CN103031056A - Metal surface silane treating agent containing aqueous nano-zinc oxide and preparation method thereof - Google Patents
Metal surface silane treating agent containing aqueous nano-zinc oxide and preparation method thereof Download PDFInfo
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- CN103031056A CN103031056A CN2012105509339A CN201210550933A CN103031056A CN 103031056 A CN103031056 A CN 103031056A CN 2012105509339 A CN2012105509339 A CN 2012105509339A CN 201210550933 A CN201210550933 A CN 201210550933A CN 103031056 A CN103031056 A CN 103031056A
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Abstract
The invention discloses a metal surface silane treating agent containing aqueous nano-zinc oxide. The metal surface silane treating agent is characterized by being a mixture solution prepared from the following ingredients in parts by weight (gram) in each liter of the mixture: 20-30 parts of propyl trimethoxy silane, 30-40 parts of aminopropyl triethoxy silane, 100-200 parts of aqueous nano-zinc oxide, 2-4 parts of propylene glycol, 2-4 parts of zirconium fluoride, 1-2 parts of ethylene glycol monobutyl ether, 0.8-1 parts of sodium monofluorophosphate, 2-3 parts of ethylene diamine tetramethylene risedremate sodium, 1-2 parts of urea, 0.6-0.8 parts of crylic acid, 0.4-0.6 parts of carboxymethyl cellulose and the balance of water. The metal surface silane treating agent has the advantages that a silane coating layer formed on the surface of a metal after the metal is treated by using the surface silane treating agent provided by the invention has excellent corrosion resistance performance, the service life of the metal is prolonged, and by combining the propyl trimethoxy silane and the aminopropyl triethoxy silane, a compact and solid coating layer is formed on the surface of the metal.
Description
Technical field
The present invention relates generally to a kind of metallic surface silane finish and preparation method thereof, relates in particular to a kind of metallic surface silane finish that contains water nano zinc oxide material 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 contain zinc in the waste liquid of discharging in the treating processes, manganese, nickel, the carcinogenic substances such as the heavy metal ion such as chromium and nitrite, environmental pollution is very serious, and the metallic surface silanization treatment technology is because the material of hurm involved environment not, energy consumption in production process is low, technical applications is extensive, be considered to be expected to replace phosphate conversion processing and chromating processing, that the recent development direction is protected separately in the metallic surface, the rete that the surface of workpiece that solution of silane was processed in the existing technology forms, Density inhomogeneity, the cavity is arranged, split sunken, put forth effort not strong with holding up of metallic object, ethylenediamine tetramethylene fork Alendronate belongs to the cathode type inhibiter, compare with inorganic polyphosphate, the high 3-5 of corrosion inhibition rate doubly can be miscible with water, nontoxic pollution-free, chemical stability and temperature tolerance are good, still have good scale inhibition effect under 200 ℃.
Summary of the invention
The object of the invention is exactly in order to remedy the defective of prior art, metallic surface silane finish of a kind of water nano zinc oxide material and preparation method thereof to be provided.
The present invention is achieved by the following technical solutions:
A kind of metallic surface silane finish that contains water nano zinc oxide material, by the formulated mixed solution of following component, the weight part (gram) of each component is in every liter of mixed solution:
Propyl trimethoxy silicane 20-30, aminopropyl triethoxysilane 30-40, water nano zinc oxide material 100-200, propylene glycol 2-4, Zirconium tetrafluoride 2-4, ethylenediamine tetramethylene fork Alendronate 2-3, ethylene glycol monobutyl ether 1-2, urea 1-2, sodium monoflurophosphate 0.8-1, vinylformic acid 0.6-0.8, carboxymethyl cellulose 0.4-0.6, remaining be water.
The preparation method of described water nano zinc oxide material is:
(1) with the nano zine oxide ultra-sonic dispersion in its quality 5-10 dehydrated alcohol doubly, obtain dispersion liquid, then the dicumyl peroxide of its quality 3-4%, the vinyl three of 1-2% ('beta '-methoxy oxyethyl group) silane are added in the above-mentioned dispersion liquid, under 80-90 ℃ of temperature back flow reaction 1-2 hour, obtain the coupling agent modified nano zine oxide-alcohol suspension with reactive group after the reaction, then filter, centrifugation filtrate obtains modified nano zinc oxide;
(2) with TriMethylolPropane(TMP), water-soluble, then add above-mentioned modified nano zinc oxide, in ball mill ball-milling processing 1-2 hour, obtain the modified nano zinc oxide slurry;
(3) vinyl three ('beta '-methoxy oxyethyl group) silane is dissolved in the ethanol, be prepared into the solution that mass concentration is 2-4%, join in the above-mentioned modified nano zinc oxide slurry, regulating the pH value with acetic acid or deionized water is 3-5, ball-milling processing 2-3 hour again, obtain described water nano zinc oxide material.
