CN101942254B - Aqueous conducting anti-corrosive paint containing nano core-shell structure polypyrrole - Google Patents
Aqueous conducting anti-corrosive paint containing nano core-shell structure polypyrrole Download PDFInfo
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- CN101942254B CN101942254B CN2010102969702A CN201010296970A CN101942254B CN 101942254 B CN101942254 B CN 101942254B CN 2010102969702 A CN2010102969702 A CN 2010102969702A CN 201010296970 A CN201010296970 A CN 201010296970A CN 101942254 B CN101942254 B CN 101942254B
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Abstract
The invention discloses an aqueous conducting anti-corrosive paint containing nano core-shell structure polypyrrole, which comprises nano core-shell structure polypyrrole compound particles and aqueous resin emulsion, wherein the nano core-shell structure polypyrrole accounts for 5.5-25 wt% of aqueous resin emulsion. When in use, the aqueous conducting anti-corrosive paint containing nano core-shell structure polypyrrole is applied or sprayed on the metal surface which is processed by oil removal and anti-corrosive treatment, the coating thickness is controlled at 20-200 mu m, and the coating is cured at room temperature. The nano core-shell polypyrrole compound particles are synthesized by using a micro emulsion method. The method has the advantages of simple experimental apparatus, low energy consumption and easy operation; and the prepared nano particles have uniform and controllable particle size. Compared with the common paint, the aqueous conducting anti-corrosive paint has incomparable advantages and high application value, and is beneficial to market popularization.
Description
Technical field
The present invention relates to a kind of waterborne conductive protective system that contains nano core-shell structure polypyrrole.
Background technology
1977, Heeger, discoveries such as MacDiarmid and Bai Chuanying tree, the adulterated polyacetylene film of arsenic pentafluoride or iodine has metallic conductivity, and specific conductivity reaches 103Scm
-1, the traditional concept that polymkeric substance is generally isolator has been broken in this discovery, causes the interesting basic science problem of a series of relevant conductive polymers structures and character.Conductive polymers is in wide application prospects in aspect such as electrode materials, modified electrode and the enzyme electrodes of chemical power source, electrochromism demonstration, electrostatic shielding in addition, thereby excited the research boom of conductive polymers in the world wide.1979, American I BM company prepared specific conductivity up to 100Scm with electrochemically oxidative polymerization
-1The electric polypyrrole film.Polypyrrole is prone to advantage such as synthetic, that electric conductivity is high, stability is better and becomes one of emphasis of studying in the conducting polymer field because of having, and develops to the industrial application direction gradually.
The loss that the annual metallic corrosion in the whole world causes is huge, has statistical figure to show, global annual metallic corrosion total amount reaches the 20%-40% of metal output, about 1,000 hundred million yuan of financial loss.And the loss that causes because of static that relates to more than ten industry of u. s. published in the recent period is just up to more than 200 hundred million dollars.And use coating that metal or electronic component are carried out the effective means the most that the surface-coated processing is minimizing metallic corrosion, reduction static hazard.
At present, be main still mainly to the protection of hardware, and mostly current effective anti-corrosion of metal pigment is sexavalence chromium compounds and plumbiferous compound to apply protective system, wherein the sexavalence chromium compounds is a carcinogenic substance, lead also is the heavy metal of serious environment pollution.And electric polypyrrole has electroconductibility as metal, can make the metallic surface active passivation, and the heavy metal that can be used for substituting in the coating plays preservative activity.Therefore to be expected be environmentally acceptable high-efficiency anticorrosive paint of new generation to electric polypyrrole.
Yet, be generally black powder according to the electric polypyrrole of traditional method preparation, make with the polypyrrole to be the difficult toning of coating of conductive filler material.In addition, because the big conjugated in the linear molecule chain makes polypyrrole have extremely strong rigidity; Polypyrrole can not can not dissolve in fusion, and this makes it be difficult to machine-shaping, the also non-constant of mechanical property; And if electrically conducting coating is made as water-borne coatings, then can be very unstable, very easily precipitate.
In sum, there are many weak points in prior art, and preparing the waterborne conductive protective system that a kind of polypyrrole content is high, chemical compatibility is good, electric conductivity is high becomes problem demanding prompt solution.
Summary of the invention
To above-mentioned prior art, the invention provides a kind of waterborne conductive protective system that contains nano core-shell structure polypyrrole, and preparation method thereof.Utilize the waterborne conductive protective system of this method preparation to have advantages such as chemical compatibility is good, electric conductivity is high, preservative effect is good.
The present invention realizes through following technical scheme:
A kind of waterborne conductive protective system that contains nano core-shell structure polypyrrole; Be composed of the following components: nano core-shell structure polypyrrole composite particles and resin aqueous emulsion; Wherein, nano core-shell structure polypyrrole accounts for 5.5%～25% of resin aqueous emulsion quality.
Preferably, nano core-shell structure polypyrrole accounts for 5.5%～8.5% o'clock of resin aqueous emulsion quality, and preservative effect is best.
