CN101143991A - Polyaniline anticorrosion paint easy to disperse - Google Patents
Polyaniline anticorrosion paint easy to disperse Download PDFInfo
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- CN101143991A CN101143991A CNA2007100473664A CN200710047366A CN101143991A CN 101143991 A CN101143991 A CN 101143991A CN A2007100473664 A CNA2007100473664 A CN A2007100473664A CN 200710047366 A CN200710047366 A CN 200710047366A CN 101143991 A CN101143991 A CN 101143991A
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Abstract
The invention relates to an anticorrosive coating, wherein the anticorrosive coating is two-component composition, which includes A component: 35wt percent-50wt percent of epoxy resin, 1wt percent-50wt percent of doping-polyaniline ultrafine cellulose, 5wt percent-50wt percent of diluent, 0.5wt percent-1wt percent of dispersant, 1.5wt percent-3wt percent of anti-sedimentation agent , 0.5wt percent-1wt percent of defoaming agent; B component: 30wt percent-50wt percent of aliphatic polyamide and 50wt percent-70wt percent of diluent. Compared with the existing polyaniline anticorrosive coating, the anticorrosive coating prepared by the invention has good antiseptic property and stability, which is environment friendly.
Description
Technical field
The present invention relates to a kind of protective system.Specifically, relate to the ultra-fine polyaniline/corrosion-resistant epoxy paint of a kind of one dimension.
Background technology
Metallic corrosion is the rotten behavior of material very common in the material industry.In order to prevent or to slow down corrosion of metal, the protective coating system that adopts generally includes bottom, middle layer and surface layer three parts at present: bottom mainly is some corrosion inhibitors (as chromic salt or phosphoric acid salt), the middle layer is the organic coating (as zinc rich primer) that contains various inorganic or pigment dyestuff or fillers, and surface layer mainly is in order to decorate and to guarantee that priming paint and outside atmosphere are isolated.Though this type coating system is effective relatively, in use can discharge a large amount of poisonous and hazardous metal ions, environment is caused severe contamination; In case and coating has slight scuffing, preservative effect is had a greatly reduced quality.Therefore, seeking better protective system is very important.
Characteristics such as that polyaniline has is inexpensive, environmental stability good, Corrosion Protection is excellent and toxicity is little.Polyaniline causes people's attention gradually as protective system.Existing polyaniline type protective system mainly contains two kinds: (1) electrochemical polymerization forms polyaniline coating.This protective system uses inconvenience (being not suitable for the anticorrosion of site operation and bigger metal parts); (2) polyaniline (adopting existing chemical oxidative polymerization to make polyaniline in eigenstate) mixes the organic composite coating of formation with conventional filmogen (as Resins, epoxy, urethane and polyacrylic resin etc.).The deficiency that this kind protective system exists is: (a) selected polyaniline in eigenstate polyaniline is dissolved in the conventional organic solvent hardly, be only soluble in some strong polarity high boiling solvent, in N-Methyl pyrrolidone (NMP) and meta-cresol etc., these high boiling solvents will influence coating quality, make to use to be restricted; (b) toxicity of solvent for use is big, and environment is polluted.
Summary of the invention
The object of the invention is, a kind of easy dispersion, environmentally friendly and have a polyaniline anti-corrosive paint of good Corrosion Protection is provided.
The said polyaniline anti-corrosive paint of the present invention is a two-component composition, by weight percentage, comprises following material,
The A component:
Resins, epoxy 35wt%～50wt%
Polyaniline 1wt%～50wt%
Thinner 5wt%～50wt%
Dispersion agent 0.5wt%～1wt%
Anti-settling agent 1.5wt%～3wt%
Defoamer 0.5wt%～1wt%
The B component:
Fatty polyamide 30wt%～50wt%
Thinner 50wt%～70wt%
Wherein: described Resins, epoxy is bisphenol A type epoxy resin; Described polyaniline is the polyaniline in eigenstate ultra-fine fibre, and the diameter of fiber is 30nm～120nm; The aliphatic alcohol of described thinner, ester or ketone compound; Described dispersion agent is Disperbyk-160 (German BYK Chemie company produce); Described anti-settling agent is organobentonite (" coatings industry material technology manual of standards ", Chemical Industry Press are seen in technical requirements) or aerosil; Described defoamer is that kinematic viscosity (25 ℃) is 100mm
2/ s～1000mm
2/ s dimethyl silicone oil.
