CN105694664A

CN105694664A - Polyaniline-modified zinc-containing anti-corrosive coating and preparation method thereof

Info

Publication number: CN105694664A
Application number: CN201610056228.1A
Authority: CN
Inventors: 赵栋
Original assignee: Individual
Current assignee: Individual
Priority date: 2016-01-28
Filing date: 2016-01-28
Publication date: 2016-06-22

Abstract

The invention relates to a polyaniline-modified zinc-containing anti-corrosive coating. The polyaniline-modified zinc-containing anti-corrosive coating comprises the following raw materials in parts by weight: 50 to 80 parts of graphene, 10 to 15 parts of polypropylene vinyl acetate, 20 to 38 parts of epoxy resin, 70 to 210 parts of zinc powder, 17 to 40 parts of talcum powder, 10 to 20 parts of defoaming agent, 5 to 8 parts of flatting agent, 5 to 8 parts of curing agent, 30 to 70 parts of filling agent, and 10 to 15 parts of polyaniline-based nanometer material. The polyaniline-modified zinc-containing anti-corrosive coating has good waterproof property, and is suitable for protecting marine wind power equipment under marine environments, and is also suitable for long-time corrosion resistance of land steel structures of inland pipe diameters.

Description

A kind of polyaniline-modified Zinc-containing anticorrosion paint and preparation method thereof

Technical field

The present invention relates to anticorrosive paint field, be specifically related to a kind of polyaniline-modified Zinc-containing anticorrosion paint。

Background technology

Prior art has all kinds, varied, CN101407650A proposes to be undertaken blended by oligomer, reactive diluent, polyaniline, filler, light trigger, auxiliary agent, agitated, grinding, filtration etc., obtain UV curing polyaniline anticorrosive coating, the solidification of this patent gained coating is limited to the penetration depth of ultraviolet light, it is easy to solidify not exclusively, thus causing that coating performance is not good；Chinese patent CN101418146A proposes to prepare ultraviolet-heat dual curing polyaniline anticorrosion paint with oligomer, reactive diluent, polyurethane polyol, polyaniline, filler, light trigger and auxiliary agent, this patent improves the performance of coating, but diluent is still organic solvent, is unfavorable for environmental protection。JP2010031292A is using white carbon black as conductive agent, with polysiloxanes, silicone oil for organic siliconresin, mixes with firming agent and organic solvent and prepares conduction silicon composition。But, white carbon black is poor with the compatibility of organic siliconresin, it is more difficult to be uniformly dispersed, and the color of white carbon black resulting product is not because being liked by people in black simultaneously。

Anticorrosive paint field is by adding various fillers, but its effect can not meet the market demand, does not reach the hardness that people pursue, adhesive force, shock resistance, pliability and the significant product requirement of water proofing property。

Summary of the invention

For the deficiencies in the prior art, an object of the present invention is in that to provide new syncretic zinc cold spray coating。The technical scheme is that a kind of polyaniline-modified Zinc-containing anticorrosion paint, particular by adding polyaniline nano material in coating, the weight portion of its constitutive material is: Graphene 50-80, polypropylene vinylacetate 10-15, epoxy resin 20-38, zinc powder 70-210, Pulvis Talci 17-40, defoamer 10-20, levelling agent 5-8, firming agent 5-8, filler 30-70, polyaniline nano material 10-15。

Wherein, the preparation process of described polyaniline nano composite material is: is distributed to by a nanometer corner zinc oxide in water and forms nano material dispersion liquid, then in nanometer corner zinc oxide fluid dispersion, it is separately added into aniline and p-methyl benzenesulfonic acid aqueous solution, stir, be addition ammonium persulfate aqueous solution at 15～30 DEG C in reaction temperature, be stirred continuously, after reaction 1～24h, through sucking filtration, and washing is colourless to filtrate, and gained filter cake is polyaniline nano composite material；Wherein, the mass ratio of nanometer corner zinc oxide and water is 40-45: 100, the mass ratio of aniline and nanometer corner zinc oxide is 1.1-1.3: 1, the mol ratio of p-methyl benzenesulfonic acid and aniline is 3-7: 1, the concentration of p-methyl benzenesulfonic acid is 5-8mol/L, the mol ratio of Ammonium persulfate. and aniline is 1.5-1.8: 1, and the molar concentration of ammonium persulfate solution is 2-4mol/L。

