CN103060787B - A kind of Metal surface silane treatment agent containing diethanolamine and preparation method thereof - Google Patents

A kind of Metal surface silane treatment agent containing diethanolamine and preparation method thereof Download PDF

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CN103060787B
CN103060787B CN201210550790.1A CN201210550790A CN103060787B CN 103060787 B CN103060787 B CN 103060787B CN 201210550790 A CN201210550790 A CN 201210550790A CN 103060787 B CN103060787 B CN 103060787B
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water
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zinc oxide
treatment agent
nano zinc
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CN103060787A (en
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王立新
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Anhui Liufang Zhonglian Mechanical Share Co Ltd
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Anhui Liufang Zhonglian Mechanical Share Co Ltd
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Abstract

The invention discloses a kind of Metal surface silane treatment agent containing diethanolamine, 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: 1, two (triethoxy is silica-based) ethane 28-35 of 2-, γ-aminopropyl triethoxysilane 32-40, water nano zinc oxide material 100-160, vinylcarbinol 2-3, ethylene glycol 1-2, tripoly phosphate sodium STPP 2-3, propylene glycol 2-4, zirconium tetrafluoride 2-3, diethanolamine 2-3, ammonium chloride 2-3, butyl 1-2, TriMethylolPropane(TMP) 1-2, Sodium dodecylbenzene sulfonate 0.3-0.5, remaining is 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, by 1, two (triethoxy the is silica-based) ethane of 2-and γ-aminopropyl triethoxysilane combine use, can form densification and firmly coating in metallic surface.

Description

A kind of Metal surface silane treatment agent containing diethanolamine and preparation method thereof
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 diethanolamine 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 diethanolamine, the mixed solution formulated by following component, in often liter of mixed solution, the weight part (gram) of each component is:
1,2-two (triethoxy is silica-based) ethane 28-35, γ-aminopropyl triethoxysilane 32-40, water nano zinc oxide material 100-160, vinylcarbinol 2-3, ethylene glycol 1-2, tripoly phosphate sodium STPP 2-3, propylene glycol 2-4, zirconium tetrafluoride 2-3, diethanolamine 2-3, ammonium chloride 2-3, butyl 1-2, TriMethylolPropane(TMP) 1-2, Sodium dodecylbenzene sulfonate 0.3-0.5, 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) by 1, two (triethoxy the is silica-based) ethane of 2-dissolves 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.
In the preparation method of described water nano zinc oxide material, described nano zine oxide, glycerol, 1, the mass ratio of the water in two (triethoxy the is silica-based) ethane of 2-and step (2), the ethanol in step (3) is: two (triethoxy is silica-based) ethane of nano zine oxide: glycerol: 1,2-: 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 diethanolamine, comprises the following steps:
(1) 1,2-of above-mentioned weight part two (triethoxy is silica-based) ethane is added in the water of above-mentioned weight part 60-70%, add the γ-aminopropyl triethoxysilane of above-mentioned weight part after fully dissolving again, fully stir, obtain compound A;
(2) 60-70% of residue water is got, add the water nano zinc oxide material of above-mentioned weight part, after abundant stirring, add the tripoly phosphate sodium STPP of above-mentioned weight part, zirconium tetrafluoride, diethanolamine, ammonium chloride, butyl, TriMethylolPropane(TMP) fully stir, obtain compound B;
(3) vinylcarbinol of above-mentioned weight part and ethylene glycol are mixed with remaining water, be heated to 40-50 DEG C, then add the Sodium dodecylbenzene sulfonate of above-mentioned weight part, be stirred to Sodium dodecylbenzene sulfonate 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 propylene glycol of above-mentioned weight part, namely obtains the described Metal surface silane treatment agent containing diethanolamine 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, by 1, two (triethoxy the is silica-based) ethane of 2-and γ-aminopropyl triethoxysilane combine use, 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 zirconium 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 diethanolamine, the mixed solution formulated by following component, in often liter of mixed solution, the weight part (gram) of each component is:
Two (triethoxy the is silica-based) ethane 35 of 1,2-, γ-aminopropyl triethoxysilane 40, water nano zinc oxide material 160, vinylcarbinol 3, ethylene glycol 2, tripoly phosphate sodium STPP 3, propylene glycol 4, zirconium tetrafluoride 3, diethanolamine 3, ammonium chloride 3, butyl 2, TriMethylolPropane(TMP) 2, Sodium dodecylbenzene sulfonate 0.5, 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 5 times, obtain dispersion liquid, then the dicumyl peroxide of its quality 4%, 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) by 1, two (triethoxy the is silica-based) ethane of 2-dissolves in ethanol, be prepared into the solution that mass concentration is 2%, 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, described nano zine oxide, glycerol, 1, the mass ratio of the water in two (triethoxy the is silica-based) ethane of 2-and step (2), the ethanol in step (3) is: two (triethoxy is silica-based) ethane of nano zine oxide: glycerol: 1,2-: water: ethanol is 15g:2g:4g:105 gram: 105 grams.
The granularity of described nano zine oxide is 50nm.
A preparation method for Metal surface silane treatment agent containing diethanolamine, comprises the following steps:
(1) 1,2-of above-mentioned weight part two (triethoxy is silica-based) ethane is added in the water of above-mentioned weight part 70%, add the γ-aminopropyl triethoxysilane of above-mentioned weight part after fully dissolving again, fully stir, obtain compound A;
(2) 70% of residue water is got, add the water nano zinc oxide material of above-mentioned weight part, after abundant stirring, add the tripoly phosphate sodium STPP of above-mentioned weight part, zirconium tetrafluoride, diethanolamine, ammonium chloride, butyl, TriMethylolPropane(TMP) fully stir, obtain compound B;
(3) vinylcarbinol of above-mentioned weight part and ethylene glycol are mixed with remaining water, be heated to 50 DEG C, then add the Sodium dodecylbenzene sulfonate of above-mentioned weight part, be stirred to Sodium dodecylbenzene sulfonate and dissolve completely, obtain compound C;
(4) by compound A, B and C mixing obtained above, then acetic acid or sodium-acetate, regulates PH to be 5, finally adds the propylene glycol of above-mentioned weight part, namely obtains the described Metal surface silane treatment agent containing diethanolamine 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 (4)

