium lauryl sulphate is dissolved in 86g zero(ppm) water; Again 11g TEB 3K, 3.5g Bing Xisuandingzhi, 0.55g vinylformic acid, 0.38g n-hexadecane blended oil solution are added in the aqueous solution and stir, put in the ultrasonic cleaner that fills frozen water ultrasonic 30 minutes into.Be warmed up to 70 ℃, add Potassium Persulphate 0.3g, react and obtained the terpolymer resin miniemulsion in 5 hours; This terpolymer resin miniemulsion of 2g, 0.33g aniline and 0.1g hydrochloric acid (wt=36%) joined in the 115g water stir; Add the aqueous solution (30g) (being controlled at 45min drips) that is dissolved with the 0.66g ammonium persulphate, be reflected at and carried out under ice bath, the nitrogen protection 20 hours.The product purification is gathered (methyl methacrylate-butyl acrylate-vinylformic acid)/polyaniline core-shell nano, that is: P (MMA-BA-AA)/PANI composite particles.
3. composite: it is that dispersed with stirring evenly gets final product in 70% the water-borne acrylic resin emulsion that nanometer P (the MMA-BA-AA)/PANI particle of micron PS-PSS/PANI particle and the water-borne acrylic resin quality of the emulsion 0.875% of water-borne acrylic resin quality of the emulsion 3.5% is joined solid content simultaneously.
Embodiment 6: prepare a kind of nuclear shell conductive polyaniline aqueous antistatic coating
Step is following:
1. prepare micron order conductive polymers nucleocapsid composite particles earlier: 1.8g Vinylpyrrolidone polymer, 16g zero(ppm) water, 13g vinylbenzene, 100g ethanol, 0.12g Diisopropyl azodicarboxylate are joined stirring and dissolving in the there-necked flask, and reaction is 7 hours when being warming up to 70 ℃; Add the solution (being controlled at 20min adds) that 1.8g SSS, 2.5g water, 0.001g Potassium Persulphate and 20g ethanol are formed again, reaction continues to be gathered in 5 hours (vinylbenzene-SSS) microballoon.The 1g exsiccant is gathered (vinylbenzene-SSS) microballoon, 0.25g hydrochloric acid (wt=36%), 0.9g aniline monomer to join in the 90g water; Fully disperse the back to add the aqueous solution that 50g is dissolved with the 0.9g ammonium persulphate; Reaction 20h; Centrifugation is gathered (vinylbenzene-SSS)/polyaniline nucleocapsid micron particle, that is: (PS-PSS/PANI) composite particles after the drying.
2. refabrication nano-level conducting polymer core shell particles: earlier the 0.43g sodium lauryl sulphate is dissolved in 86g zero(ppm) water; Again 9.5g TEB 3K, 4g Bing Xisuandingzhi, 0.7g vinylformic acid, 0.36g n-hexadecane blended oil solution are added in the aqueous solution and stir, put in the ultrasonic cleaner that fills frozen water ultrasonic 30 minutes into.Be warmed up to 70 ℃, add Potassium Persulphate 0.3g, react and obtained the terpolymer resin miniemulsion in 5.5 hours; This terpolymer resin miniemulsion of 2g, 0.22g aniline and 0.17g hydrochloric acid (wt=36%) joined in the 110g water stir; Add the aqueous solution (30g) (being controlled at 45min drips) that is dissolved with the 0.18g ammonium persulphate, be reflected at and carried out under ice bath, the nitrogen protection 23 hours.The product purification is gathered (methyl methacrylate-butyl acrylate-vinylformic acid)/polyaniline core-shell nano, that is: P (MMA-BA-AA)/PANI composite particles.
3. composite: it is that dispersed with stirring evenly gets final product in 80% the aqueous polyurethane emulsion that nanometer P (the MMA-BA-AA)/PANI particle of micron PS-PSS/PANI particle and the aqueous polyurethane emulsion quality 3.75% of aqueous polyurethane emulsion quality 15% is joined solid content simultaneously.