Preferably, nano core-shell structure polypyrrole accounts for 6.4%～15% o'clock of resin aqueous emulsion quality, and conductivity is good, can be used as antistatic coating.
The kernel of said nano core-shell structure polypyrrole composite particles is an iodine dopen Nano electric polypyrrole, and the shell of electric polypyrrole composite particles is polymethylmethacrylate (PMMA).
Said water-borne coatings resin emulsion is that solid content is 40%～80% water-borne acrylic resin emulsion.
A kind of preparation method who contains the waterborne conductive protective system of nano core-shell structure polypyrrole may further comprise the steps:
(1) nano core-shell structure polypyrrole is synthetic:
1. at room temperature in there-necked flask, add zero(ppm) water, cats product cetyl trimethylammonium bromide (CTAB) and cosurfactant Pentyl alcohol successively, and magnetic agitation forms the micellar solution of tensio-active agent;
2. pyrrole monomer (Py) is added drop-wise in the above-mentioned micellar solution that configures;
3. in there-necked flask, add iodine;
4. previously prepd is dissolved in the FeCl of zero(ppm) water
3Dropwise splash in the there-necked flask, at room temperature, system is carried out magnetic agitation, after 3 hours, pyrroles's chemical oxidising polymerisation is accomplished in micella;
5. in there-necked flask, add monomers methyl methacrylate (MMA), and temperature is risen to 70 ℃ of heating in water bath;
6. the Potassium Persulphate for preparing (KPS) solution is added drop-wise in the system with constant pressure funnel, 70 ℃ of isothermal reaction 3h, promptly being able to iodine doping polypyrrole is the nano core-shell structure polypyrrole of shell for nuclear, polymethylmethacrylate;
(2) composite: behind above-mentioned nano core-shell structure polypyrrole washing whiz; Be added in the water-borne coatings resin emulsion; Dispersed with stirring is even; Promptly get the waterborne conductive protective system of nano core-shell structure polypyrrole, wherein, nano core-shell structure polypyrrole accounts for 5.5%～25% of water-borne coatings resin solution quality.
In the said step (1), cats product cetyl trimethylammonium bromide (CTAB) is 0.034～0.068 with the mass ratio of zero(ppm) water; The mass ratio of cosurfactant Pentyl alcohol and zero(ppm) water is 0.02～0.04; The mass ratio of pyrrole monomer and zero(ppm) water is 0.01～0.03; The mass ratio of pyrrole monomer and MMA MONOMER is 0.40～0.67; The mass ratio of doping agent elemental iodine and pyrrole monomer is 0.3～0.4; Oxygenant FeCl
3With the mass ratio of pyrrole monomer be 3.9～6.2; The mass ratio of oxygenant Potassium Persulphate and TEB 3K is 0.04～0.07.
A kind of method of use that contains the waterborne conductive protective system of nano core-shell structure polypyrrole; For: the waterborne conductive protective system of nano core-shell structure polypyrrole is applied or is sprayed on the metallic surface through oil removing and antirust processing; Coat-thickness is controlled at 20～200 μ m, and self-vulcanizing gets final product.
Waterborne conductive protective system of the present invention has excellent in chemical consistency, high electric conductivity, can effectively slow down corrosion of metal simultaneously, is a kind of novel environment friendly conductive nano protective system.The nano core-shell polypyrrole of the present invention's preparation has intact globosity, and its shell is about 10nm, and interior nuclear diameter is 50nm～70nm.Adopt the waterborne conductive protective system of the present invention's preparation, the content of nano core-shell structure polypyrrole accounts for 5.5% of resin aqueous emulsion quality～8.5% o'clock, and preservative effect is best.Adopt the waterborne conductive protective system of the present invention's preparation, accounting for the resin aqueous emulsion quality at the content of nano core-shell structure polypyrrole is 6.4%～15% o'clock, and conductivity is good, can be used as antistatic coating.
It is emphasized that the present invention has realized the nucleocapsid modification of polypyrrole, and carried out the iodine doping.The contriver has successfully synthesized the nanometer shell of polymethylmethacrylate on the nanometer polypyrrole surface, make the polypyrrole conductive filler material have excellent comprehensive performances.Plasticity insulating polymer polymethylmethacrylate on polypyrrole surface makes polypyrrole have good thermoplasticity and snappiness, with matrix resin better consistency is arranged.Because the shell polymkeric substance as thin as a wafer, the swelling action of polymkeric substance makes the polypyrrole molecular chain partly to swell in the matrix resin, forms conductive network.Therefore the existence of shell insulating polymer polymethylmethacrylate does not influence the conductive capability of polypyrrole.And the electric conductivity of iodine doping also raising nanometer polypyrrole.As thin as a wafer existence and the swelling action of polymkeric substance of nanoshell polymer can more help coating toning in use so that the color of intrinsic polypyrrole is thin out in addition.