Further, the preparation method that the present invention also provides for a kind of described cold spray zinc anticorrosive paint of Graphene, particularly as follows: (1) is according to aforementioned proportion relation, by zinc powder, Graphene and polyaniline nano material mix homogeneously, it is stirred dispersion 30-80min at the rotating speed of 200-500 rev/min；(2) keep the mixing speed of 200-500 rev/min, add polypropylene vinylacetate, epoxy resin, then stand 10-15min；(3) add Pulvis Talci, and the defoamer deaeration under vacuo adding the half amount in aforementioned proportion processes；(4) levelling agent, firming agent, filler are added, mixing speed is increased to 1000-1200 rev/min, insulation is at the uniform velocity stirred 30-40min (5) at 80-90 DEG C and is added the defoamer of residue half amount, continue to stir 10min under the rotating speed of 1000-1200 rev/min, obtain the cold spray zinc anticorrosive paint of Graphene。

Preferably, described implant is selected from silicon dioxde solution, and described silicon dioxde solution is selected from the nanometer grade silica solution with tridimensional network；In described nanometer grade silica solution, the particle diameter of silicon dioxide is 10-50nm, and concentration is 10-50wt%。

Preferably, described defoamer is OPEO；Described levelling agent is acrylic acid。

Preferably, described firming agent is trimethylhexamethylenediamine, it is preferred that the Martin Heat Resistant Temperature of trimethylhexamethylenediamine is 94 DEG C, middle temperature-curable is effective, and cryogenic property is good。

To the method it is preferred that, optional following concrete steps, (1) according to aforementioned proportion relation, molten zinc powder, Graphene and polyaniline nano composite material mix homogeneously, be stirred dispersion 50min at the rotating speeds of 250 revs/min；(2) keep the mixing speed of 280 revs/min, add polypropylene vinylacetate, epoxy resin, then stand 12min；(3) add Pulvis Talci, and the defoamer deaeration under vacuo adding the half amount in aforementioned proportion processes。(4) adding levelling agent, firming agent, filler, mixing speed is increased to 1100 revs/min, insulation at the uniform velocity stirs 35min at 90 DEG C。(5) add the defoamer of residue half amount, continue to stir 10min under the rotating speed of 1100 revs/min, obtain a kind of polyaniline-modified Zinc-containing anticorrosion paint。

The present invention also provides for the concrete application of said method or above-mentioned anticorrosive paint, for instance polyaniline-modified Zinc-containing anticorrosion paint protects suitable in the offshore wind power equipment of marine environment, or the long-effective corrosion of the land steel construction for inland caliber。

The application of a kind of polyaniline-modified Zinc-containing anticorrosion paint of the present invention, described syncretic zinc cold spray coating is applicable to the long-effective corrosion of marine and land steel construction。Owing to have adjusted Graphene and zinc powder weight ratio, the solidification effect of the coating obtained is better, it is in the expection of those skilled in the art, reinforced stirring stage by stage, ensure that the fineness of coating, and pliability, in preparation process stand during, inventor have found that add polypropylene vinylacetate, epoxy resin standing make coating have excellent adhesive force and impact strength。Improve the serviceability of coating。

Detailed description of the invention

For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment。It will be understood by those skilled in the art that described embodiment is only that the present invention is understood in help, be not construed as the concrete restriction to the present invention。

Embodiment 1

A kind of preparation method of the polyaniline-modified Zinc-containing anticorrosion paint of the present invention, comprise the steps: that first drafting product proportioning is, the weight portion of its constitutive material is: Graphene 80, polypropylene vinylacetate 15, epoxy resin 38, zinc powder 210, Pulvis Talci 40, defoamer 20, levelling agent 8, firming agent 8, filler 70 polyaniline nano material 10-15；Specifically, in this embodiment, preferred implant is selected from silicon dioxde solution, and described silicon dioxde solution is selected from the nanometer grade silica solution with tridimensional network；In described nanometer grade silica solution, the particle diameter of silicon dioxide is 50nm, and concentration is 50wt%, and described defoamer is OPEO；Described levelling agent is acrylic acid, and described firming agent is trimethylhexamethylenediamine, and the Martin Heat Resistant Temperature of further trimethylhexamethylenediamine is 94 DEG C。Wherein, the preparation process of described polyaniline nano composite material is: is distributed to by a nanometer corner zinc oxide in water and forms nano material dispersion liquid, then in nanometer corner zinc oxide fluid dispersion, it is separately added into aniline and p-methyl benzenesulfonic acid aqueous solution, stir, be addition ammonium persulfate aqueous solution at 15 DEG C in reaction temperature, be stirred continuously, after reaction 7h, through sucking filtration, and washing is colourless to filtrate, and gained filter cake is polyaniline nano composite material；Wherein, the mass ratio of nanometer corner zinc oxide and water is 40: 100, the mass ratio of aniline and nanometer corner zinc oxide is 1.1: 1, the mol ratio of p-methyl benzenesulfonic acid and aniline is 3: 1, the concentration of p-methyl benzenesulfonic acid is 5mol/L, the mol ratio of Ammonium persulfate. and aniline is 1.5: 1, and the molar concentration of ammonium persulfate solution is 2mol/L。Described method comprises the steps: that (1) is according to aforementioned proportion relation, by zinc powder, Graphene and polyaniline nano composite material mix homogeneously, is stirred dispersion 80min at the rotating speeds of 500 revs/min；(2) keep the mixing speed of 500 revs/min, add polypropylene vinylacetate, epoxy resin, then stand 15min；(3) add Pulvis Talci, and the defoamer deaeration under vacuo adding the half amount in aforementioned proportion processes。(4) adding levelling agent, firming agent, filler, mixing speed is increased to 1200 revs/min, insulation at the uniform velocity stirs 40min at 90 DEG C。(5) add the defoamer of residue half amount, continue to stir 10min under the rotating speed of 1200 revs/min, obtain the cold spray zinc anticorrosive paint of Graphene。