In optimal technical scheme of the present invention, described Resins, epoxy is E-51, E-44 or the E-20 Resins, epoxy (by the name of GB GB/T1630-1989 Resins, epoxy nomenclature) of bisphenol A-type.
In another optimal technical scheme of the present invention, the amine value of described fatty polyamide is that 200mgKOH/g～400mgKOH/g, viscosity (40 ℃) are 500cps～20000cps.
In another optimal technical scheme of the present invention, described thinner is C
1～C
6Aliphatic monobasic alcohol; Preferred thinner is ethanol, Virahol or propyl carbinol.
Embodiment
Prepare the method for the said polyaniline anti-corrosive paint of the present invention, comprise the steps:
The preparation of I.A component:
(1) aniline monomer is dissolved in the organic solvent (as chloroform, tetracol phenixin, normal hexane or toluene etc.), ammonium persulphate is dissolved in mineral acid (example hydrochloric acid, sulfuric acid or the perchloric acid etc.) aqueous solution.Press aniline monomer and ammonium persulphate mol ratio and be (6～2): 1, the organic solution of aniline monomer is joined in the inorganic acid solution of ammonium persulphate (in this process, guaranteeing to form the good organic phase and the interface of water), add the back and left standstill 8 hours to 24 hours at 15 ℃～35 ℃.After filtration with washing after must the mix polyaniline ultra-fine fibre of attitude.The mix polyaniline ultra-fine fibre of attitude of gained is placed the ammoniacal liquor of 10wt%, under 15 ℃～35 ℃ conditions, stirred 24 hours, after filtration, must the polyaniline in eigenstate ultra-fine fibre after washing (being neutral) and the drying to filtrate.
(2) promptly get the said A component of the present invention after will mixing by aforementioned weight percent by polyaniline in eigenstate ultra-fine fibre, Resins, epoxy, thinner, dispersion agent, anti-settling agent and the defoamer that step (1) makes.
The preparation of II.B component:
Being 200mgKOH/g～400mgKOH/g, viscosity (40 ℃) with the amine value promptly gets the said B component of the present invention after mixing by aforementioned weight percent for the fatty polyamide of 500cps～20000cps and thinner.
The using method of polyaniline anti-corrosive paint of the present invention is: at first with A component and B component by weight (1～3): 1 mixes, then the gained mixture is applied or is sprayed on metallic surface through oil removing, processing of rust removing, coat-thickness is controlled 80 μ m～200 μ m and is advisable, and at room temperature solidifies to get final product in 5～7 days.
To be immersed in the NaCl solution of 5wt% through the metal that the said protective system of the present invention applies, with the electrochemical etching method test, find that the metallic corrosion current potential increases substantially, the electric current of metallic corrosion simultaneously also reduces greatly, has slowed down medium to corrosion of metal.
Compare with existing polyaniline anti-corrosive paint, the prepared protective system of the present invention has excellent antiseptic property and satisfactory stability performance and environmentally friendly.
The present invention is further illustrated by the following examples, and its purpose only is better to understand content of the present invention.Therefore, the cited case does not limit protection scope of the present invention.
Comparative example 1
I. the preparation of protective system
(1) A component preparation:
A, the common polyaniline in eigenstate (reference literature: Cao Y that will adopt the traditional chemical oxidative polymerization method to make, et al.Polymer1989,30,2305) put into dehydrated alcohol, through supersound process 1 hour, form the dispersion liquid that contains 10wt% state of aggregation polyaniline, after this dispersion liquid leaves standstill 3 hours, complete sedimentation phenomenon occurs, show that the dispersion stabilization of common polyaniline in dehydrated alcohol that traditional method makes is very poor.
B, the common polyaniline in eigenstate dispersion liquid that will make by step a, E-44 Resins, epoxy, propyl carbinol, Disperbyk-160 (German BYK Chemie company produce), BT-838A organobentonite (sky, Anji, Zhejiang dragon organobentonite company produces), get mixture (A component) after dimethyl silicone oil [kinematic viscosity is 500mm2/s (25 ℃)] mixes, and make common polyaniline in eigenstate, E-44 Resins, epoxy, propyl carbinol, Disperbyk-160, BT-838A organobentonite and the dimethyl silicone oil content (in weight percent concentration) in this mixture is followed successively by 50wt%, 40wt%, 7wt%, 0.5wt%, 2wt% and 0.5wt%.