The nano core-shell polypyrrole composite particles of the present invention's preparation adopts microemulsion method synthetic, and this method experimental installation is simple, and energy consumption is low, processing ease, and the nano particle diameter homogeneous and controllable of preparation.
The filmogen that the present invention uses is a resin aqueous emulsion, and it only contains a spot of organic solvent, compares the advantage with tangible environmental protection with the solvent-borne type product, can reduce production costs with water to replace organic solvent simultaneously.
In sum, the waterborne conductive protective system of the present invention's preparation has incomparable advantage with respect to common coating, has very high using value, and marketing is highly advantageous to.
Description of drawings
Fig. 1 is the transmission electron microscope photo of the prepared electric polypyrrole kernel of the present invention.
Fig. 2 is the ESEM picture of the prepared electric polypyrrole kernel of the present invention.
Fig. 3 is the transmission electron microscope photo of the prepared electric polypyrrole composite particles with nucleocapsid structure of the present invention.
Fig. 4 is the stereoscan photograph of the prepared electric polypyrrole composite particles with nucleocapsid structure of the present invention.
Embodiment
Below in conjunction with embodiment the present invention is further described:
Embodiment 1: prepare a kind of waterborne conductive protective system that contains nano core-shell structure polypyrrole
Step is following:
(1) preparation nano level iodine doping polypyrrole:
1. at room temperature in there-necked flask, add zero(ppm) water 200g, cats product cetyl trimethylammonium bromide (CTAB) 10.2g, cosurfactant Pentyl alcohol 6g, and magnetic agitation forms the micellar solution of tensio-active agent;
2. the 4g pyrrole monomer is added drop-wise in the there-necked flask, and continues magnetic agitation, form the micellar solution of the tensio-active agent that contains pyrrole monomer;
3. in there-necked flask, add the 1.4g elemental iodine, and continue magnetic agitation;
4. in there-necked flask, slowly drip 20.4g FeCl
3(being dissolved in the 40g zero(ppm) water), magnetic agitation 3h can obtain iodine dopen Nano polypyrrole, its transmission electron microscope photo such as Fig. 1, stereoscan photograph such as Fig. 2.We can see that the diameter of prepared nanometer polypyrrole is about 40nm～50nm through photo, and pattern is spherical.
5. in there-necked flask, add TEB 3K (MMA) 7.41g, and be warmed up to 70 ℃ of heating in water bath;
6. slowly be added drop-wise to the Potassium Persulphate that configures (KPS) 0.41g (being dissolved in the 5g water) solution in the there-necked flask; 70 ℃ of isothermal reaction 3h; Promptly being able to polypyrrole is the nano core-shell structure polypyrrole composite particles of shell for nuclear, polymethylmethacrylate; Its transmission electron microscope photo such as Fig. 3, stereoscan photograph such as Fig. 4.We can see through photo, and the interior nuclear diameter of nano core-shell structure polypyrrole is about 40nm～50nm, and outer casing thickness is about 20nm.With its whiz, subsequent use.
(2) the waterborne conductive protective system is composite: 5.5% the nano core-shell structure polypyrrole composite particles that will account for the resin aqueous emulsion quality joins (solid content is 40%) in the aqueous acroleic acid resin emulsion; And stir, promptly get the waterborne conductive protective system that contains nano core-shell structure polypyrrole.
During use, the waterborne conductive protective system of the above-mentioned nano core-shell structure polypyrrole for preparing is applied or is sprayed on through the metallic surface of oil removing and antirust processing, coat-thickness is controlled at 20～200 μ m, self-vulcanizing.
Embodiment 2: prepare a kind of waterborne conductive protective system that contains nano core-shell structure polypyrrole
Step is following:
(1) preparation nano level iodine doping polypyrrole:
1. at room temperature in there-necked flask, add zero(ppm) water 200g, cats product cetyl trimethylammonium bromide (CTAB) 6.8g, cosurfactant Pentyl alcohol 4g, and magnetic agitation forms the micellar solution of tensio-active agent;
2. the 2g pyrrole monomer is added drop-wise in the there-necked flask, and continues magnetic agitation, form the micellar solution of the tensio-active agent that contains pyrrole monomer;
3. in there-necked flask, add the 0.6g elemental iodine, and continue magnetic agitation;
4. in there-necked flask, slowly drip 7.8g FeCl
3(being dissolved in the 40g zero(ppm) water), magnetic agitation 3h can obtain iodine dopen Nano polypyrrole.
5. in there-necked flask, add TEB 3K (MMA) 5g, and be warmed up to 70 ℃ of heating in water bath;
6. slowly be added drop-wise to the Potassium Persulphate that configures (KPS) 0.2g (being dissolved in the 5g water) solution in the there-necked flask; 70 ℃ of isothermal reaction 3h; Promptly being able to polypyrrole is the nano core-shell structure polypyrrole of shell for nuclear, polymethylmethacrylate, with its whiz, subsequent use.
