CN105063594A - Special surface treating agent for antioxidant corrosion-resistant galvanized sheet and preparation method for special surface treating agent - Google Patents
Special surface treating agent for antioxidant corrosion-resistant galvanized sheet and preparation method for special surface treating agent Download PDFInfo
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Abstract
The invention discloses a special surface treating agent for an antioxidant corrosion-resistant galvanized sheet and a preparation method for the special surface treating agent. Acrylate adhesive solution particle surfaces contain a great number of carboxyl groups; aniline is added into an acrylate adhesive solution; an aniline monomer is firstly diffused into a micelle, then is doped with the carboxyl groups; then, under the action of the oxidant, the aniline generates polymerization reaction on latex particle surfaces, so that a contact angle between an aniline coating and water is increased, and adhesive force and water resistance are improved; the coating can enable a metal surface to passivate to generate protective effect by virtue of electron transfer effect and oxidation reduction effect; fluotitanic acid modified by silanization is formed into TiO2 particles in a heating and curing process because of an introduced inorganic component Ti<4+>; the TiO2 particles are uniformly filled into gaps of a silane film, so that the whole film layer is relatively uniform and compact, and micro-electrochemical reaction of the film layer surface can be effectively restrained, and therefore, 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 anti-oxidant anticorrosive galvanized sheet special surface treating agent 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 anti-oxidant anticorrosive galvanized sheet special surface treating agent and preparation method thereof.
The present invention is achieved by the following technical solutions:
A kind of anti-oxidant anticorrosive galvanized sheet special surface treating agent, it is made up of the raw material of following weight parts:
Zirconium tetrafluoride 1-2, sp-801.8-2, aniline 0.5-0.6, Potassium Persulphate 0.38-0.4, butyl acrylate 40-50, sodium bicarbonate 0.16-0.2, two (the silica-based propyl group of γ-triethoxy) tetrasulfide 20-30, the ethanol 100-110 of 70-75%, 30% hydrogen peroxidase 10 .2-0.3, deionized water 100-130, hydrofluotitanic acid 4-6, polyoxylethylene abietate 0.1-0.2, sal enixum 1-2, lauryl mercaptan 1-2, ammonium metaborate 2-3, maleic anhydride 1.8-2, Amino Trimethylene Phosphonic Acid 0.1-0.3.
Further scheme, it is made up of the raw material of following weight parts: Zirconium tetrafluoride 2-3, sp-801.9-2.1, aniline 0.5-0.7, Potassium Persulphate 0.39-0.41, butyl acrylate 40-50, sodium bicarbonate 0.16-0.2, two (the silica-based propyl group of γ-triethoxy) tetrasulfide 20-30, the ethanol 100-105 of 70-75%, 30% hydrogen peroxidase 10 .2-0.3, deionized water 100-125, hydrofluotitanic acid 4-6, polyoxylethylene abietate 0.1-0.2, sal enixum 1-2, lauryl mercaptan 1-2, ammonium metaborate 2-3, maleic anhydride 1.7-2, Amino Trimethylene Phosphonic Acid 0.1-0.3.
Further scheme, it is made up of the raw material of following weight parts:
Zirconium tetrafluoride 2, sp-801.9, aniline 0.5, Potassium Persulphate 0.39, butyl acrylate 40, sodium bicarbonate 0.16, two (the silica-based propyl group of γ-triethoxy) tetrasulfide 20, ethanol 100, the 30% hydrogen peroxidase 10 .2 of 70-75%, deionized water 100, hydrofluotitanic acid 4, polyoxylethylene abietate 0.1, sal enixum 1, lauryl mercaptan 1, ammonium metaborate 2, maleic anhydride 1.7, Amino Trimethylene Phosphonic Acid 0.1.
Further scheme, it is made up of the raw material of following weight parts:
Zirconium tetrafluoride 2, sp-802.0, aniline 0.6, Potassium Persulphate 0.40, butyl acrylate 42, sodium bicarbonate 0.17, two (the silica-based propyl group of γ-triethoxy) tetrasulfide 22, ethanol 103, the 30% hydrogen peroxidase 10 .22 of 70-75%, deionized water 110, hydrofluotitanic acid 5, polyoxylethylene abietate 0.13, sal enixum 1, lauryl mercaptan 1, ammonium metaborate 2, maleic anhydride 1.7, Amino Trimethylene Phosphonic Acid 0.1.