(2) B component preparation
With fatty polyamide (the amine value be 200mgKOH/g, viscosity (40 ℃) for 500cps～5000cps) and propyl carbinol by mechanical stirring mix mixture (B component), and fatty polyamide and the content (in weight percent concentration) of propyl carbinol in the gained mixture are 50wt%.
II. the test of antiseptic property
With A component and B component after the mixing of 2: 1 ratios mixture, with the medium carbon steel surface of this mixture brushing in oil removing, processing of rust removing, build is controlled at about 100 μ m.After the self-vulcanizing 7 days, it is immersed in the NaCl aqueous solution of 5wt%, uses electrochemical etching method, recording its corrosion potential is-407mV that corrosion current is 0.11 μ Acm-2.
Embodiment 1
I. the preparation of protective system
(1) A component preparation
A, be that 30-60nm polyaniline in eigenstate nanofiber is put into dehydrated alcohol with diameter, through supersound process 1 hour, form the dispersion liquid that contains 10wt% state of aggregation polyaniline, after this dispersion liquid leaves standstill 48 hours, still present the stable dispersion liquid of black, sedimentation phenomenon do not occur.Show that polyaniline nano fiber has good dispersion stabilization in dehydrated alcohol;
[kinematic viscosity is 500mm for b, polyaniline in eigenstate nanofiber dispersion liquid, E-44 Resins, epoxy, propyl carbinol, Disperbyk-160, BT-838A organobentonite, the dimethyl silicone oil that will be made by step a
2/ s (25 ℃)] after mixing mixture (A component), and make polyaniline nano fiber dispersion liquid, E-44 Resins, epoxy, propyl carbinol, Disperbyk-160, BT-838A organobentonite and the dimethyl silicone oil content (in weight percent concentration) in this mixture be followed successively by 50wt%, 40wt%, 7wt%, 0.5wt%, 2wt% and 0.5wt%.
(2) B component preparation
With fatty polyamide (the amine value be 200mgKOH/g, viscosity (40 ℃) for 500cps～20000cps) and propyl carbinol by mechanical stirring mix mixture (B component), and fatty polyamide and the content (in weight percent concentration) of propyl carbinol in the gained mixture are 50wt%.
II. the test of antiseptic property
With A component and B component after the mixing of 2: 1 ratios mixture, with the medium carbon steel surface of this mixture brushing in oil removing, processing of rust removing, build is controlled at about 100 μ m.After the self-vulcanizing 7 days, it is immersed in the NaCl aqueous solution of 5wt%, uses electrochemical etching method, recording its corrosion potential is-314mV that corrosion current is 0.04 μ Acm
-2, to compare corrosion potential with comparative example 1 and improve 93mV, corrosion current reduces nearly 3 times, illustrates that the protective system that present embodiment makes has good preservative effect.
Embodiment 2
I. the preparation of protective system
(1) A component preparation
A, be that 30-60nm polyaniline in eigenstate nanofiber is put into Virahol,, form the homodisperse liquid that contains the 10wt% polyaniline nano fiber through supersound process 0.5 hour with diameter;
[kinematic viscosity is 100mm for b, polyaniline in eigenstate nanofiber dispersion liquid, E-51 Resins, epoxy, N-BUTYL ACETATE, Disperbyk-160, BT-838A organobentonite, the dimethyl silicone oil that will be made by step a
2/ s (25 ℃)] after mixing mixture (A component), and make polyaniline nano fiber dispersion liquid, E-51 Resins, epoxy, N-BUTYL ACETATE, Disperbyk-160, BT-838A organobentonite and the dimethyl silicone oil content (in weight percent concentration) in this mixture be followed successively by 10wt%, 50wt%, 36wt%, 0.5wt%, 3wt% and 0.5wt%.
(2) B component preparation
With fatty polyamide (the amine value be 200mgKOH/g, viscosity (40 ℃) for 500cps～5000cps) and propyl carbinol by mechanical stirring mix mixture (B component), and fatty polyamide and the content (in weight percent concentration) of propyl carbinol in the gained mixture are respectively 40wt% and 60wt%.