Embodiment 2

A kind of preparation method of the polyaniline-modified Zinc-containing anticorrosion paint of the present invention, comprise the steps: that first drafting product proportioning is, the weight portion of its constitutive material is: Graphene 50, polypropylene vinylacetate 10, epoxy resin 20, zinc powder 70, Pulvis Talci 17, defoamer 10, levelling agent 5, firming agent 5, filler 30-70, polyaniline nano material 10-15；Specifically, in this embodiment, preferred implant is selected from silicon dioxde solution, and described silicon dioxde solution is selected from the nanometer grade silica solution with tridimensional network；In described nanometer grade silica solution, the particle diameter of silicon dioxide is 10nm, and concentration is 10wt%, and described defoamer is OPEO；Described levelling agent is acrylic acid, and described firming agent is trimethylhexamethylenediamine, it is preferable that the Martin Heat Resistant Temperature of trimethylhexamethylenediamine is 94 DEG C。Wherein, the preparation process of described polyaniline nano composite material is: is distributed to by a nanometer corner zinc oxide in water and forms nano material dispersion liquid, then in nanometer corner zinc oxide fluid dispersion, it is separately added into aniline and p-methyl benzenesulfonic acid aqueous solution, stir, be addition ammonium persulfate aqueous solution at 30 DEG C in reaction temperature, be stirred continuously, after reaction 4h, through sucking filtration, and washing is colourless to filtrate, and gained filter cake is polyaniline nano composite material；Wherein, the mass ratio of nanometer corner zinc oxide and water is 45: 100, the mass ratio of aniline and nanometer corner zinc oxide is 1.3: 1, the mol ratio of p-methyl benzenesulfonic acid and aniline is 7: 1, the concentration of p-methyl benzenesulfonic acid is 8mol/L, the mol ratio of Ammonium persulfate. and aniline is-1.8: 1, and the molar concentration of ammonium persulfate solution is 4mol/L。Described method comprises the steps: that (1) is according to aforementioned proportion relation, by zinc powder, Graphene and polyaniline nano composite material mix homogeneously, is stirred dispersion 30min at the rotating speeds of 500 revs/min；(2) keep the mixing speed of 200 revs/min, add polypropylene vinylacetate, epoxy resin, then stand 10min；(3) add Pulvis Talci, and the defoamer deaeration under vacuo adding the half amount in aforementioned proportion processes。(4) adding levelling agent, firming agent, filler, mixing speed is increased to 1000 revs/min, insulation at the uniform velocity stirs 30min at 80 DEG C。(5) add the defoamer of residue half amount, continue to stir 10min under the rotating speed of 1000 revs/min, obtain the cold spray zinc anticorrosive paint of Graphene。

Formula according to the present embodiment and preparation method thereof obtains the property indices of anti-corrosion material, and result is table 1 such as。

Table 1 embodiment prepares coating quality index (averaging)

Applicant states, the present invention illustrates detailed process equipment and the technological process of the present invention by above-described embodiment, but the invention is not limited in above-mentioned detailed process equipment and technological process, namely do not mean that the present invention has to rely on above-mentioned detailed process equipment and technological process could be implemented。Person of ordinary skill in the field should be understood that any improvement in the present invention, and the equivalence of each raw material of product of the present invention is replaced and the interpolation of auxiliary element, concrete way choice etc., all falls within protection scope of the present invention and open scope。