(2) the waterborne conductive protective system is composite: 15.25% the nano core-shell structure polypyrrole composite particles that will account for the resin aqueous emulsion quality joins (solid content is 60%) in the aqueous acroleic acid resin emulsion; And stir, promptly get the waterborne conductive protective system that contains nano core-shell structure polypyrrole.
During use, the waterborne conductive protective system of the above-mentioned nano core-shell structure polypyrrole for preparing is applied or is sprayed on through the metallic surface of oil removing and antirust processing, coat-thickness is controlled at 20～200 μ m, self-vulcanizing.
Embodiment 3: prepare a kind of waterborne conductive protective system that contains nano core-shell structure polypyrrole
Step is following:
(1) preparation nano level iodine doping polypyrrole:
1. at room temperature in there-necked flask, add zero(ppm) water 200g, cats product cetyl trimethylammonium bromide (CTAB) 13.6g, cosurfactant Pentyl alcohol 8g, and magnetic agitation forms the micellar solution of tensio-active agent;
2. the 6g pyrrole monomer is added drop-wise in the there-necked flask, and continues magnetic agitation, form the micellar solution of the tensio-active agent that contains pyrrole monomer;
3. in there-necked flask, add the 2.4g elemental iodine, and continue magnetic agitation;
4. in there-necked flask, slowly drip 37.2g FeCl
3(being dissolved in the 40g zero(ppm) water), magnetic agitation 3h can obtain iodine dopen Nano polypyrrole.
5. in there-necked flask, add TEB 3K (MMA) 8.96g, and be warmed up to 70 ℃ of heating in water bath;
6. slowly be added drop-wise to the Potassium Persulphate that configures (KPS) 0.63g (being dissolved in the 5g water) solution in the there-necked flask; 70 ℃ of isothermal reaction 3h; Promptly being able to polypyrrole is the nano core-shell structure polypyrrole of shell for nuclear, polymethylmethacrylate, with its whiz, subsequent use.
(2) the waterborne conductive protective system is composite: 25% the nano core-shell structure polypyrrole composite particles that will account for the resin aqueous emulsion quality joins (solid content is 80%) in the aqueous acroleic acid resin emulsion; And stir, promptly get the waterborne conductive protective system that contains nano core-shell structure polypyrrole.
During use, the waterborne conductive protective system of the above-mentioned nano core-shell structure polypyrrole for preparing is applied or is sprayed on through the metallic surface of oil removing and antirust processing, coat-thickness is controlled at 20～200 μ m, self-vulcanizing.
Embodiment 4: prepare a kind of waterborne conductive protective system that contains nano core-shell structure polypyrrole
Step is following:
(1) preparation nano level iodine doping polypyrrole:
1. at room temperature in there-necked flask, add zero(ppm) water 200g, cats product cetyl trimethylammonium bromide (CTAB) 6.8g, cosurfactant Pentyl alcohol 4g, and magnetic agitation forms the micellar solution of tensio-active agent;
2. the 6g pyrrole monomer is added drop-wise in the there-necked flask, and continues magnetic agitation, form the micellar solution of the tensio-active agent that contains pyrrole monomer;
3. in there-necked flask, add the 2.4g elemental iodine, and continue magnetic agitation;
4. in there-necked flask, slowly drip 37.2g FeCl
3(being dissolved in the 40g zero(ppm) water), magnetic agitation 3h can obtain iodine dopen Nano polypyrrole.
5. in there-necked flask, add TEB 3K (MMA) 15g, and be warmed up to 70 ℃ of heating in water bath;
6. slowly be added drop-wise to the Potassium Persulphate that configures (KPS) 1.05g (being dissolved in the 5g water) solution in the there-necked flask; 70 ℃ of isothermal reaction 3h; Promptly being able to polypyrrole is the nano core-shell structure polypyrrole of shell for nuclear, polymethylmethacrylate, with its whiz, subsequent use.
(2) the waterborne conductive protective system is composite: 5.5% the nano core-shell structure polypyrrole composite particles that will account for the resin aqueous emulsion quality joins (solid content 40%) in the water-borne acrylic resin emulsion; And stir, promptly get the waterborne conductive protective system that contains nano core-shell structure polypyrrole.
During use, the waterborne conductive protective system of the above-mentioned nano core-shell structure polypyrrole for preparing is applied or is sprayed on through the metallic surface of oil removing and antirust processing, coat-thickness is controlled at 20～200 μ m, self-vulcanizing.
Embodiment 5: prepare a kind of waterborne conductive protective system that contains nano core-shell structure polypyrrole
Step is following:
(1) preparation nano level iodine doping polypyrrole:
1. at room temperature in there-necked flask, add zero(ppm) water 200g, cats product cetyl trimethylammonium bromide (CTAB) 10.2g, cosurfactant Pentyl alcohol 8g, and magnetic agitation forms the micellar solution of tensio-active agent;
2. the 2g pyrrole monomer is added drop-wise in the there-necked flask, and continues magnetic agitation, form the micellar solution of the tensio-active agent that contains pyrrole monomer;
3. in there-necked flask, add the 0.7g elemental iodine, and continue magnetic agitation;
4. in there-necked flask, slowly drip 7.8g FeCl
3(being dissolved in the 40g zero(ppm) water), magnetic agitation 3h can obtain iodine dopen Nano polypyrrole.