Embodiment 7: prepare a kind of nuclear shell conductive polyaniline aqueous antistatic coating
Step is following:
1. prepare micron order conductive polymers nucleocapsid composite particles earlier: 1.5g Vinylpyrrolidone polymer, 5g zero(ppm) water, 15g vinylbenzene, 120g ethanol, 0.1g Diisopropyl azodicarboxylate are joined stirring and dissolving in the there-necked flask, and reaction is 8 hours when being warming up to 70 ℃; Add the solution (being controlled at 30min adds) that 0.5g SSS, 1.5g water, 0.001g Potassium Persulphate and 20g ethanol are formed again, reaction continues to be gathered in 5 hours (vinylbenzene-SSS) microballoon.The 1g exsiccant is gathered (vinylbenzene-SSS) microballoon, 0.25g hydrochloric acid (wt=36%), 0.6g aniline monomer to join in the 100g water; Fully disperse the back to add the aqueous solution that 50g is dissolved with the 0.6g ammonium persulphate; Reaction 20h; Centrifugation is gathered (vinylbenzene-SSS)/polyaniline nucleocapsid micron particle, that is: (PS-PSS/PANI) composite particles after the drying.
2. refabrication nano-level conducting polymer core shell particles: earlier the 0.5g sodium lauryl sulphate is dissolved in 86g zero(ppm) water; Again 12g TEB 3K, 2g Bing Xisuandingzhi, 0.5g vinylformic acid, 0.6g n-hexadecane blended oil solution are added in the aqueous solution and stir, put in the ultrasonic cleaner that fills frozen water ultrasonic 30 minutes into.Be warmed up to 70 ℃, add Potassium Persulphate 0.4g, react and obtained the terpolymer resin miniemulsion in 4 hours; This terpolymer resin miniemulsion of 2g, 0.2g aniline and 0.1g hydrochloric acid (wt=36%) joined in the 150g water stir; Add the aqueous solution (30g) (being controlled at 45min drips) that is dissolved with the 0.2g ammonium persulphate, be reflected at and carried out under ice bath, the nitrogen protection 18 hours.The product purification is gathered (methyl methacrylate-butyl acrylate-vinylformic acid)/polyaniline core-shell nano, that is: P (MMA-BA-AA)/PANI composite particles.
3. composite: it is that dispersed with stirring evenly gets final product in 45% the aqueous epoxy resin emulsion that nanometer P (the MMA-BA-AA)/PANI particle of micron PS-PSS/PANI particle and the aqueous epoxy resin emulsion quality 2.5% of aqueous epoxy resin emulsion quality 10% is joined solid content simultaneously.
Embodiment 8: prepare a kind of nuclear shell conductive polyaniline aqueous antistatic coating
Step is following:
1. prepare micron order conductive polymers nucleocapsid composite particles earlier: 3g Vinylpyrrolidone polymer, 20g zero(ppm) water, 8g vinylbenzene, 150g ethanol, 0.15g Diisopropyl azodicarboxylate are joined stirring and dissolving in the there-necked flask, and reaction is 4 hours when being warming up to 70 ℃; Add the solution (being controlled at 10min adds) that 2.5g SSS, 4g water, 0.001g Potassium Persulphate and 30g ethanol are formed again, reaction continues to be gathered in 3 hours (vinylbenzene-SSS) microballoon.The 1g exsiccant is gathered (vinylbenzene-SSS) microballoon, 0.25g hydrochloric acid (wt=36%), 0.3g aniline monomer to join in the 50g water; Fully disperse the back to add the aqueous solution that 50g is dissolved with the 0.3g ammonium persulphate; Reaction 24h; Centrifugation is gathered (vinylbenzene-SSS)/polyaniline nucleocapsid micron particle, that is: (PS-PSS/PANI) composite particles after the drying.
