CN104988478A - Metal surface treatment agent for gelatinous film and preparation method of metal surface treatment agent - Google Patents
Metal surface treatment agent for gelatinous film and preparation method of metal surface treatment agent Download PDFInfo
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- CN104988478A CN104988478A CN201510411504.7A CN201510411504A CN104988478A CN 104988478 A CN104988478 A CN 104988478A CN 201510411504 A CN201510411504 A CN 201510411504A CN 104988478 A CN104988478 A CN 104988478A
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Abstract
The invention discloses a metal surface treatment agent for a gelatinous film. The surfaces of acrylate adhesive solution particles in the metal surface treatment agent contain a large amount of carboxyls; aniline is added into the acrylate adhesive solution; aniline monomers diffuse to the inside of a micelle first, and are then doped with the carboxyls; subsequently, under the action of an oxidant, the aniline generates a polymerization reaction on the surfaces of emulsion particles, so that a contact angle of a polyaniline coating to water is increased, and the adhesive force and the water resistance are improved; according to the coating, the surface of metal is passivated to form a protecting action under the actions of electron transfer and oxidation reduction; an inorganic component Ti<4+> introduced by silanization-modified hexafluorotitanic acid forms TiO2 particles in a heating and curing process, and the TiO2 particles are uniformly filled in the gaps of a silane film, so that the whole film layer is more uniform and compact, a micro electrochemical reaction on the surface of the film layer can be effectively inhibited, and further the corrosion resistance is greatly improved.
Description
Technical field
The present invention relates to a kind for the treatment of agent, particularly relate to a kind of gelatinous membrane metal conditioner and preparation method thereof.
Background technology
Polyaniline is a class conducting polymer composite; stable performance, environmental friendliness, and redox potential is far above metal; its coating can by transfer transport effect and redoxomorphism in acidity or neutral medium; making metal surface passivation produce provide protection, is the good material of anticorrosive metal, but; polyaniline molecule chain rigidity is strong; insolublely not melt, be difficult to processing, usually will with other filmogen compound uses.Acrylate resin is conventional filmogen, has good film-forming properties and sticking power.
At present, the mode of polyaniline and acrylate resin compound masking has 3 kinds: polyaniline coating applies acrylate finish paint and form compound coating, and 2 kinds of coatings play a role separately; Polyaniline powder is directly dispersed in acrylic resin as filler prepares coating; Both to be dissolved in same solvent brushing film forming on metal more altogether.Adopt emulsion latex interpenetrating polymerization legal system for polyaniline-acrylic resin anticorrosive coating, its coating has good Corrosion Protection.Utilize the carboxyl in acrylate polymer chains to the chanza of aniline, adopt situ aggregation method to synthesize acrylate-aniline; But research, mainly for the impact of aniline content on multipolymer dielectric properties, does not discuss the Corrosion Protection of multipolymer.At present, the report of anticorrosive is prepared about acrylate and aniline copolymerization also little.
Summary of the invention
The invention provides a kind of gelatinous membrane metal conditioner and preparation method thereof.
The present invention is achieved by the following technical solutions:
A kind of gelatinous membrane metal conditioner, it is made up of the raw material of following weight parts:
Zinc dibenzoate 0.1-0.2, Modulan 2.1-3, plant sterol 0.4-0.6, sp-80 1.8-2, aniline 0.5-0.6, butyl acrylate 40-50, sodium bicarbonate 0.16-0.2, the ethanol 100-110 of two (the silica-based propyl group of γ-triethoxy) tetrasulfide 20-30,70-75%, 30% hydrogen peroxidase 10 .2-0.3, deionized water 110-120, hydrofluotitanic acid 4-6, Potassium Persulphate 0.38-0.4, glyceryl monostearate 2-3, sodium bisulfite 1-2.
A preparation method for gelatinous membrane metal conditioner, comprises the following steps:
(1) get the 80-86% of 40-50%, sp-80 weight of above-mentioned Potassium Persulphate weight, mix with sodium bicarbonate, add deionized water weight 50-60%, stir, obtain initiator emulsion;
(2) get the 50-60% of residue deionized water weight, be heated to 80-90 DEG C, put into magnetic stirring apparatus, add glyceryl monostearate under agitation condition, be uniformly mixed 20-30 minute, add Zinc dibenzoate, stir, obtain esterification emulsion;
(3) get the 50-60% of residue deionized water weight, add remaining sp-80, after stirring, add above-mentioned Modulan, plant sterol, insulated and stirred 30-40 minute at 60-70 DEG C, obtain emulsification Wool wax alcohol;
(4) get the 45-50% of above-mentioned initiator emulsion weight, raised temperature is 80-86 DEG C, drips the mixed solution of remaining initiator emulsion and butyl acrylate, esterification emulsion is added after dropwising, send in the water-bath of 50-60 DEG C, insulated and stirred 1-2 hour, obtains acrylate glue;
(5) remaining Potassium Persulphate is joined in remaining deionized water, stir, obtain initiator solution;
(6) get the ethanol of above-mentioned 70-75%, add two (the silica-based propyl group of γ-triethoxy) tetrasulfide, adjustment PH is 3-4, and add hydrofluotitanic acid, 30% hydrogen peroxide, stirring reaction 6-7 hour, obtains fluorinated silane;
(7) aniline is mixed with aforesaid propylene acid esters glue, stir, drip initiator solution, at 10-15 DEG C, react 8-10 hour after dropwising, add sodium bisulfite, stir, send in the water-bath of 65-70 DEG C, add fluorinated silane, insulated and stirred reaction 1-2 hour, discharging cools, and obtains silanization vinylformic acid-aniline copolymer emulsion;
(8) mixed with emulsification Wool wax alcohol by above-mentioned silanization vinylformic acid-aniline copolymer emulsion, 500-600 rev/min is stirred 20-30 minute, adds each raw material of residue, and 800-1000 rev/min is stirred 40-50 minute, obtain described gelatinous membrane metal conditioner.