Further scheme, it is made up of the raw material of following weight parts:
Zirconium tetrafluoride 3, sp-802.1, aniline 0.7, Potassium Persulphate 0.40, butyl acrylate 45, sodium bicarbonate 0.19, two (the silica-based propyl group of γ-triethoxy) tetrasulfide 25, ethanol 103, the 30% hydrogen peroxidase 10 .3 of 70-75%, deionized water 120, hydrofluotitanic acid 5, polyoxylethylene abietate 0.2, sal enixum 2, lauryl mercaptan 2, ammonium metaborate 3, maleic anhydride 2, Amino Trimethylene Phosphonic Acid 0.3.
Further scheme, it is made up of the raw material of following weight parts:
Zirconium tetrafluoride 3, sp-802.1, aniline 0.7, Potassium Persulphate 0.41, butyl acrylate 50, sodium bicarbonate 0.2, two (the silica-based propyl group of γ-triethoxy) tetrasulfide 30, ethanol 105, the 30% hydrogen peroxidase 10 .3 of 70-75%, deionized water 125, hydrofluotitanic acid 6, polyoxylethylene abietate 0.2, sal enixum 2, lauryl mercaptan 2, ammonium metaborate 3, maleic anhydride 2, Amino Trimethylene Phosphonic Acid 0.3.
A preparation method for anti-oxidant anticorrosive galvanized sheet special surface treating agent, comprises the following steps:
(1) get the 86-90% of 40-50%, sp-80 weight of above-mentioned Potassium Persulphate weight, mix with sodium bicarbonate, add the 60-70% of deionized water weight, stir, obtain initiator emulsion;
(2) maleic anhydride is mixed with Amino Trimethylene Phosphonic Acid, join in 6-10 times of deionized water, at 60-70 DEG C, stir 6-10 minute, add lauryl mercaptan, adjustment PH is 3-4, stirring reaction 1-2 hour, add Zirconium tetrafluoride, 80-100 rev/min is stirred 20-30 minute, obtains rust protection liquid;
(3) 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, dropwises rear insulation reaction 1-2 hour, obtains acrylate glue;
(4) remaining Potassium Persulphate is joined in remaining deionized water, stir, obtain initiator solution;
(5) get the 12-15% of the ethanol weight of above-mentioned 70-75%, add polyoxylethylene abietate, 200-300 rev/min is stirred 10-20 minute, add sal enixum, ammonium metaborate, send in the water-bath of 70-80 DEG C, insulated and stirred 7-10 minute, obtains inorganic emulsion;
(6) by above-mentioned rust protection liquid, the mixing of inorganic emulsion, stir 1-2 hour, add acrylate glue, remaining sp-80, send in mulser, 800-1000 rev/min is stirred 3-5 minute, obtains acrylate emulsifying glue;
(7) get the ethanol of remaining 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;
(8) aniline is mixed with above-mentioned anti-oxidant acrylate emulsifying glue, stir, drip initiator solution, at 10-15 DEG C, 8-10 hour is reacted after dropwising, send in the water-bath of 65-70 DEG C, add fluorinated silane rust protection liquid, insulated and stirred reaction 1-2 hour, obtains silanization vinylformic acid-aniline copolymer emulsion;
(9) mixed with each raw material of residue by above-mentioned silanization vinylformic acid-aniline copolymer emulsion, 800-1000 rev/min is stirred 40-50 minute, obtains described galvanized sheet special surface treating agent.
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;
Treatment agent of the present invention is particularly suitable for zinc-plated plate surface, can galvanized sheet surface formed sticking power good, hardness is high and the passive film of excellent corrosion resistance.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail:
Embodiment 1:
A kind of anti-oxidant anticorrosive galvanized sheet special surface treating agent, is characterized in that what it was made up of the raw material of following weight parts:
Zirconium tetrafluoride 2, sp-801.9, aniline 0.5, Potassium Persulphate 0.39, butyl acrylate 40, sodium bicarbonate 0.16, two (the silica-based propyl group of γ-triethoxy) tetrasulfide 20, ethanol 100, the 30% hydrogen peroxidase 10 .2 of 70-75%, deionized water 100, hydrofluotitanic acid 4, polyoxylethylene abietate 0.1, sal enixum 1, lauryl mercaptan 1, ammonium metaborate 2, maleic anhydride 1.7, Amino Trimethylene Phosphonic Acid 0.1.