Among the preparation method of described water nano zinc oxide material, the water in described nano zine oxide, TriMethylolPropane(TMP), vinyl three ('beta '-methoxy oxyethyl group) silane and the step (2), the mass ratio of the ethanol in the step (3) are: nano zine oxide: TriMethylolPropane(TMP): vinyl three ('beta '-methoxy oxyethyl group) silane: water: ethanol is the 10-15g:1g:2-3g:90-110 gram: the 95-105 gram.
The granularity of described nano zine oxide is 40-50nm.
A kind of preparation method who contains the metallic surface silane finish of water nano zinc oxide material may further comprise the steps:
(1) propyl trimethoxy silicane with above-mentioned weight part adds in the water of above-mentioned weight part 60-70%, fully adds the aminopropyl triethoxysilane of above-mentioned weight part after the dissolving again, fully stirs, and gets compound A;
(2) the water nano zinc oxide material of the above-mentioned weight part of adding in remaining water after fully stirring, adds Zirconium tetrafluoride, ethylene glycol monobutyl ether, urea, vinylformic acid, sodium monoflurophosphate, the carboxymethyl cellulose of above-mentioned weight part, fully stirs, and gets compound B;
(3) compound A obtained above and B are mixed, add acetic acid or deionized water, adjusting PH is 3-5, then adds each raw material of residue, namely gets the described metallic surface silane finish that contains water nano zinc oxide material after fully stirring.
Advantage of the present invention is:
Use silane surface treatment agent of the present invention to process the silane coating that forms in the metallic surface behind the metal and have excellent corrosion resistance nature, prolonged the work-ing life of metal, by the use that combines of propyl trimethoxy silicane and aminopropyl triethoxysilane, can form densification in the metallic surface and coating firmly, and have high dispersion stability and efficient binding property with the water nano zinc oxide material of technique preparation of the present invention, it is evenly distributed in the metallic surface, so that metal has high compactness and the perviousness of anti-ion, the Zirconium tetrafluoride that adds, the auxiliary agents such as ethylenediamine tetramethylene fork Alendronate, increased the density of silane adsorption film, improved quality of forming film, so that rete has strong adhesion, without the cavity, split sunken, evenly fine and close, the characteristics that polarized current density is little, and production process environmental protection, pollution-free.
Embodiment
Embodiment 1
A kind of metallic surface silane finish that contains water nano zinc oxide material, by the formulated mixed solution of following component, the weight part (gram) of each component is in every liter of mixed solution:
Propyl trimethoxy silicane 30, aminopropyl triethoxysilane 40, water nano zinc oxide material 200, propylene glycol 4, Zirconium tetrafluoride 4, ethylene glycol monobutyl ether 2, sodium monoflurophosphate 1, ethylenediamine tetramethylene fork Alendronate 2, urea 2, vinylformic acid 0.8, carboxymethyl cellulose 0.6, remaining be water.
The preparation method of described water nano zinc oxide material is:
(1) with the nano zine oxide ultra-sonic dispersion in the dehydrated alcohol of 10 times of its quality, obtain dispersion liquid, then the dicumyl peroxide of its quality 3%, 2% vinyl three ('beta '-methoxy oxyethyl group) silane are added in the above-mentioned dispersion liquid, back flow reaction is 2 hours under 90 ℃ of temperature, obtain the coupling agent modified nano zine oxide-alcohol suspension with reactive group after the reaction, then filter, centrifugation filtrate obtains modified nano zinc oxide;
(2) with TriMethylolPropane(TMP), water-soluble, then add above-mentioned modified nano zinc oxide, ball-milling processing is 1 hour in ball mill, obtains the modified nano zinc oxide slurry;
(3) vinyl three ('beta '-methoxy oxyethyl group) silane is dissolved in the ethanol, be prepared into mass concentration and be 4% solution, join in the above-mentioned modified nano zinc oxide slurry, regulating the pH value with acetic acid or deionized water is 3, ball-milling processing is 2 hours again, obtains described water nano zinc oxide material.