Advantage of the present invention is:
Acrylate adhesive liquid particles surface of the present invention is containing a large amount of carboxyls, aniline is joined in acrylate glue, first aniline monomer is diffused into micella inside, then adulterate with carboxyl, subsequently under the effect of oxygenant, aniline is at latex particle surface polymerization reaction take place, increase the contact angle of polyaniline coating to water, improve sticking power and water tolerance, this coating can by transfer transport effect and redoxomorphism, metal surface passivation is made to produce provide protection, the propylene glycol phenylate added can strengthen stability and the film-forming properties of coating, corrosive medium is effectively inhibit to immerse the process of post-etching,
And through the hydrofluotitanic acid of silylating reagent, the inorganic component Ti of introducing
4+tiO is formed in heat curing process
2particle, is filled in the space of silane film equably, makes whole rete even compact more, effectively can suppress micro-electrochemical reaction of film surface, thus corrosion resistance nature is greatly improved;
The present invention, by modified for hydrofluotitanic acid silane passive film and vinylformic acid-aniline copolymer membrane compound, makes rete finer and close, stable, and stronger to the resistance capabilities of corrosive medium, corrosion resistance nature is more excellent;
The surface treatment agent that the present invention adds can form gelatinous membrane in metallic substrate surface, can effectively suppress to get rusty.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail:
Embodiment 1:
A kind of gelatinous membrane metal conditioner, is characterized in that what it was made up of the raw material of following weight parts:
Ethanol 110,30% hydrogen peroxidase 10 .3, deionized water 120, hydrofluotitanic acid 4, Potassium Persulphate 0.38, glyceryl monostearate 3, the sodium bisulfite 1 of Zinc dibenzoate 0.1, Modulan 2.1, plant sterol 0.6, sp-80 1.8, aniline 0.6, butyl acrylate 50, sodium bicarbonate 0.16, two (the silica-based propyl group of γ-triethoxy) tetrasulfide 30,75%.
A preparation method for gelatinous membrane metal conditioner, comprises the following steps:
(1) get 50% of above-mentioned Potassium Persulphate weight, 86% of sp-80 weight, mix with sodium bicarbonate, add deionized water weight 60%, stir, obtain initiator emulsion;
(2) get 60% of residue deionized water weight, be heated to 90 DEG C, put into magnetic stirring apparatus, under agitation condition, add glyceryl monostearate, be uniformly mixed 30 minutes, add Zinc dibenzoate, stir, obtain esterification emulsion;
(3) get 60% of residue deionized water weight, add remaining sp-80, add above-mentioned Modulan, plant sterol after stirring, at 70 DEG C, insulated and stirred 30 minutes, obtains emulsification Wool wax alcohol;
(4) get 50% of above-mentioned initiator emulsion weight, raised temperature is 86 DEG C, drips the mixed solution of remaining initiator emulsion and butyl acrylate, adds esterification emulsion after dropwising, and send in the water-bath of 60 DEG C, insulated and stirred 1 hour, obtains acrylate glue;
(5) remaining Potassium Persulphate is joined in remaining deionized water, stir, obtain initiator solution;
(6) get the ethanol of above-mentioned 75%, add two (the silica-based propyl group of γ-triethoxy) tetrasulfide, regulate PH to be 3, add hydrofluotitanic acid, 30% hydrogen peroxide, stirring reaction 6 hours, obtains fluorinated silane;
(7) aniline is mixed with aforesaid propylene acid esters glue, stir, drip initiator solution, react 10 hours at 15 DEG C after dropwising, add sodium bisulfite, stir, send in the water-bath of 70 DEG C, add fluorinated silane, insulated and stirred reacts 1 hour, discharging cools, and obtains silanization vinylformic acid-aniline copolymer emulsion;
(8) mixed with emulsification Wool wax alcohol by above-mentioned silanization vinylformic acid-aniline copolymer emulsion, 600 revs/min are stirred 20 minutes, add each raw material of residue, and 1000 revs/min are stirred 40 minutes, obtain described gelatinous membrane metal conditioner.