1. the Metal surface silane treatment agent containing diethanolamine, it is characterized in that by the formulated mixed solution of following component, in often liter of mixed solution, the weight part of each component is: 1, two (triethoxy is silica-based) ethane 28-35g of 2-, γ-aminopropyl triethoxysilane 32-40g, water nano zinc oxide material 100-160g, vinylcarbinol 2-3g, ethylene glycol 1-2g, tripoly phosphate sodium STPP 2-3g, propylene glycol 2-4g, zirconium tetrafluoride 2-3g, diethanolamine 2-3g, ammonium chloride 2-3g, butyl 1-2g, TriMethylolPropane(TMP) 1-2g, Sodium dodecylbenzene sulfonate 0.3-0.5g, remaining is 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) by 1, two (triethoxy the is silica-based) ethane of 2-dissolves 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.
2. a kind of Metal surface silane treatment agent containing diethanolamine according to claim 1, it is characterized in that, in the preparation method of described water nano zinc oxide material, described nano zine oxide, glycerol, 1, the mass ratio of the water in two (triethoxy the is silica-based) ethane of 2-and step (2), the ethanol in step (3) is: two (triethoxy is silica-based) ethane of nano zine oxide: glycerol: 1,2-: water: ethanol is 10-15g:1-2g:2-4g:95-105g:95-105g.
3. a kind of Metal surface silane treatment agent containing diethanolamine according to claim 1, is characterized in that the granularity of described nano zine oxide is 40-50nm.
4. a preparation method for the Metal surface silane treatment agent containing diethanolamine as claimed in claim 1, is characterized in that comprising the following steps:
(1) 1,2-of above-mentioned weight part two (triethoxy is silica-based) ethane is added in the water of above-mentioned weight part 60-70%, add the γ-aminopropyl triethoxysilane of above-mentioned weight part after fully dissolving again, fully stir, obtain compound A;
(2) 60-70% of residue water is got, add the water nano zinc oxide material of above-mentioned weight part, after abundant stirring, add the tripoly phosphate sodium STPP of above-mentioned weight part, zirconium tetrafluoride, diethanolamine, ammonium chloride, butyl, TriMethylolPropane(TMP) fully stir, obtain compound B;
(3) vinylcarbinol of above-mentioned weight part and ethylene glycol are mixed with remaining water, be heated to 40-50 DEG C, then add the Sodium dodecylbenzene sulfonate of above-mentioned weight part, be stirred to Sodium dodecylbenzene sulfonate and dissolve completely, obtain compound C;
(4) by compound A, B and C mixing obtained above, then add acetic acid or sodium-acetate, adjustment pH is 3-5, finally adds the propylene glycol of above-mentioned weight part, namely obtains the described Metal surface silane treatment agent containing diethanolamine after fully stirring.
CN201210550790.1A 2012-12-18 2012-12-18 A kind of Metal surface silane treatment agent containing diethanolamine and preparation method thereof Active CN103060787B (en)

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CN104099003A (en) * 2014-06-17 2014-10-15 安徽省六安市朝晖机械制造有限公司 Environment-friendly aluminum alloy surface treatment agent
CN109468009B (en) * 2018-10-29 2020-12-18 重庆炫吉科技有限公司 Environment-friendly metal surface coating pretreatment agent and preparation method thereof
CN109485087A (en) * 2018-12-18 2019-03-19 兴化市万润锌业有限公司 A kind of processing method of modified nano zinc oxide

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CN101434748A (en) * 2008-12-04 2009-05-20 上海大学 Preparation of nano zinc oxide modified organosilicon encapsulation adhesive
CN102121104A (en) * 2011-01-22 2011-07-13 安徽工业大学 Aqueous chromium-free surface treatment solution for combining color coating pretreatment and base paint coating of galvanized plate

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JP4537377B2 (en) * 2003-02-25 2010-09-01 ヒェメタル ゲゼルシャフト ミット ベシュレンクテル ハフツング Method for coating a metal surface with a polymer-rich composition
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101287784A (en) * 2005-08-26 2008-10-15 Ppg工业俄亥俄公司 Coating compositions exhibiting corrosion resistance properties, related coated substrates, and methods
CN101434748A (en) * 2008-12-04 2009-05-20 上海大学 Preparation of nano zinc oxide modified organosilicon encapsulation adhesive
CN102121104A (en) * 2011-01-22 2011-07-13 安徽工业大学 Aqueous chromium-free surface treatment solution for combining color coating pretreatment and base paint coating of galvanized plate

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Denomination of invention: A metal surface silane treatment agent containing diethanolamine and its preparation method

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