2. refabrication nano-level conducting polymer core shell particles: earlier the 0.3g sodium lauryl sulphate is dissolved in 86g zero(ppm) water; Again 10g TEB 3K, 4g Bing Xisuandingzhi, 0.9g vinylformic acid, 0.3g n-hexadecane blended oil solution are added in the aqueous solution and stir, put in the ultrasonic cleaner that fills frozen water ultrasonic 30 minutes into.Be warmed up to 70 ℃, add Potassium Persulphate 0.25g, react and obtained the terpolymer resin miniemulsion in 6 hours; This terpolymer resin miniemulsion of 2g, 0.12g aniline and 0.12g hydrochloric acid (wt=36%) joined in the 100g water stir; Add the aqueous solution (30g) (being controlled at 35min drips) that is dissolved with the 0.12g ammonium persulphate, be reflected at and carried out under ice bath, the nitrogen protection 22 hours.The product purification is gathered (methyl methacrylate-butyl acrylate-vinylformic acid)/polyaniline core-shell nano, that is: P (MMA-BA-AA)/PANI composite particles.
3. composite: it is that dispersed with stirring evenly gets final product in 55% the aqueous epoxy resin emulsion that nanometer P (the MMA-BA-AA)/PANI particle of micron PS-PSS/PANI particle and the aqueous epoxy resin emulsion quality 1% of aqueous epoxy resin emulsion quality 3% is joined solid content simultaneously.
Embodiment 9: prepare a kind of nuclear shell conductive polyaniline aqueous antistatic coating
Step is following:
1. prepare micron order conductive polymers nucleocapsid composite particles earlier: 2.8g Vinylpyrrolidone polymer, 14g zero(ppm) water, 11.5g vinylbenzene, 95g ethanol, 0.1g Diisopropyl azodicarboxylate are joined stirring and dissolving in the there-necked flask, and reaction is 7 hours when being warming up to 70 ℃; Add the solution (being controlled at 25min adds) that 1.9g SSS, 4g water, 0.001g Potassium Persulphate and 28g ethanol are formed again, reaction continues to be gathered in 4 hours (vinylbenzene-SSS) microballoon.The 1g exsiccant is gathered (vinylbenzene-SSS) microballoon, 0.25g hydrochloric acid (wt=36%), 0.7g aniline monomer to join in the 80g water; Fully disperse the back to add the aqueous solution that 50g is dissolved with the 0.7g ammonium persulphate; Reaction 21h; Centrifugation is gathered (vinylbenzene-SSS)/polyaniline nucleocapsid micron particle, that is: (PS-PSS/PANI) composite particles after the drying.
2. prepare nano-level conducting polymer core shell particles: the 0.45g sodium lauryl sulphate is dissolved in 86g zero(ppm) water; Again 11.5g TEB 3K, 3.8g Bing Xisuandingzhi, 0.75g vinylformic acid, 0.39g n-hexadecane blended oil solution are added in the aqueous solution and stir, put in the ultrasonic cleaner that fills frozen water ultrasonic 30 minutes into.Be warmed up to 70 ℃, add Potassium Persulphate 0.2g, react and obtained the terpolymer resin miniemulsion in 4 hours; 2g terpolymer resin miniemulsion, 0.3g aniline and 0.27g hydrochloric acid (wt=36%) joined in the 100g water stir; Add the aqueous solution (30g) (being controlled at 35min drips) that is dissolved with the 0.4g ammonium persulphate, be reflected at and carry out 21h under ice bath, the nitrogen protection.The product purification is gathered (methyl methacrylate-butyl acrylate-vinylformic acid)/polyaniline core-shell nano, that is: P (MMA-BA-AA)/PANI.
3. composite: it is that dispersed with stirring evenly gets final product in 50% aqueous polyurethane emulsion that nanometer P (the MMA-BA-AA)/PANI particle of micron PS-PSS/PANI particle and the aqueous polyurethane emulsion quality 0.6% of aqueous polyurethane emulsion quality 1% is joined solid content simultaneously.