Using method: cleaned up by sheet metal surface, drops in sheet metal surface uniformly by surface treatment agent of the present invention, first at 120 DEG C, toasts 30-40s, seasoning film forming, then at 80 DEG C drying and processing 15-20 minute.
Performance test:
Water-intake rate: according to the method described above surface treatment agent of the present invention is coated on the surface of steel plate being of a size of 5cm × 6cm, soaks 48 h in the deionized water of 25 DEG C, and recording water-intake rate is 16.6%;
Sticking power: 1 grade;
Erosion resistance: neutral salt spray test 72 hours, be corroded area 2.2%;
Hardness: 2H.
Claims (2)
1. a gelatinous membrane metal conditioner, is characterized in that what it was made up of the raw material of following weight parts:
Zinc dibenzoate 0.1-0.2, Modulan 2.1-3, plant sterol 0.4-0.6, sp-80 1.8-2, aniline 0.5-0.6, butyl acrylate 40-50, sodium bicarbonate 0.16-0.2, the ethanol 100-110 of two (the silica-based propyl group of γ-triethoxy) tetrasulfide 20-30,70-75%, 30% hydrogen peroxidase 10 .2-0.3, deionized water 110-120, hydrofluotitanic acid 4-6, Potassium Persulphate 0.38-0.4, glyceryl monostearate 2-3, sodium bisulfite 1-2.
2. a preparation method for gelatinous membrane metal conditioner as claimed in claim 1, is characterized in that comprising the following steps:
(1) get the 80-86% of 40-50%, sp-80 weight of above-mentioned Potassium Persulphate weight, mix with sodium bicarbonate, add deionized water weight 50-60%, stir, obtain initiator emulsion;
(2) get the 50-60% of residue deionized water weight, be heated to 80-90 DEG C, put into magnetic stirring apparatus, add glyceryl monostearate under agitation condition, be uniformly mixed 20-30 minute, add Zinc dibenzoate, stir, obtain esterification emulsion;
(3) get the 50-60% of residue deionized water weight, add remaining sp-80, after stirring, add above-mentioned Modulan, plant sterol, insulated and stirred 30-40 minute at 60-70 DEG C, obtain emulsification Wool wax alcohol;
(4) get the 45-50% of above-mentioned initiator emulsion weight, raised temperature is 80-86 DEG C, drips the mixed solution of remaining initiator emulsion and butyl acrylate, esterification emulsion is added after dropwising, send in the water-bath of 50-60 DEG C, insulated and stirred 1-2 hour, obtains acrylate glue;
(5) remaining Potassium Persulphate is joined in remaining deionized water, stir, obtain initiator solution;
(6) get the ethanol of above-mentioned 70-75%, add two (the silica-based propyl group of γ-triethoxy) tetrasulfide, adjustment PH is 3-4, and add hydrofluotitanic acid, 30% hydrogen peroxide, stirring reaction 6-7 hour, obtains fluorinated silane;
(7) aniline is mixed with aforesaid propylene acid esters glue, stir, drip initiator solution, at 10-15 DEG C, react 8-10 hour after dropwising, add sodium bisulfite, stir, send in the water-bath of 65-70 DEG C, add fluorinated silane, insulated and stirred reaction 1-2 hour, discharging cools, and obtains silanization vinylformic acid-aniline copolymer emulsion;
(8) mixed with emulsification Wool wax alcohol by above-mentioned silanization vinylformic acid-aniline copolymer emulsion, 500-600 rev/min is stirred 20-30 minute, adds each raw material of residue, and 800-1000 rev/min is stirred 40-50 minute, obtain described gelatinous membrane metal conditioner.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105401141A (en) * | 2015-11-04 | 2016-03-16 | 合肥海源机械有限公司 | Gel aluminum alloy cured film forming solution and preparation method thereof |
| CN107083188A (en) * | 2017-04-26 | 2017-08-22 | 芜湖亨益汽车运输有限公司 | A kind of automobile engine cover sheetmetal surface conditioning agent and preparation method thereof |
| CN107418437A (en) * | 2017-04-26 | 2017-12-01 | 芜湖亨益汽车运输有限公司 | A kind of car door metal conditioner and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105401141A (en) * | 2015-11-04 | 2016-03-16 | 合肥海源机械有限公司 | Gel aluminum alloy cured film forming solution and preparation method thereof |
| CN107083188A (en) * | 2017-04-26 | 2017-08-22 | 芜湖亨益汽车运输有限公司 | A kind of automobile engine cover sheetmetal surface conditioning agent and preparation method thereof |
| CN107418437A (en) * | 2017-04-26 | 2017-12-01 | 芜湖亨益汽车运输有限公司 | A kind of car door metal conditioner and preparation method thereof |
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