CN103059727B - A kind of Metal surface silane treatment agent containing HMPA and preparation method thereof - Google Patents
A kind of Metal surface silane treatment agent containing HMPA and preparation method thereof Download PDFInfo
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- CN103059727B CN103059727B CN201210550732.9A CN201210550732A CN103059727B CN 103059727 B CN103059727 B CN 103059727B CN 201210550732 A CN201210550732 A CN 201210550732A CN 103059727 B CN103059727 B CN 103059727B
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Abstract
The invention discloses a kind of Metal surface silane treatment agent containing HMPA, it is characterized in that, by the formulated mixed solution of following component, in often liter of mixed solution, the weight part (gram) of each component is: anilinomethyl triethoxysilane 35-45, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane 35-45, water nano zinc oxide material 100-180, glycerine 3-4, glycol ether 2-3, ethylene glycol monobutyl ether 2-4, titanium tetrafluoride 2-3, HMPA 2-3, urea 2-3, citric acid 1-2, azimidobenzene 0.3-0.6, remaining for water; Advantage of the present invention is: the silane coating formed in metallic surface after using silane surface treatment agent process metal of the present invention has excellent corrosion resistance nature, extend the work-ing life of metal, to be combined use by anilinomethyl triethoxysilane and N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, densification can be formed in metallic surface and firmly coating.
Description
Technical field
The present invention relates generally to a kind of Metal surface silane treatment agent and preparation method thereof, particularly relates to a kind of Metal surface silane treatment agent containing HMPA and preparation method thereof.
Background technology
In field of metal surface treatment, although traditional phosphate conversion and chromating process for treating surface can obtain good effect, but containing zinc in the waste liquid of discharging in treating processes, manganese, nickel, the carcinogenic substances such as heavy metal ion and nitrite such as chromium, environmental pollution is very serious, and metallic surface silanization treatment technology is due to the material of not hurm involved environment, energy consumption in production process is low, technical applications is extensive, be considered to be expected to replace phosphate conversion process and chromating process, that recent development direction is protected separately in metallic surface, the rete of the surface of workpiece formation of solution of silane process in existing technology, Density inhomogeneity, there is cavity, split sunken, with metallic object hold up put forth effort not strong.
Summary of the invention
The object of the invention is exactly the defect in order to make up prior art, provides Metal surface silane treatment agent of a kind of water nano zinc oxide material and preparation method thereof.
The present invention is achieved by the following technical solutions:
A Metal surface silane treatment agent containing HMPA, the mixed solution formulated by following component, in often liter of mixed solution, the weight part (gram) of each component is:
Anilinomethyl triethoxysilane 35-45, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane 35-45, water nano zinc oxide material 100-180, glycerine 3-4, glycol ether 2-3, ethylene glycol monobutyl ether 2-4, titanium tetrafluoride 2-3, HMPA 2-3, urea 2-3, citric acid 1-2, azimidobenzene 0.3-0.6, remaining be water;
The preparation method of described water nano zinc oxide material is:
(1) by nano zine oxide ultrasonic disperse in its quality 5-10 dehydrated alcohol doubly, obtain dispersion liquid, then the dicumyl peroxide of its quality 3-4%, the anilinomethyl triethoxysilane of 1-2% are added in above-mentioned dispersion liquid, back flow reaction 1-2 hour at 80-90 DEG C of temperature, coupling agent modified nano zine oxide-the alcohol suspension with reactive group is obtained after reaction, then filter, centrifugation filtrate, obtains modified nano zinc oxide;
(2) glycerol is water-soluble, then add above-mentioned modified nano zinc oxide, ball-milling processing 1-2 hour in ball mill, obtain modified nano zinc oxide slurry;
(3) N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane is dissolved in ethanol, be prepared into the solution that mass concentration is 2-4%, join in above-mentioned modified nano zinc oxide slurry, be 4-5 by acetic acid or sodium-acetate adjust ph, ball-milling processing 2-3 hour again, obtains described water nano zinc oxide material.
A kind of Metal surface silane treatment agent containing HMPA, in the preparation method of described water nano zinc oxide material, the mass ratio of the water in described nano zine oxide, glycerol, vinyl three ('beta '-methoxy oxyethyl group) silane and step (2), the ethanol in step (3) is: nano zine oxide: glycerol: N-(β-aminoethyl)-γ-aminopropyl trimethoxy silicon: water: ethanol is 10-15g:1-2g:2-4g:95-105 gram: 95-105 gram.