Among the preparation method of described water nano zinc oxide material, the water in described nano zine oxide, TriMethylolPropane(TMP), vinyl three ('beta '-methoxy oxyethyl group) silane and the step (2), the mass ratio of the ethanol in the step (3) are: nano zine oxide: TriMethylolPropane(TMP): vinyl three ('beta '-methoxy oxyethyl group) silane: water: ethanol is the 10g:1g:2g:110 gram: 95 grams.
The granularity of described nano zine oxide is 50nm.
A kind of preparation method who contains the metallic surface silane finish of water nano zinc oxide material may further comprise the steps:
(1) propyl trimethoxy silicane with above-mentioned weight part adds in the water of above-mentioned weight part 70%, fully adds the aminopropyl triethoxysilane of above-mentioned weight part after the dissolving again, fully stirs, and gets compound A;
(2) the water nano zinc oxide material of the above-mentioned weight part of adding in remaining water after fully stirring, adds Zirconium tetrafluoride, ethylene glycol monobutyl ether, urea, sodium monoflurophosphate, vinylformic acid, the carboxymethyl cellulose of above-mentioned weight part, fully stirs, and gets compound B;
(3) compound A obtained above and B are mixed, add acetic acid or deionized water, regulating PH is 3, then adds each raw material of residue, namely gets the described metallic surface silane finish that contains water nano zinc oxide material after fully stirring.
Performance test:
Crooked viscosity:
Process the metal aluminium flake with silane surface treatment agent of the present invention, with crooked 60 degree of aluminium flake doubling, peel off curved part 3 times with adhesive tape, under the X20 magnifying glass, detect extent of exfoliation, as a result flawless; Process the metal aluminium flake with silane surface treatment agent of the present invention, aluminium flake was soaked in boiling water 1 hour, at room temperature placed 24 hours, then with crooked 60 degree of aluminium flake doubling, peel off curved part 3 times with adhesive tape, under the X20 magnifying glass, detect extent of exfoliation, as a result flawless;
Erosion resistance:
Process the steel plate galvanized metallic substance with silane surface treatment agent of the present invention, with this material lateral dissection, carry out spray test, agents useful for same is that concentration is 5% sodium chloride solution, test period 300 hours is measured the bubbling width that forms in line of cut one side, and the bubbling width is 0 as a result; Process metallic substance with silane surface treatment agent of the present invention, it is in 5% the sodium chloride solution that this material is immersed in concentration, soaks 300 hours, and material surface is substantially unchanged, soaks 400 hours, and the minute quantity rust staining appears in the edge.
Claims (4)
1. a metallic surface silane finish that contains water nano zinc oxide material it is characterized in that by the formulated mixed solution of following component, and the weight part (gram) of each component is in every liter of mixed solution:
Propyl trimethoxy silicane 20-30, aminopropyl triethoxysilane 30-40, water nano zinc oxide material 100-200, propylene glycol 2-4, Zirconium tetrafluoride 2-4, ethylene glycol monobutyl ether 1-2, ethylenediamine tetramethylene fork Alendronate 2-3, urea 1-2, sodium monoflurophosphate 0.8-1, vinylformic acid 0.6-0.8, carboxymethyl cellulose 0.4-0.6, remaining be water;
The preparation method of described water nano zinc oxide material is:
(1) with the nano zine oxide ultra-sonic dispersion in its quality 5-10 dehydrated alcohol doubly, obtain dispersion liquid, then the dicumyl peroxide of its quality 3-4%, the vinyl three of 1-2% ('beta '-methoxy oxyethyl group) silane are added in the above-mentioned dispersion liquid, under 80-90 ℃ of temperature back flow reaction 1-2 hour, obtain the coupling agent modified nano zine oxide-alcohol suspension with reactive group after the reaction, then filter, centrifugation filtrate obtains modified nano zinc oxide;
(2) TriMethylolPropane(TMP) is water-soluble, then add above-mentioned modified nano zinc oxide, in ball mill ball-milling processing 1-2 hour, obtain the modified nano zinc oxide slurry;
(3) vinyl three ('beta '-methoxy oxyethyl group) silane is dissolved in the ethanol, be prepared into the solution that mass concentration is 2-4%, join in the above-mentioned modified nano zinc oxide slurry, regulating the pH value with acetic acid or deionized water is 3-5, ball-milling processing 2-3 hour again, obtain described water nano zinc oxide material.
2. a kind of metallic surface silane finish that contains water nano zinc oxide material according to claim 1, it is characterized in that, among the preparation method of described water nano zinc oxide material, the water in described nano zine oxide, TriMethylolPropane(TMP), vinyl three ('beta '-methoxy oxyethyl group) silane and the step (2), the mass ratio of the ethanol in the step (3) are: nano zine oxide: TriMethylolPropane(TMP): vinyl three ('beta '-methoxy oxyethyl group) silane: water: ethanol is the 10-15g:1g:2-3g:90-110 gram: the 95-105 gram.
