CN102993870B - Modified silanized metal surface pre-treating agent containing polyoxyethylene oleate and preparation method thereof - Google Patents
Modified silanized metal surface pre-treating agent containing polyoxyethylene oleate and preparation method thereof Download PDFInfo
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- CN102993870B CN102993870B CN201210510487.9A CN201210510487A CN102993870B CN 102993870 B CN102993870 B CN 102993870B CN 201210510487 A CN201210510487 A CN 201210510487A CN 102993870 B CN102993870 B CN 102993870B
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Abstract
The invention discloses a modified silanized metal surface pre-treating agent containing polyoxyethylene oleate. The pre-treating agent is prepared from the following raw material components in parts by weight: 100 parts of de-ionized water, 10-15 parts of modified coupling agent, 10-15 parts of propyl alcohol, 30-40 parts of silane coupling agent KH-912, 20-30 parts of silane coupling agent KH-69, 1-2 parts of dicumyl peroxide, 0.002-0.003 part of sodium perfluorooctane sulfonate, 0.3-0.5 part of butyltin trichloride, 4-6 parts of acroleic acid emulsion, 2-3 parts of sodium carboxymethyl cellulose, 0.4-1.0 part of Span 60, 0.2-0.6 part of polyoxyethylene oleate, 0.005-0.01 part of lanthanum acetate, and 0.1-0.3 part of phytic acid. By adopting coupling agent modification and compounding, and adding auxiliary agents, the mixture reacts to obtain the end product. The modified silanized metal surface pre-treating agent has the characteristics of being non-toxic, environment-friendly, and convenient to use; and a silane film is compact, uniform, large in adhesive force and good in corrosion resistance.
Description
Technical field
The present invention relates to metal conditioner technology, be specifically related to a kind of modified silicon alkanisation metallic surface pretreating reagent containing polyoxyethylene oleic acid ester and preparation method thereof.
Background technology
The corrosion of metallic substance all occurs all the time around us.Approximately there is every year according to statistics 10% metallic substance cannot reclaim for corrosion, this not only causes the huge waste of metals resources, also normal production and personnel safety are brought to serious threat, it is a kind of conventional anti-corrosion method that metallic substance is carried out to surface treatment, is parco-lubrizing at present for coated metal pre-treatment main method.Environment is had to the problems such as pollution but traditional metal surface treating method exists because containing hazardous and noxious substances, be not suitable for the environmental requirement that human society is more and more higher.
Metallic substance, after phosphatization, can strengthen the sticking power between metallic matrix and coating, improves corrosion resistance nature.Bonderizing no doubt has plurality of advantages, but also there is the drawback that much himself cannot overcome: in etching solution, all contain the objectionable impurities such as phosphoric acid salt and heavy metal, and in treating processes, all more or less can produce sediment and obnoxious flavour, what impact was produced normally carries out, and the waste water COD of discharge and heavy metal will endanger environment if do not entered environmental protection treatment; In addition, bonderizing major part need be carried out under the condition of heating, and energy consumption is larger, complex process, and operation is also inconvenient.Along with social development and progress, people are also more and more high to the requirement of coated metal prefinished products, not only wish that its self performance is good, more wish that it can meet growing environmental protection needs, HUMAN HEALTH requires and resources conservation requirement.These drawbacks of conventional phosphatizing processing are just seriously restricting further developing and applying of it.So people hope and can develop a kind of brand-new treatment process, when it can keep conventional phosphatizing treatment process advantage, can accomplish that again technique is simple, environmental protection, comprehensive cost is low.
Silanization is processed has following multiple advantage compared with conventional phosphatizing: without harmful heavy metal ion, not phosphorous, and without heating.Silane treatment process does not produce sediment, and the treatment time is short, controls easy.Treatment step is few, can save table and adjust operation, and tank liquor is reusable.Effectively improve the sticking power of paint to base material.Can collineation processing iron plate, the multiple base material such as galvanized sheet, aluminium sheet.But with regard to current domestic technique, not very ripe, especially, in the type selecting of silane and auxiliary agent, also have a lot of not enough places.