5. in there-necked flask, add TEB 3K (MMA) 3.71g, and be warmed up to 70 ℃ of heating in water bath;
6. slowly be added drop-wise to the Potassium Persulphate that configures (KPS) 0.15g (being dissolved in the 5g water) solution in the there-necked flask; 70 ℃ of isothermal reaction 3h; Promptly being able to polypyrrole is the nano core-shell structure polypyrrole of shell for nuclear, polymethylmethacrylate, with its whiz, subsequent use.
(2) the waterborne conductive protective system is composite: 15.25% the nano core-shell structure polypyrrole composite particles that will account for the resin aqueous emulsion quality joins (solid content 40%) in the water-borne acrylic resin emulsion; And stir, promptly get the waterborne conductive protective system that contains nano core-shell structure polypyrrole.
During use, the waterborne conductive protective system of the above-mentioned nano core-shell structure polypyrrole for preparing is applied or is sprayed on through the metallic surface of oil removing and antirust processing, coat-thickness is controlled at 20～200 μ m, self-vulcanizing.
Embodiment 6: prepare a kind of waterborne conductive protective system that contains nano core-shell structure polypyrrole
Step is following:
(1) preparation nano level iodine doping polypyrrole:
1. at room temperature in there-necked flask, add zero(ppm) water 200g, cats product cetyl trimethylammonium bromide (CTAB) 13.6g, cosurfactant Pentyl alcohol 6g, and magnetic agitation forms the micellar solution of tensio-active agent;
2. the 4g pyrrole monomer is added drop-wise in the there-necked flask, and continues magnetic agitation, form the micellar solution of the tensio-active agent that contains pyrrole monomer;
3. in there-necked flask, add the 1.2g elemental iodine, and continue magnetic agitation;
4. in there-necked flask, slowly drip 24.8g FeCl
3(being dissolved in the 40g zero(ppm) water), magnetic agitation 3h can obtain iodine dopen Nano polypyrrole.
5. in there-necked flask, add TEB 3K (MMA) 7.41g, and be warmed up to 70 ℃ of heating in water bath;
6. slowly be added drop-wise to the Potassium Persulphate that configures (KPS) 0.52g (being dissolved in the 5g water) solution in the there-necked flask; 70 ℃ of isothermal reaction 3h; Promptly being able to polypyrrole is the nano core-shell structure polypyrrole of shell for nuclear, polymethylmethacrylate, with its whiz, subsequent use.
(2) the waterborne conductive protective system is composite: 25% the nano core-shell structure polypyrrole composite particles that will account for the resin aqueous emulsion quality joins (solid content 80%) in the water-borne acrylic resin emulsion; And stir, promptly get the waterborne conductive protective system that contains nano core-shell structure polypyrrole.
During use, the waterborne conductive protective system of the above-mentioned nano core-shell structure polypyrrole for preparing is applied or is sprayed on through the metallic surface of oil removing and antirust processing, coat-thickness is controlled at 20～200 μ m, self-vulcanizing.
Embodiment 7: prepare a kind of waterborne conductive protective system that contains nano core-shell structure polypyrrole
Step is following:
(1) preparation nano level iodine doping polypyrrole:
1. at room temperature in there-necked flask, add zero(ppm) water 200g, cats product cetyl trimethylammonium bromide (CTAB) 6.8g, cosurfactant Pentyl alcohol 8g, and magnetic agitation forms the micellar solution of tensio-active agent;
2. the 4g pyrrole monomer is added drop-wise in the there-necked flask, and continues magnetic agitation, form the micellar solution of the tensio-active agent that contains pyrrole monomer;
3. in there-necked flask, add the 1.2g elemental iodine, and continue magnetic agitation;
4. in there-necked flask, slowly drip 20.4g FeCl
3(being dissolved in the 40g zero(ppm) water), magnetic agitation 3h can obtain iodine dopen Nano polypyrrole.
5. in there-necked flask, add TEB 3K (MMA) 5.97g, and be warmed up to 70 ℃ of heating in water bath;
6. slowly be added drop-wise to the Potassium Persulphate that configures (KPS) 0.24g (being dissolved in the 5g water) solution in the there-necked flask; 70 ℃ of isothermal reaction 3h; Promptly being able to polypyrrole is the nano core-shell structure polypyrrole of shell for nuclear, polymethylmethacrylate, with its whiz, subsequent use.
(2) the waterborne conductive protective system is composite: 25% the nano core-shell structure polypyrrole composite particles that will account for the resin aqueous emulsion quality joins (solid content 40%) in the water-borne acrylic resin emulsion; And stir, promptly get the waterborne conductive protective system that contains nano core-shell structure polypyrrole.