Embodiment 2:
A kind of anti-oxidant anticorrosive galvanized sheet special surface treating agent, is characterized in that what it was made up of the raw material of following weight parts:
Zirconium tetrafluoride 2, sp-802.0, aniline 0.6, Potassium Persulphate 0.40, butyl acrylate 42, sodium bicarbonate 0.17, two (the silica-based propyl group of γ-triethoxy) tetrasulfide 22, ethanol 103, the 30% hydrogen peroxidase 10 .22 of 70-75%, deionized water 110, hydrofluotitanic acid 5, polyoxylethylene abietate 0.13, sal enixum 1, lauryl mercaptan 1, ammonium metaborate 2, maleic anhydride 1.7, Amino Trimethylene Phosphonic Acid 0.1.
Embodiment 3:
A kind of anti-oxidant anticorrosive galvanized sheet special surface treating agent, is characterized in that what it was made up of the raw material of following weight parts:
Zirconium tetrafluoride 3, sp-802.1, aniline 0.7, Potassium Persulphate 0.40, butyl acrylate 45, sodium bicarbonate 0.19, two (the silica-based propyl group of γ-triethoxy) tetrasulfide 25, ethanol 103, the 30% hydrogen peroxidase 10 .3 of 70-75%, deionized water 120, hydrofluotitanic acid 5, polyoxylethylene abietate 0.2, sal enixum 2, lauryl mercaptan 2, ammonium metaborate 3, maleic anhydride 2, Amino Trimethylene Phosphonic Acid 0.3.
Embodiment 4:
A kind of anti-oxidant anticorrosive galvanized sheet special surface treating agent, is characterized in that what it was made up of the raw material of following weight parts:
Zirconium tetrafluoride 3, sp-802.1, aniline 0.7, Potassium Persulphate 0.41, butyl acrylate 50, sodium bicarbonate 0.2, two (the silica-based propyl group of γ-triethoxy) tetrasulfide 30, ethanol 105, the 30% hydrogen peroxidase 10 .3 of 70-75%, deionized water 125, hydrofluotitanic acid 6, polyoxylethylene abietate 0.2, sal enixum 2, lauryl mercaptan 2, ammonium metaborate 3, maleic anhydride 2, Amino Trimethylene Phosphonic Acid 0.3.
Embodiment 1-4, by preparation method's making once, comprises the following steps:
(1) get 50% of above-mentioned Potassium Persulphate weight, 90% of sp-80 weight, mix with sodium bicarbonate, add 70% of deionized water weight, stir, obtain initiator emulsion;
(2) maleic anhydride is mixed with Amino Trimethylene Phosphonic Acid, join in 10 times of deionized waters, stir 10 minutes at 60 DEG C, add lauryl mercaptan, regulate PH to be 3, stirring reaction 1 hour, add Zirconium tetrafluoride, 100 revs/min are stirred 20 minutes, obtain rust protection liquid;
(3) 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, dropwises rear insulation reaction 1 hour, obtains acrylate glue;
(4) remaining Potassium Persulphate is joined in remaining deionized water, stir, obtain initiator solution;
(5) get 15% of the ethanol weight of above-mentioned 75%, add polyoxylethylene abietate, 300 revs/min are stirred 10 minutes, and add sal enixum, ammonium metaborate, send in the water-bath of 80 DEG C, insulated and stirred 7-10 minute, obtains inorganic emulsion;
(6) by above-mentioned rust protection liquid, the mixing of inorganic emulsion, stir 1 hour, add acrylate glue, remaining sp-80, send in mulser, 1000 revs/min are stirred 5 minutes, obtain acrylate emulsifying glue;
(7) get the ethanol of remaining 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 7 hours, obtains fluorinated silane;
(8) aniline is mixed with above-mentioned anti-oxidant acrylate emulsifying glue, stir, drip initiator solution, react 10 hours at 15 DEG C after dropwising, send in the water-bath of 70 DEG C, add fluorinated silane rust protection liquid, insulated and stirred reacts 1 hour, obtains silanization vinylformic acid-aniline copolymer emulsion;
(9) mixed with each raw material of residue by above-mentioned silanization vinylformic acid-aniline copolymer emulsion, 1000 revs/min are stirred 40 minutes, obtain described galvanized sheet special surface treating agent.