Claims

1. Zinc-containing anticorrosion paint one kind polyaniline-modified, it is characterized in that, the weight portion of its constitutive material is: Graphene 50-80, polypropylene vinylacetate 10-15, epoxy resin 20-38, zinc powder 70-210, Pulvis Talci 17-40, defoamer 10-20, levelling agent 5-8, firming agent 5-8, filler 30-70, polyaniline nano material 10-15；Wherein, the preparation process of described polyaniline nano composite material is: is distributed to by a nanometer corner zinc oxide in water and forms nano material dispersion liquid, then in nanometer corner zinc oxide fluid dispersion, it is separately added into aniline and p-methyl benzenesulfonic acid aqueous solution, stir, be addition ammonium persulfate aqueous solution at 15～30 DEG C in reaction temperature, be stirred continuously, after reaction 1～24h, through sucking filtration, and washing is colourless to filtrate, and gained filter cake is polyaniline nano composite material；Wherein, the mass ratio of nanometer corner zinc oxide and water is 40-45: 100, the mass ratio of aniline and nanometer corner zinc oxide is 1.1-1.3: 1, the mol ratio of p-methyl benzenesulfonic acid and aniline is 3-7: 1, the concentration of p-methyl benzenesulfonic acid is 5-8mol/L, the mol ratio of Ammonium persulfate. and aniline is 1.5-1.8: 1, and the molar concentration of ammonium persulfate solution is 2-4mol/L。

2. anticorrosive paint as claimed in claim 1, it is characterised in that: preferably, described implant is selected from silicon dioxde solution。

3. anticorrosive paint as claimed in claim 1, it is characterised in that: preferably, described silicon dioxde solution is selected from the nanometer grade silica solution with tridimensional network；In described nanometer grade silica solution, the particle diameter of silicon dioxide is 10-50nm, and concentration is 10-50wt%。

4. anticorrosive paint as claimed in claim 1, it is characterised in that: preferably, described defoamer is OPEO；Described levelling agent is acrylic acid。

5. anticorrosive paint as claimed in claim 1, it is characterised in that: preferably, described firming agent is trimethylhexamethylenediamine, it is preferred that the Martin Heat Resistant Temperature of trimethylhexamethylenediamine is 94 DEG C。

6. anticorrosive paint as claimed in claim 1, it is characterised in that: preferably Graphene 80, polypropylene vinylacetate 15, epoxy resin 38, zinc powder 210, Pulvis Talci 40, defoamer 20, levelling agent 8, firming agent 8, filler 70。

7. anticorrosive paint as claimed in claim 1, it is characterised in that: preferably Graphene 50, polypropylene vinylacetate 10, epoxy resin 20, zinc powder 70, Pulvis Talci 17, defoamer 10, levelling agent 5-8, firming agent 5, filler 30。

8. the preparation method of an anticorrosive paint as claimed in claim 1, it is characterized in that: described method comprises the steps: that (1) is according to aforementioned proportion relation, by zinc powder, Graphene and polyaniline nano composite material mix homogeneously, it is stirred dispersion 30-80min at the rotating speed of 200-500 rev/min。(2) keep the mixing speed of 200-500 rev/min, add polypropylene vinylacetate, epoxy resin, then stand 10-15min；(3) add Pulvis Talci, and the defoamer deaeration under vacuo adding the half amount in aforementioned proportion processes。(4) adding levelling agent, firming agent, filler, mixing speed is increased to 1000-1200 rev/min, insulation at the uniform velocity stirs 30-40min at 80-90 DEG C。(5) add the defoamer of residue half amount, continue to stir 10min under the rotating speed of 1000-1200 rev/min, obtain the cold spray zinc anticorrosive paint of Graphene。

9. method as claimed in claim 8, it is characterised in that: (1), according to aforementioned proportion relation, by zinc powder and Graphene mix homogeneously, is stirred dispersion 50min at the rotating speeds of 250 revs/min；(2) keep the mixing speed of 280 revs/min, add polypropylene vinylacetate, epoxy resin, then stand 12min；(3) add Pulvis Talci, and the defoamer deaeration under vacuo adding the half amount in aforementioned proportion processes。(4) adding levelling agent, firming agent, filler, mixing speed is increased to 1100 revs/min, insulation at the uniform velocity stirs 35min at 90 DEG C。(5) add the defoamer of residue half amount, continue to stir 10min under the rotating speed of 1100 revs/min, obtain the cold spray zinc anticorrosive paint of Graphene。

10. the application of the coating as described in the syncretic zinc cold spray coating that prepared by the method as described in aforementioned any one of claim or any one claim, it is characterized in that, described syncretic zinc cold spray coating is protected suitable in the offshore wind power equipment of marine environment, or the long-effective corrosion of the land steel construction for inland caliber。