During use, the waterborne conductive protective system of the above-mentioned nano core-shell structure polypyrrole for preparing is applied or is sprayed on through the metallic surface of oil removing and antirust processing, coat-thickness is controlled at 20～200 μ m, self-vulcanizing.
Embodiment 8: prepare a kind of waterborne conductive protective system that contains nano core-shell structure polypyrrole
Step is following:
(1) preparation nano level iodine doping polypyrrole:
1. at room temperature in there-necked flask, add zero(ppm) water 200g, cats product cetyl trimethylammonium bromide (CTAB) 10.2g, cosurfactant Pentyl alcohol 6g, and magnetic agitation forms the micellar solution of tensio-active agent;
2. the 2g pyrrole monomer is added drop-wise in the there-necked flask, and continues magnetic agitation, form the micellar solution of the tensio-active agent that contains pyrrole monomer;
3. in there-necked flask, add the 0.8g elemental iodine, and continue magnetic agitation;
4. in there-necked flask, slowly drip 7.8g FeCl
3(being dissolved in the 40g zero(ppm) water), magnetic agitation 3h can obtain iodine dopen Nano polypyrrole.
5. in there-necked flask, add TEB 3K (MMA) 2.99g, and be warmed up to 70 ℃ of heating in water bath;
6. slowly be added drop-wise to the Potassium Persulphate that configures (KPS) 0.21g (being dissolved in the 5g water) solution in the there-necked flask; 70 ℃ of isothermal reaction 3h; Promptly being able to polypyrrole is the nano core-shell structure polypyrrole of shell for nuclear, polymethylmethacrylate, with its whiz, subsequent use.
(2) the waterborne conductive protective system is composite: 5.5% the nano core-shell structure polypyrrole composite particles that will account for the resin aqueous emulsion quality joins (solid content 80%) in the aqueous acroleic acid resin emulsion; And stir, promptly get the waterborne conductive protective system that contains nano core-shell structure polypyrrole.
During use, the waterborne conductive protective system of the above-mentioned nano core-shell structure polypyrrole for preparing is applied or is sprayed on through the metallic surface of oil removing and antirust processing, coat-thickness is controlled at 20～200 μ m, self-vulcanizing.
Embodiment 9: prepare a kind of waterborne conductive protective system that contains nano core-shell structure polypyrrole
Step is following:
(1) preparation nano level iodine doping polypyrrole:
1. at room temperature in there-necked flask, add zero(ppm) water 200g, cats product cetyl trimethylammonium bromide (CTAB) 13.6g, cosurfactant Pentyl alcohol 4g, and magnetic agitation forms the micellar solution of tensio-active agent;
2. the 6g pyrrole monomer is added drop-wise in the there-necked flask, and continues magnetic agitation, form the micellar solution of the tensio-active agent that contains pyrrole monomer;
3. in there-necked flask, add the 2.1g elemental iodine, and continue magnetic agitation;
4. in there-necked flask, slowly drip 30.6g FeCl
3(being dissolved in the 40g zero(ppm) water), magnetic agitation 3h can obtain iodine dopen Nano polypyrrole.
5. in there-necked flask, add TEB 3K (MMA) 15g, and be warmed up to 70 ℃ of heating in water bath;
6. slowly be added drop-wise to the Potassium Persulphate that configures (KPS) 0.83g (being dissolved in the 5g water) solution in the there-necked flask; 70 ℃ of isothermal reaction 3h; Promptly being able to polypyrrole is the nano core-shell structure polypyrrole of shell for nuclear, polymethylmethacrylate, with its whiz, subsequent use.
(2) the waterborne conductive protective system is composite: 8.5% the nano core-shell structure polypyrrole composite particles that will account for the resin aqueous emulsion quality joins (solid content 50%) in the aqueous acroleic acid resin emulsion; And stir, promptly get the waterborne conductive protective system that contains nano core-shell structure polypyrrole.
During use, the waterborne conductive protective system of the above-mentioned nano core-shell structure polypyrrole for preparing is applied or is sprayed on through the metallic surface of oil removing and antirust processing, coat-thickness is controlled at 20～200 μ m, self-vulcanizing.
Embodiment 10: prepare a kind of waterborne conductive protective system that contains nano core-shell structure polypyrrole
Step is following:
(1) preparation nano level iodine doping polypyrrole:
1. at room temperature in there-necked flask, add zero(ppm) water 200g, cats product cetyl trimethylammonium bromide (CTAB) 6.8g, cosurfactant Pentyl alcohol 6g, and magnetic agitation forms the micellar solution of tensio-active agent;
2. the 2g pyrrole monomer is added drop-wise in the there-necked flask, and continues magnetic agitation, form the micellar solution of the tensio-active agent that contains pyrrole monomer;
3. in there-necked flask, add the 0.8g elemental iodine, and continue magnetic agitation;
4. in there-necked flask, slowly drip 10.2g FeCl
3(being dissolved in the 40g zero(ppm) water), magnetic agitation 3h can obtain iodine dopen Nano polypyrrole.