Using method: zinc-plated sheet material surface cleaning is clean, drops in zinc-plated plate 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.
The performance test results is in table 1:
Water-intake rate: according to the method described above surface treatment agent of the present invention is coated on the zinc-plated plate surface being of a size of 5cm × 6cm, tests after soaking 48h in the deionized water of 25 DEG C;
Sticking power;
Erosion resistance: neutral salt spray test test in 72 hours;
Hardness.
Table 1 the performance test results
| Performance | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Water-intake rate/% | 15.8 | 15.6 | 15.9 | 15.4 |
| Sticking power | 1 grade | 1 grade | 1 grade | 1 grade |
| Erosion resistance/% | 1.6 | 1.5 | 1 | 1.3 |
| Hardness | 2H | 2H | 2H | 2H |
Claims (7)
1. an anti-oxidant anticorrosive galvanized sheet special surface treating agent, is characterized in that what it was made up of the raw material of following weight parts:
Zirconium tetrafluoride 1-3, sp-801.6-2.2, aniline 0.5-0.8, Potassium Persulphate 0.36-0.42, butyl acrylate 38-52, sodium bicarbonate 0.15-0.22, two (the silica-based propyl group of γ-triethoxy) tetrasulfide 18-32, the alcohol 95-110 of 70-75%, 30% hydrogen peroxidase 10 .1-0.3, deionized water 95-130, hydrofluotitanic acid 3-6, polyoxylethylene abietate 0.1-0.3, sal enixum 1-3, lauryl mercaptan 1-3, ammonium metaborate 2-4, maleic anhydride 1.6-2, Amino Trimethylene Phosphonic Acid 0.1-0.4.
2. the anti-oxidant anticorrosive galvanized sheet special surface treating agent of one according to claim 1, is characterized in that what it was made up of the raw material of following weight parts:
Zirconium tetrafluoride 2-3, sp-801.9-2.1, aniline 0.5-0.7, Potassium Persulphate 0.39-0.41, butyl acrylate 40-50, sodium bicarbonate 0.16-0.2, two (the silica-based propyl group of γ-triethoxy) tetrasulfide 20-30, the ethanol 100-105 of 70-75%, 30% hydrogen peroxidase 10 .2-0.3, deionized water 100-125, hydrofluotitanic acid 4-6, polyoxylethylene abietate 0.1-0.2, sal enixum 1-2, lauryl mercaptan 1-2, ammonium metaborate 2-3, maleic anhydride 1.7-2, Amino Trimethylene Phosphonic Acid 0.1-0.3.
3. the anti-oxidant anticorrosive galvanized sheet special surface treating agent of one according to claim 2, is characterized in that what it was made up of the raw material of following weight parts:
Zirconium tetrafluoride 2, sp-801.9, aniline 0.5, Potassium Persulphate 0.39, butyl acrylate 40, sodium bicarbonate 0.16, two (the silica-based propyl group of γ-triethoxy) tetrasulfide 20, ethanol 100, the 30% hydrogen peroxidase 10 .2 of 70-75%, deionized water 100, hydrofluotitanic acid 4, polyoxylethylene abietate 0.1, sal enixum 1, lauryl mercaptan 1, ammonium metaborate 2, maleic anhydride 1.7, Amino Trimethylene Phosphonic Acid 0.1.