The granularity of described nano zine oxide is 40-50nm.
A preparation method for Metal surface silane treatment agent containing HMPA, comprises the following steps:
(1) anilinomethyl triethoxysilane of above-mentioned weight part is added in the water of above-mentioned weight part 60-70%, add N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane of above-mentioned weight part after fully dissolving again, fully stir, obtain compound A;
(2) get the 60-70% of residue water, add the water nano zinc oxide material of above-mentioned weight part, after fully stirring, add the titanium tetrafluoride of above-mentioned weight part, HMPA, urea, citric acid fully stir, obtain compound B;
(3) glycerine of above-mentioned weight part and glycol ether are mixed with remaining water, be heated to 40-50 DEG C, then add the azimidobenzene of above-mentioned weight part, be stirred to azimidobenzene and dissolve completely, obtain compound C;
(4) by compound A, B and C mixing obtained above, then acetic acid or sodium-acetate, adjustment PH is 3-5, finally adds the ethylene glycol monobutyl ether of above-mentioned weight part, namely obtains the described Metal surface silane treatment agent containing HMPA after fully stirring.
Advantage of the present invention is:
The silane coating formed in metallic surface after using silane surface treatment agent process metal of the present invention has excellent corrosion resistance nature, extend the work-ing life of metal, to be combined use by anilinomethyl triethoxysilane and N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, densification can be formed and firmly coating in metallic surface, and with water nano zinc oxide material prepared by technique of the present invention, there is high dispersion stability and efficient binding property, it is evenly distributed in metallic surface, metal is made to have the perviousness of high compactness and anti-ion, the auxiliary agents such as the titanium tetrafluoride added, add the density of silane adsorption film, improve quality of forming film, rete is made to have strong adhesion, without cavity, split sunken, dense uniform, the feature that polarized current density is little, and production process environmental protection, pollution-free.
Embodiment
Embodiment 1
A Metal surface silane treatment agent containing HMPA, the mixed solution formulated by following component, in often liter of mixed solution, the weight part (gram) of each component is:
Anilinomethyl triethoxysilane 45, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane 45, water nano zinc oxide material 140, glycerine 4, glycol ether 3, ethylene glycol monobutyl ether 4, titanium tetrafluoride 3, HMPA 3, urea 3, citric acid 1, azimidobenzene 0.6, remaining be water;
The preparation method of described water nano zinc oxide material is:
(1) by nano zine oxide ultrasonic disperse in the dehydrated alcohol of its quality 10 times, obtain dispersion liquid, then the dicumyl peroxide of its quality 3%, the anilinomethyl triethoxysilane of 2% are added in above-mentioned dispersion liquid, back flow reaction 2 hours at 90 DEG C of temperature, coupling agent modified nano zine oxide-the alcohol suspension with reactive group is obtained after reaction, then filter, centrifugation filtrate, obtains modified nano zinc oxide;
(2) glycerol is water-soluble, then add above-mentioned modified nano zinc oxide, in ball mill, ball-milling processing 1 hour, obtains modified nano zinc oxide slurry;
(3) N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane is dissolved in ethanol, be prepared into the solution that mass concentration is 4%, join in above-mentioned modified nano zinc oxide slurry, be 4-5 by acetic acid or sodium-acetate adjust ph, ball-milling processing 2-3 hour again, obtains described water nano zinc oxide material.
In the preparation method of described water nano zinc oxide material, the mass ratio of the water in described nano zine oxide, glycerol, vinyl three ('beta '-methoxy oxyethyl group) silane and step (2), the ethanol in step (3) is: nano zine oxide: glycerol: N-(β-aminoethyl)-γ-aminopropyl trimethoxy silicon: water: ethanol is 10-15g:1-2g:2-4g:95-105 gram: 95-105 gram.
The granularity of described nano zine oxide is 40-50nm.