II. the test of antiseptic property
After A component and B component mixed by 1: 1 weight ratio mixture, with the medium carbon steel surface of this mixture brushing in oil removing, processing of rust removing, build is controlled at about 100 μ m.After the self-vulcanizing 7 days, it is immersed in the NaCl aqueous solution of 5wt%, uses electrochemical etching method, recording its corrosion potential is-322mV that corrosion current is 0.06 μ Acm
-2, to compare corrosion potential with comparative example 1 and improve 85mV, corrosion current reduces nearly 2 times, illustrates that the protective system that present embodiment makes has good preservative effect.
Embodiment 3
I. the preparation of protective system
(1) A component preparation
A, 60-120nm polyaniline in eigenstate nanofiber is put into propyl carbinol,, form the homodisperse liquid that contains the 20wt% polyaniline nano fiber through supersound process 2 hours;
B, the polyaniline in eigenstate nanofiber dispersion liquid that will be made by step a, E-44 Resins, epoxy, propyl carbinol, Disperbyk-160, aerosil, [kinematic viscosity (25 ℃) is 1000mm to dimethyl silicone oil
2/ s] after mixing mixture (A component), and make polyaniline nano fiber dispersion liquid, E-44 Resins, epoxy, propyl carbinol, Disperbyk-160, aerosil and the dimethyl silicone oil content (in weight percent concentration) in this mixture be followed successively by 50wt%, 40wt%, 7wt%, 1wt%, 1.5wt% and 0.5wt%.
(2) B component preparation
With fatty polyamide (the amine value be 200mgKOH/g, viscosity (40 ℃) for 500cps～5000cps) and propyl carbinol by mechanical stirring mix mixture (B component), and fatty polyamide and the content (in weight percent concentration) of propyl carbinol in the gained mixture are 50wt%.
II. the test of antiseptic property
With the A component with after the B component is mixed by 2: 1 weight ratio mixture, with the medium carbon steel surface of this mixture brushing in oil removing, processing of rust removing, build is controlled at about 100 μ m.After the self-vulcanizing 5 days, it is immersed in the NaCl aqueous solution of 5wt%, uses electrochemical etching method, recording its corrosion potential is-302mV that corrosion current is 0.02 μ Acm
-2, to compare corrosion potential with comparative example 1 and improve 105mV, corrosion current reduces nearly 6 times, illustrates that the protective system that present embodiment makes has good preservative effect.
Embodiment 4
I. the preparation of protective system
(1) A component preparation
A, be that 30-60nm polyaniline in eigenstate nanofiber is put into propyl carbinol,, form the homodisperse liquid that contains the 20wt% polyaniline nano fiber through supersound process 1 hour with diameter;
[kinematic viscosity is 500mm for b, polyaniline in eigenstate nanofiber dispersion liquid, E-20 Resins, epoxy, methyl iso-butyl ketone (MIBK), Disperbyk-160, BT-838A organobentonite, the dimethyl silicone oil that will be made by step a
2/ s (25 ℃)] after mixing mixture (A component), and make polyaniline nano fiber dispersion liquid, E-20 Resins, epoxy, methyl iso-butyl ketone (MIBK), Disperbyk-160, BT-838A organobentonite and the dimethyl silicone oil content (in weight percent concentration) in this mixture be followed successively by 25wt%, 35wt%, 37wt%, 0.5wt%, 1.5wt% and 1wt%.
(2) B component preparation
With fatty polyamide (the amine value be 200mgKOH/g, viscosity (40 ℃) for 500cps～5000cps) and methyl iso-butyl ketone (MIBK) by mechanical stirring mix mixture (B component), and fatty polyamide and the content (in weight percent concentration) of methyl iso-butyl ketone (MIBK) in the gained mixture are respectively 30wt% and 70wt%.
II. the test of antiseptic property
With the A component with after the B component is mixed by 3: 1 weight ratio mixture, with the medium carbon steel surface of this mixture brushing in oil removing, processing of rust removing, build is controlled at about 100 μ m.After the self-vulcanizing 7 days, it is immersed in the NaCl aqueous solution of 5wt%, uses electrochemical etching method, recording its corrosion potential is-316mV that corrosion current is 0.04 μ Acm
-2, to compare corrosion potential with comparative example 1 and improve 91mV, corrosion current reduces nearly 3 times, illustrates that the protective system that present embodiment makes has good preservative effect.