4. the anti-oxidant anticorrosive galvanized sheet special surface treating agent of one according to claim 2, is characterized in that what it was made up of the raw material of following weight parts:
Zirconium tetrafluoride 2, sp-802.0, aniline 0.6, Potassium Persulphate 0.40, butyl acrylate 42, sodium bicarbonate 0.17, two (the silica-based propyl group of γ-triethoxy) tetrasulfide 22, ethanol 103, the 30% hydrogen peroxidase 10 .22 of 70-75%, deionized water 110, hydrofluotitanic acid 5, polyoxylethylene abietate 0.13, sal enixum 1, lauryl mercaptan 1, ammonium metaborate 2, maleic anhydride 1.7, Amino Trimethylene Phosphonic Acid 0.1.
5. the anti-oxidant anticorrosive galvanized sheet special surface treating agent of one according to claim 2, is characterized in that what it was made up of the raw material of following weight parts:
Zirconium tetrafluoride 3, sp-802.1, aniline 0.7, Potassium Persulphate 0.40, butyl acrylate 45, sodium bicarbonate 0.19, two (the silica-based propyl group of γ-triethoxy) tetrasulfide 25, ethanol 103, the 30% hydrogen peroxidase 10 .3 of 70-75%, deionized water 120, hydrofluotitanic acid 5, polyoxylethylene abietate 0.2, sal enixum 2, lauryl mercaptan 2, ammonium metaborate 3, maleic anhydride 2, Amino Trimethylene Phosphonic Acid 0.3.
6. the anti-oxidant anticorrosive galvanized sheet special surface treating agent of one according to claim 2, is characterized in that what it was made up of the raw material of following weight parts:
Zirconium tetrafluoride 3, sp-802.1, aniline 0.7, Potassium Persulphate 0.41, butyl acrylate 50, sodium bicarbonate 0.2, two (the silica-based propyl group of γ-triethoxy) tetrasulfide 30, ethanol 105, the 30% hydrogen peroxidase 10 .3 of 70-75%, deionized water 125, hydrofluotitanic acid 6, polyoxylethylene abietate 0.2, sal enixum 2, lauryl mercaptan 2, ammonium metaborate 3, maleic anhydride 2, Amino Trimethylene Phosphonic Acid 0.3.
7. a preparation method for the anti-oxidant anticorrosive galvanized sheet special surface treating agent as described in claim 1-6, is characterized in that comprising the following steps:
(1) get the 86-90% of 40-50%, sp-80 weight of above-mentioned Potassium Persulphate weight, mix with sodium bicarbonate, add the 60-70% of deionized water weight, stir, obtain initiator emulsion;
(2) maleic anhydride is mixed with Amino Trimethylene Phosphonic Acid, join in 6-10 times of deionized water, at 60-70 DEG C, stir 6-10 minute, add lauryl mercaptan, adjustment PH is 3-4, stirring reaction 1-2 hour, add Zirconium tetrafluoride, 80-100 rev/min is stirred 20-30 minute, obtains rust protection liquid;
(3) 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, dropwises rear insulation reaction 1-2 hour, obtains acrylate glue;
(4) remaining Potassium Persulphate is joined in remaining deionized water, stir, obtain initiator solution;
(5) get the 12-15% of the ethanol weight of above-mentioned 70-75%, add polyoxylethylene abietate, 200-300 rev/min is stirred 10-20 minute, add sal enixum, ammonium metaborate, send in the water-bath of 70-80 DEG C, insulated and stirred 7-10 minute, obtains inorganic emulsion;
(6) by above-mentioned rust protection liquid, the mixing of inorganic emulsion, stir 1-2 hour, add acrylate glue, remaining sp-80, send in mulser, 800-1000 rev/min is stirred 3-5 minute, obtains acrylate emulsifying glue;
(7) get the ethanol of remaining 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;
(8) aniline is mixed with above-mentioned anti-oxidant acrylate emulsifying glue, stir, drip initiator solution, at 10-15 DEG C, 8-10 hour is reacted after dropwising, send in the water-bath of 65-70 DEG C, add fluorinated silane rust protection liquid, insulated and stirred reaction 1-2 hour, obtains silanization vinylformic acid-aniline copolymer emulsion;
(9) mixed with each raw material of residue by above-mentioned silanization vinylformic acid-aniline copolymer emulsion, 800-1000 rev/min is stirred 40-50 minute, obtains described galvanized sheet special surface treating agent.
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Application publication date: 20151118 |