A preparation method for Metal surface silane treatment agent containing HMPA, comprises the following steps:
(1) anilinomethyl triethoxysilane of above-mentioned weight part is added in the water of above-mentioned weight part 60-70%, add N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane of above-mentioned weight part after fully dissolving again, fully stir, obtain compound A;
(2) get the 60-70% of residue water, add the water nano zinc oxide material of above-mentioned weight part, after fully stirring, add the titanium tetrafluoride of above-mentioned weight part, HMPA, urea, citric acid fully stir, obtain compound B;
(3) glycerine of above-mentioned weight part and glycol ether are mixed with remaining water, be heated to 40-50 DEG C, then add the azimidobenzene of above-mentioned weight part, be stirred to azimidobenzene and dissolve completely, obtain compound C;
(4) by compound A, B and C mixing obtained above, then acetic acid or sodium-acetate, adjustment PH is 3-5, finally adds the ethylene glycol monobutyl ether of above-mentioned weight part, namely obtains the described Metal surface silane treatment agent containing HMPA after fully stirring.
Performance test:
Bending viscosity:
With silane surface treatment agent process metal aluminium flake of the present invention, by bending 60 degree of aluminium flake doubling, peel off curved part 3 times with adhesive tape, under X20 magnifying glass, detect extent of exfoliation, result flawless; With silane surface treatment agent process metal aluminium flake of the present invention, aluminium flake is soaked 1 hour in boiling water, at room temperature place 24 hours, then by bending 60 degree of aluminium flake doubling, peel off curved part 3 times with adhesive tape, under X20 magnifying glass, detect extent of exfoliation, result flawless;
Erosion resistance:
With silane surface treatment agent process steel plate galvanized metallic substance of the present invention, by this material lateral dissection, carry out spray test, agents useful for same to be concentration be 5% sodium chloride solution, test period 300 hours, measure the bubbling width formed in line of cut side, result bubbling width is 0; With silane surface treatment agent process metallic substance of the present invention, this material being immersed in concentration is in the sodium chloride solution of 5%, and soak 300 hours, material surface is substantially unchanged, and soak 400 hours, minute quantity rust staining appears in edge.
Claims (2)
1. the Metal surface silane treatment agent containing HMPA, is characterized in that by the formulated mixed solution of following component, by the weight part of each component in gram calculating often liter of mixed solution is:
Anilinomethyl triethoxysilane 35-45, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane 35-45, water nano zinc oxide material 100-180, glycerine 3-4, glycol ether 2-3, ethylene glycol monobutyl ether 2-4, titanium tetrafluoride 2-3, stablizer HMPA 2-3, urea 2-3, citric acid 1-2, azimidobenzene 0.3-0.6, remaining be water;
The preparation method of described water nano zinc oxide material is:
(1) by nano zine oxide ultrasonic disperse in its quality 5-10 dehydrated alcohol doubly, obtain dispersion liquid, then the dicumyl peroxide of its quality 3-4%, the anilinomethyl triethoxysilane of 1-2% are added in above-mentioned dispersion liquid, back flow reaction 1-2 hour at 80-90 DEG C of temperature, coupling agent modified nano zine oxide-the alcohol suspension with reactive group is obtained after reaction, then filter, centrifugation filtrate, obtains modified nano zinc oxide;
(2) glycerol is water-soluble, then add above-mentioned modified nano zinc oxide, ball-milling processing 1-2 hour in ball mill, obtain modified nano zinc oxide slurry;
(3) N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane is dissolved in ethanol, be prepared into the solution that mass concentration is 2-4%, join in above-mentioned modified nano zinc oxide slurry, be 4-5 by acetic acid adjust ph, ball-milling processing 2-3 hour again, obtains described water nano zinc oxide material.
2. a kind of Metal surface silane treatment agent containing HMPA according to claim 1, is characterized in that the granularity of described nano zine oxide is 40-50nm.
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| CN201210550732.9A CN103059727B (en) | 2012-12-18 | 2012-12-18 | A kind of Metal surface silane treatment agent containing HMPA and preparation method thereof |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008062618A1 (en) * | 2006-11-21 | 2008-05-29 | Nihon Parkerizing Co., Ltd. | Aqueous surface treatment for environment-friendly precoated metal materials, surface-treated metal materials, and environment-friendly precoated metal materials |
| CN101857755A (en) * | 2010-06-30 | 2010-10-13 | 张俊锋 | Emulsion paint coating surface water-repellent coating agent and preparation method thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008062618A1 (en) * | 2006-11-21 | 2008-05-29 | Nihon Parkerizing Co., Ltd. | Aqueous surface treatment for environment-friendly precoated metal materials, surface-treated metal materials, and environment-friendly precoated metal materials |
| CN101857755A (en) * | 2010-06-30 | 2010-10-13 | 张俊锋 | Emulsion paint coating surface water-repellent coating agent and preparation method thereof |
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