5. in there-necked flask, add TEB 3K (MMA) 5g, and be warmed up to 70 ℃ of heating in water bath;
6. slowly be added drop-wise to the Potassium Persulphate that configures (KPS) 0.2g (being dissolved in the 5g water) solution in the there-necked flask; 70 ℃ of isothermal reaction 3h; Promptly being able to polypyrrole is the nano core-shell structure polypyrrole of shell for nuclear, polymethylmethacrylate, with its whiz, subsequent use.
(2) the waterborne conductive protective system is composite: 6.4% the nano core-shell structure polypyrrole composite particles that will account for the resin aqueous emulsion quality joins (solid content 60%) in the aqueous acroleic acid resin emulsion; And stir, promptly get the waterborne conductive protective system that contains nano core-shell structure polypyrrole.
During use, the waterborne conductive protective system of the above-mentioned nano core-shell structure polypyrrole for preparing is applied or is sprayed on through the metallic surface of oil removing and antirust processing, coat-thickness is controlled at 20～200 μ m, self-vulcanizing.
Embodiment 11: prepare a kind of waterborne conductive protective system that contains nano core-shell structure polypyrrole
Step is following:
(1) preparation nano level iodine doping polypyrrole:
1. at room temperature in there-necked flask, add zero(ppm) water 200g, cats product cetyl trimethylammonium bromide (CTAB) 10.2g, cosurfactant Pentyl alcohol 8g, and magnetic agitation forms the micellar solution of tensio-active agent;
2. the 6g pyrrole monomer is added drop-wise in the there-necked flask, and continues magnetic agitation, form the micellar solution of the tensio-active agent that contains pyrrole monomer;
3. in there-necked flask, add the 2.1g elemental iodine, and continue magnetic agitation;
4. in there-necked flask, slowly drip 23.4g FeCl
3(being dissolved in the 40g zero(ppm) water), magnetic agitation 3h can obtain iodine dopen Nano polypyrrole.
5. in there-necked flask, add TEB 3K (MMA) 8.96g, and be warmed up to 70 ℃ of heating in water bath;
6. slowly be added drop-wise to the Potassium Persulphate that configures (KPS) 0.63g (being dissolved in the 5g water) solution in the there-necked flask; 70 ℃ of isothermal reaction 3h; Promptly being able to polypyrrole is the nano core-shell structure polypyrrole of shell for nuclear, polymethylmethacrylate, with its whiz, subsequent use.
(2) the waterborne conductive protective system is composite: 20% the nano core-shell structure polypyrrole composite particles that will account for the resin aqueous emulsion quality joins (solid content 70%) in the aqueous acroleic acid resin emulsion; And stir, promptly get the waterborne conductive protective system that contains nano core-shell structure polypyrrole.
During use, the waterborne conductive protective system of the above-mentioned nano core-shell structure polypyrrole for preparing is applied or is sprayed on through the metallic surface of oil removing and antirust processing, coat-thickness is controlled at 20～200 μ m, self-vulcanizing.
Embodiment 12: prepare a kind of waterborne conductive protective system that contains nano core-shell structure polypyrrole
Step is following:
(1) preparation nano level iodine doping polypyrrole:
1. at room temperature in there-necked flask, add zero(ppm) water 200g, cats product cetyl trimethylammonium bromide (CTAB) 13.6g, cosurfactant Pentyl alcohol 4g, and magnetic agitation forms the micellar solution of tensio-active agent;
2. the 4g pyrrole monomer is added drop-wise in the there-necked flask, and continues magnetic agitation, form the micellar solution of the tensio-active agent that contains pyrrole monomer;
3. in there-necked flask, add the 1.2g elemental iodine, and continue magnetic agitation;
4. in there-necked flask, slowly drip 24.8g FeCl
3(being dissolved in the 40g zero(ppm) water), magnetic agitation 3h can obtain iodine dopen Nano polypyrrole.
5. in there-necked flask, add TEB 3K (MMA) 7.41g, and be warmed up to 70 ℃ of heating in water bath;
6. slowly be added drop-wise to the Potassium Persulphate that configures (KPS) 0.41g (being dissolved in the 5g water) solution in the there-necked flask; 70 ℃ of isothermal reaction 3h; Promptly being able to polypyrrole is the nano core-shell structure polypyrrole of shell for nuclear, polymethylmethacrylate, with its whiz, subsequent use.
(2) the waterborne conductive protective system is composite: 15% the nano core-shell structure polypyrrole composite particles that will account for the resin aqueous emulsion quality joins (solid content 60%) in the aqueous acroleic acid resin emulsion; And stir, promptly get the waterborne conductive protective system that contains nano core-shell structure polypyrrole.
During use, the waterborne conductive protective system of the above-mentioned nano core-shell structure polypyrrole for preparing is applied or is sprayed on through the metallic surface of oil removing and antirust processing, coat-thickness is controlled at 20～200 μ m, self-vulcanizing.