Metallic surface silanization processing has broad application prospects, but the silane film that prior art becomes exists, corrosion resistance is not strong, film forming is inhomogeneous, do not possess the defect such as " selfreparing " performance or " selfreparing " poor performance, has limited its development.
Summary of the invention
The invention discloses a kind of modified silicon alkanisation metallic surface pretreating reagent containing polyoxyethylene oleic acid ester and preparation method thereof.
The technical solution used in the present invention is as follows:
A kind of modified silicon alkanisation metallic surface pretreating reagent containing polyoxyethylene oleic acid ester, it is characterized in that, feed composition by following weight part is made: deionized water 100, modification coupling agent 10-15, propyl alcohol 10-15, silane coupling agent KH-912 30-40, silane coupling agent KH-69 20-30, dicumyl peroxide 1-2, perfluoro octyl sulfonic acid sodium 0.002-0.003, monobutyl-tin-trichloride 0.3-0.5, ACRYLIC EMULSION 4-6, Xylo-Mucine 2-3, sorbester p18 0.4-1.0, polyoxyethylene oleic acid ester 0.2-0.6, lanthanum acetate 0.005-0.01, phytic acid 0.1-0.3.
Described a kind of modified silicon alkanisation metallic surface pretreating reagent containing polyoxyethylene oleic acid ester, it is characterized in that, made by the feed composition of following weight part: deionized water 100, modification coupling agent 12, propyl alcohol 14, silane coupling agent KH-69 25, silane coupling agent KH-912 35, dicumyl peroxide 1.5, Sodium perfluorooctanoate 0.0024, monobutyl-tin-trichloride 0.4, ACRYLIC EMULSION 5, Xylo-Mucine 2, sorbester p18 0.6, polyoxyethylene oleic acid ester 0.4, lanthanum acetate 0.007, phytic acid 0.25.
The preparation method of the described modified silicon alkanisation metallic surface pretreating reagent containing polyoxyethylene oleic acid ester, is characterized in that, comprises the following steps:
(1) modification coupling agent preparation
Water-soluble nano grade silica sol is added to 4-5% nano zinc powder, 3-5% ferric oxide, 4-6%2-aminoethyl 17 alkenyl imidazolines, be mixed and heated to 100-120 DEG C, cooling after 20-30 minute;
(2) in stirring tank, first add silane coupling agent KH-69 by formula rate amount, then add dicumyl peroxide, stir after 3-4 minute with the speed of 300-400rpm, add again silane coupling agent KH-912, stir after 3-5 minute with the speed of 300-400rpm, Sodium perfluorooctanoate and monobutyl-tin-trichloride added wherein, at room temperature with the condition of protection of inert gas under, stir 30-40 minute with the speed of 350-450rpm again, obtain built up silane couple A;
(3) by formula rate, deionized water is injected to stirring tank, the modification coupling agent under whipped state, step (1) being made adds in still, stir after 1-2 minute, add again propyl alcohol, continue to stir after 2-3 minute, then add ACRYLIC EMULSION, stir 5-6 minute, obtain mixing solutions B, stirring velocity is 2000～2500rpm;
(4) A and B are mixed, then add successively Xylo-Mucine, sorbester p18, polyoxyethylene oleic acid ester, phytic acid, under whipped state, isothermal reaction under 50-60 DEG C of condition, obtains mixed solution C;
(5) finally add lanthanum acetate, stir after 10-15 minute, obtain the finished product.
Use temperature: normal temperature, treatment time: 3～6 minutes (drill traverse) 1～3 minute (spray)
Working fluid pH value: 4-5, working concentration: 4-5%
Beneficial effect of the present invention:
The modification of the present invention by coupling agent and composite, overcome in prior art silane film and had that corrosion resistance is strong, the inhomogeneous shortcoming of film forming, the present invention is by regulating formula materials, improve preparation technology, the modified silicon alkanisation surface pretreatment agent obtaining, has feature nontoxic, environmental protection, the silane film corrosion resistance that forms in metallic surface is strong, film is fine and close evenly, strong adhesion, produces without dust phenomenon, is widely used in the pre-treatment of the spraying paint that dusts of various metallic surfaces.