Claims (1)
1. nuclear shell conductive polyaniline aqueous antistatic coating; It is characterized in that: form: micron order conductive polymers nucleocapsid composite particles by following; Nano-level conducting polyalcohol nucleocapsid composite particles, the water-borne coatings resin emulsion, wherein; The quality of micron order conductive polymers nucleocapsid composite particles accounts for 0.5～20% of water-borne coatings resin emulsion quality, and the quality of nano-level conducting polyalcohol nucleocapsid composite particles accounts for 0.125～5% of water-borne coatings resin emulsion quality;
The kernel of said micron order conductive polymers nucleocapsid composite particles is vinylbenzene-SSS multipolymer; The kernel of nano-level conducting polyalcohol nucleocapsid composite particles is methyl methacrylate-butyl acrylate-vinylformic acid terpolymer resin; The conductive polymers shell is an electrically conductive polyaniline;
Said water-borne coatings resin emulsion is aqueous epoxy resin emulsion or water-borne acrylic resin emulsion or aqueous polyurethane resin emulsion;
The preparation method of said nuclear shell conductive polyaniline aqueous antistatic coating is: may further comprise the steps:
(1) preparation micron order conductive polymers nucleocapsid composite particles: 1.5～3 parts of Vinylpyrrolidone polymers, 5～20 parts of zero(ppm) water, 8～15 parts of vinylbenzene, 80～150 parts of ethanol and 0.1～0.15 part of Diisopropyl azodicarboxylate are joined stirring and dissolving in the there-necked flask, and reaction is 4～8 hours when being warming up to 70 ℃; Add 0.5～2.5 part of SSS, 1.5～4 parts of water, 0.001 part of Potassium Persulphate and 20～30 parts of solution that ethanol is formed again, continue reaction 3～5 hours, obtain PS-SSS microballoon; Getting the PS-SSS microballoon of 1 part of purge drying, 0.25 part of hydrochloric acid, 0.3～1 part of aniline monomer then joins in 50～100 parts of water; After fully disperseing; Join in 50 parts of aqueous solution that are dissolved with 0.3～2 part of ammonium persulphate reaction 18～24h, centrifugation; Obtain PS-SSS/polyaniline nucleocapsid micron particle, that is: PS-PSS/PANI composite particles after the drying;
(2) preparation nano-level conducting polyalcohol nucleocapsid composite particles: 0.3～0.5 part of sodium lauryl sulphate is dissolved in 86 parts of zero(ppm) water obtains the aqueous solution earlier; Again 8～12 parts of TEB 3Ks, 4～2 parts of Bing Xisuandingzhis, 0.5～1 part of vinylformic acid and 0.3～0.6 part of n-hexadecane are mixed and oil solution be added to and stir in the aqueous solution, put in the ultrasonic cleaner that fills frozen water ultrasonic 30 minutes into; Be warmed up to 70 ℃ then, add 0.2～0.4 part of Potassium Persulphate, react and obtained the terpolymer resin miniemulsion in 4～6 hours; 2 parts of these terpolymer resin miniemulsions, 0.1～0.5 part of aniline and 0.1～0.5 part of hydrochloric acid joined in 100～150 parts of water stir; Join again in 30 parts of aqueous solution that are dissolved with 0.1～1 part of ammonium persulphate; Reaction is 18～24 hours under ice bath, nitrogen protection; The product that obtains is purified, obtain polymethylmethacrylate-Bing Xisuandingzhi-vinylformic acid/polyaniline nano core-shell particles, that is: the PMMA-BA-AA/PANI composite particles;
(3) composite: micron order conductive polymers nucleocapsid composite particles and nano-level conducting polyalcohol nucleocapsid composite particles are joined in the water-borne coatings resin emulsion simultaneously, and dispersed with stirring is even, has both got nuclear shell conductive polyaniline aqueous antistatic coating; Wherein, the quality of micron order conductive polymers nucleocapsid composite particles accounts for 0.5～20% of water-borne coatings resin emulsion quality, and the quality of nano-level conducting polyalcohol nucleocapsid composite particles accounts for 0.125～5% of water-borne coatings resin emulsion quality.
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| CN104098767B (en) * | 2014-06-11 | 2016-06-08 | 扬州大学 | The preparation method of polyaniline and ring oxygen grafted and mofiied acrylic ester mixture |
| CN104293075B (en) * | 2014-10-28 | 2016-08-24 | 张海红 | A kind of modified polyphenyl amine type anticorrosive paint and preparation method thereof |
| CN107418415B (en) * | 2017-09-25 | 2019-10-01 | 淄博职业学院 | A kind of preparation process of business administration equipment anticorrosion coating |
| CN109468007A (en) * | 2018-11-13 | 2019-03-15 | 广东顺德三和化工有限公司 | A kind of antistatic interior wall coating and preparation method thereof |
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