Embodiment 5
I. the preparation of protective system
(1) A component preparation
A, 60-120nm polyaniline in eigenstate nanofiber are put into propyl carbinol, through supersound process 2 hours, form the homodisperse liquid that contains 30% polyaniline nano fiber;
[kinematic viscosity is 1000mm for b, polyaniline in eigenstate nanofiber dispersion liquid, E-44 Resins, epoxy, N-BUTYL ACETATE, Disperbyk-160, aerosil, the dimethyl silicone oil that will be made by step a
2/ s (25 ℃)] after mixing mixture (A component), and make polyaniline nano fiber dispersion liquid, E-44 Resins, epoxy, N-BUTYL ACETATE, Disperbyk-160, aerosil and the dimethyl silicone oil content (in weight percent concentration) in this mixture be followed successively by 20wt%, 40wt%, 36wt%, 0.5wt%, 3wt% and 0.5wt%.
(2) B component preparation
With fatty polyamide (the amine value be 400mgKOH/g, viscosity (40 ℃) for 1000cps～20000cps) and N-BUTYL ACETATE by mechanical stirring mix mixture (B component), and fatty polyamide and the content (in weight percent concentration) of N-BUTYL ACETATE in the gained mixture are respectively 30wt% and 70wt%.
II. the test of antiseptic property
With the A component with after the B component is mixed by 2: 1 weight ratio mixture, with the medium carbon steel surface of this mixture brushing in oil removing, processing of rust removing, build is controlled at about 100 μ m.After the self-vulcanizing 7 days, it is immersed in the NaCl aqueous solution of 5wt%, uses electrochemical etching method, recording its corrosion potential is-310mV that corrosion current is 0.03 μ Acm
-2, to compare corrosion potential with comparative example 1 and improve 97mV, corrosion current reduces nearly 4 times, illustrates that the protective system that present embodiment makes has good preservative effect.
Claims (5)
1. a polyaniline anti-corrosive paint is characterized in that, said protective system is a two-component composition, by weight percentage, comprises following material,
The A component:
Resins, epoxy 35wt%～50wt%
Polyaniline 1wt%～50wt%
Thinner 5wt%～50wt%
Dispersion agent 0.5wt%～1wt%
Anti-settling agent 1.5wt%～3wt%
Defoamer 0.5wt%～1wt%
The B component:
Fatty polyamide 30wt%～50wt%
Thinner 50wt%～70wt%
Wherein: described Resins, epoxy is bisphenol A type epoxy resin; Described polyaniline is the polyaniline in eigenstate ultra-fine fibre, and the diameter of fiber is 30nm～120nm; The aliphatic alcohol of described thinner, ester or ketone compound; Described dispersion agent is Disperbyk-160; Described anti-settling agent is organobentonite or aerosil; Described defoamer is that kinematic viscosity (25 ℃) is 100-1000mm
2/ s dimethyl silicone oil.
2. polyaniline anti-corrosive paint as claimed in claim 1 is characterized in that, wherein said Resins, epoxy is E-51, E-44 or the E-20 Resins, epoxy of bisphenol A-type.
3. polyaniline anti-corrosive paint as claimed in claim 1 is characterized in that, the amine value of wherein said fatty polyamide is that 200mgKOH/g～400mgKOH/g, viscosity (40 ℃) are 500cps～20000cps.
4. polyaniline anti-corrosive paint as claimed in claim 1 is characterized in that, wherein said thinner is C
1～C
6Aliphatic monobasic alcohol.
5. polyaniline anti-corrosive paint as claimed in claim 4 is characterized in that, wherein said thinner is ethanol, Virahol or propyl carbinol.
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| CNA2007100473664A CN101143991A (en) | 2007-10-24 | 2007-10-24 | Polyaniline anticorrosion paint easy to disperse |
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|---|---|---|---|
| CNA2007100473664A CN101143991A (en) | 2007-10-24 | 2007-10-24 | Polyaniline anticorrosion paint easy to disperse |
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