Claims (6)
1. preparation method who contains the waterborne conductive protective system of nano core-shell structure polypyrrole; The said waterborne conductive protective system that contains nano core-shell structure polypyrrole is composed of the following components: nano core-shell structure polypyrrole composite particles and resin aqueous emulsion; Wherein, Nano core-shell structure polypyrrole accounts for 5.5%～25% of resin aqueous emulsion quality, it is characterized in that: may further comprise the steps:
(1) nano core-shell structure polypyrrole is synthetic:
1. at room temperature in there-necked flask, add zero(ppm) water, cats product cetyl trimethylammonium bromide and cosurfactant Pentyl alcohol successively, and magnetic agitation forms the micellar solution of tensio-active agent;
2. pyrrole monomer is added drop-wise in the above-mentioned micellar solution that configures;
3. in there-necked flask, add iodine;
4. previously prepd is dissolved in the FeCl of zero(ppm) water
3Dropwise splash in the there-necked flask, at room temperature, system is carried out magnetic agitation, after 3 hours, pyrroles's chemical oxidising polymerisation is accomplished in micella;
5. in there-necked flask, add monomers methyl methacrylate, and temperature is risen to 70 ℃ of heating in water bath;
6. the potassium persulfate solution for preparing is added drop-wise in the system with constant pressure funnel, 70 ℃ of isothermal reaction 3h, promptly being able to iodine doping polypyrrole is the nano core-shell structure polypyrrole of shell for nuclear, polymethylmethacrylate;
(2) composite: behind above-mentioned nano core-shell structure polypyrrole washing whiz, be added in the water-borne coatings resin emulsion, dispersed with stirring is even, promptly gets the waterborne conductive protective system of nano core-shell structure polypyrrole.
2. a kind of preparation method who contains the waterborne conductive protective system of nano core-shell structure polypyrrole according to claim 1; It is characterized in that: in the said step (1), the mass ratio of cats product cetyl trimethylammonium bromide and zero(ppm) water is 0.034～0.068; The mass ratio of cosurfactant Pentyl alcohol and zero(ppm) water is 0.02～0.04; The mass ratio of pyrrole monomer and zero(ppm) water is 0.01～0.03; The mass ratio of pyrrole monomer and MMA MONOMER is 0.40～0.67; The mass ratio of doping agent elemental iodine and pyrrole monomer is 0.3～0.4; Oxygenant FeCl
3With the mass ratio of pyrrole monomer be 3.9～6.2; The mass ratio of oxygenant Potassium Persulphate and TEB 3K is 0.04～0.07.
3. a kind of preparation method who contains the waterborne conductive protective system of nano core-shell structure polypyrrole according to claim 1 is characterized in that: said nano core-shell structure polypyrrole accounts for 5.5%～8.5% of resin aqueous emulsion quality.
4. a kind of preparation method who contains the waterborne conductive protective system of nano core-shell structure polypyrrole according to claim 1 is characterized in that: said nano core-shell structure polypyrrole accounts for 6.4%～15% of resin aqueous emulsion quality.
5. a kind of preparation method who contains the waterborne conductive protective system of nano core-shell structure polypyrrole according to claim 1; It is characterized in that: the kernel of said nano core-shell structure polypyrrole composite particles is an iodine dopen Nano electric polypyrrole, and the shell of electric polypyrrole composite particles is a polymethylmethacrylate.
6. a kind of preparation method who contains the waterborne conductive protective system of nano core-shell structure polypyrrole according to claim 1 is characterized in that: said water-borne coatings resin emulsion is that solid content is 40%～80% water-borne acrylic resin emulsion.
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| CN107286777A (en) * | 2017-07-24 | 2017-10-24 | 湖北启利新材料股份有限公司 | A kind of conductive anti-corrosive primer coating of water nano polyaniline epoxy acrylic resin |
| CN109957272A (en) * | 2019-03-03 | 2019-07-02 | 东北石油大学 | A kind of preparation method of anticorrosive packing, anticorrosive paint and the two |
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| CN101035630A (en) * | 2004-08-03 | 2007-09-12 | 坎梅陶尔股份有限公司 | Process for coating metallic surfaces with an anti-corrosive coating |
| WO2007119762A1 (en) * | 2006-04-13 | 2007-10-25 | Kansai Paint Co., Ltd. | Aqueous coating composition |
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| JP5717229B2 (en) * | 2007-04-27 | 2015-05-13 | 関西ペイント株式会社 | Anticorrosion coating method using water-based epoxy resin zinc rich paint |
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| CN101035630A (en) * | 2004-08-03 | 2007-09-12 | 坎梅陶尔股份有限公司 | Process for coating metallic surfaces with an anti-corrosive coating |
| WO2007119762A1 (en) * | 2006-04-13 | 2007-10-25 | Kansai Paint Co., Ltd. | Aqueous coating composition |
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