3. a kind of metallic surface silane finish that contains water nano zinc oxide material according to claim 1, the granularity that it is characterized in that described nano zine oxide is 40-50nm.
4. preparation method who contains the metallic surface silane finish of water nano zinc oxide material as claimed in claim 1 is characterized in that may further comprise the steps:
(1) propyl trimethoxy silicane with above-mentioned weight part adds in the water of above-mentioned weight part 60-70%, fully adds the aminopropyl triethoxysilane of above-mentioned weight part after the dissolving again, fully stirs, and gets compound A;
(2) the water nano zinc oxide material of the above-mentioned weight part of adding in remaining water after fully stirring, adds Zirconium tetrafluoride, ethylene glycol monobutyl ether, urea, sodium monoflurophosphate, vinylformic acid, the carboxymethyl cellulose of above-mentioned weight part, fully stirs, and gets compound B;
(3) compound A obtained above and B are mixed, add acetic acid or deionized water, adjusting PH is 3-5, then adds each raw material of residue, namely gets the described metallic surface silane finish that contains water nano zinc oxide material after fully stirring.
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| CN106046882A (en) * | 2016-06-06 | 2016-10-26 | 无锡伊佩克科技有限公司 | Corrosion-resistant metal coating and preparation method thereof |
| CN106280840A (en) * | 2016-08-24 | 2017-01-04 | 何国美 | Anti-corrosion of metal layer |
| CN107260758A (en) * | 2017-06-09 | 2017-10-20 | 浙江汇能生物股份有限公司 | A kind of preparation method of the high nano zine oxide dry suspensoid agent of biological value |
| CN109206986A (en) * | 2018-09-14 | 2019-01-15 | 太和县中科蓝海智能医疗设备有限公司 | A kind of preparation method of the antibacterial coating of medical instrument composite antibacterial |
| CN112457820A (en) * | 2020-12-09 | 2021-03-09 | 佛山市普力达科技有限公司 | Novel material for bonding organic silicon acid adhesive and plate and preparation method thereof |
| CN113563636A (en) * | 2021-08-10 | 2021-10-29 | 瑞安市超扬新材料有限公司 | Preparation method of enhanced light stabilizer for straw netting |
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| CN106046882A (en) * | 2016-06-06 | 2016-10-26 | 无锡伊佩克科技有限公司 | Corrosion-resistant metal coating and preparation method thereof |
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| CN107260758A (en) * | 2017-06-09 | 2017-10-20 | 浙江汇能生物股份有限公司 | A kind of preparation method of the high nano zine oxide dry suspensoid agent of biological value |
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| CN109206986A (en) * | 2018-09-14 | 2019-01-15 | 太和县中科蓝海智能医疗设备有限公司 | A kind of preparation method of the antibacterial coating of medical instrument composite antibacterial |
| CN114423828A (en) * | 2019-09-18 | 2022-04-29 | 诺维尔里斯公司 | Metal surface coating for improving adhesive property and preparation method thereof |
| CN114423828B (en) * | 2019-09-18 | 2023-10-27 | 诺维尔里斯公司 | Metal surface coating for improving adhesive property and preparation method thereof |
| US11827807B2 (en) | 2019-09-18 | 2023-11-28 | Novelis Inc. | Metal surface coatings for improving bond performance and methods of making the same |
| CN112457820A (en) * | 2020-12-09 | 2021-03-09 | 佛山市普力达科技有限公司 | Novel material for bonding organic silicon acid adhesive and plate and preparation method thereof |
| CN113563636A (en) * | 2021-08-10 | 2021-10-29 | 瑞安市超扬新材料有限公司 | Preparation method of enhanced light stabilizer for straw netting |
| CN113563636B (en) * | 2021-08-10 | 2022-11-18 | 瑞安市超扬新材料有限公司 | Preparation method of enhanced light stabilizer for straw netting |
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Denomination of invention: A metal surface silane treatment agent containing water-based nano zinc oxide material and its preparation method Effective date of registration: 20230829 Granted publication date: 20160224 Pledgee: Wuhu Yangzi rural commercial bank Limited by Share Ltd. Pledgor: ANHUI LIUFANG ZHONGLIAN MECHANICAL SHARE Co.,Ltd. Registration number: Y2023980054297 |
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