Embodiment
Embodiment 1
Take raw material (kg) by following weight: deionized water 100, modification coupling agent 12, propyl alcohol 14, silane coupling agent KH-69 25, silane coupling agent KH-912 35, dicumyl peroxide 1.5, Sodium perfluorooctanoate 0.0024, monobutyl-tin-trichloride 0.4, ACRYLIC EMULSION 5, Xylo-Mucine 2, sorbester p18 0.6, polyoxyethylene oleic acid ester 0.4, lanthanum acetate 0.007, phytic acid 0.25
Preparation method:
(1) modification coupling agent preparation
Water-soluble nano grade silica sol is added to 4-5% nano zinc powder, 3-5% ferric oxide, 4-6%2-aminoethyl 17 alkenyl imidazolines, be mixed and heated to 110 DEG C, cooling after 20-30 minute;
(2) in stirring tank, first add silane coupling agent KH-69 by formula rate amount, then add dicumyl peroxide, stir after 3-4 minute with the speed of 300-400rpm, add again silane coupling agent KH-912, stir after 3-5 minute with the speed of 300-400rpm, Sodium perfluorooctanoate and monobutyl-tin-trichloride added wherein, at room temperature with the condition of protection of inert gas under, stir 30-40 minute with the speed of 350-450rpm again, obtain built up silane couple A;
(3) by formula rate, deionized water is injected to stirring tank, the modification coupling agent under whipped state, step (1) being made adds in still, stir after 1-2 minute, add again propyl alcohol, continue to stir after 2-3 minute, then add ACRYLIC EMULSION, stir 5-6 minute, obtain mixing solutions B, stirring velocity is 2000～2500rpm;
(4) A and B are mixed, then add successively Xylo-Mucine, sorbester p18, polyoxyethylene oleic acid ester, phytic acid, under whipped state, isothermal reaction under 55 DEG C of conditions, obtains mixed solution C;
(5) finally add lanthanum acetate, stir after 10-15 minute, obtain the finished product.
The property indices of the silanized surface pretreating reagent that modified silicon alkanisation surface pretreatment agent of the present invention and prior art are produced contrasts as following table:
| Project | Implement 1 | Prior art |
| Treatment time min | 5 | 20 |
| Treatment temp DEG C | Normal temperature | 140 |
| Post-treatment condition | Pure water is washed | First pickling, is washing with water |
| Tank liquor pH value | 4.5 | 9.0 |
| Silane film | Evenly fine and close | Rete is inhomogeneous |
When silanization protective agent for surface treatment of the present invention is processed metal works as can be seen from the table, there are energy-saving and environmental protection, the feature that effect is high, silane film is evenly fine and close simultaneously.
Claims (1)
1. the modified silicon alkanisation metallic surface pretreating reagent containing polyoxyethylene oleic acid ester, it is characterized in that, made by the feed composition of following weight part: deionized water 100, modification coupling agent 12, propyl alcohol 14, silane coupling agent KH-69 25, silane coupling agent KH-912 35, dicumyl peroxide 1.5, Sodium perfluorooctanoate 0.0024, monobutyl-tin-trichloride 0.4, ACRYLIC EMULSION 5, Xylo-Mucine 2, sorbester p18 0.6, polyoxyethylene oleic acid ester 0.4, lanthanum acetate 0.007, phytic acid 0.25;
The preparation method of the described modified silicon alkanisation metallic surface pretreating reagent containing polyoxyethylene oleic acid ester, comprises the following steps:
(1) modification coupling agent preparation
Water-soluble nano grade silica sol is added to 4-5% nano zinc powder, 3-5% ferric oxide, 4-6%2-aminoethyl 17 alkenyl imidazolines, be mixed and heated to 100-120 DEG C, cooling after 20-30 minute;
(2) in stirring tank, first add silane coupling agent KH-69 by formula rate amount, then add dicumyl peroxide, stir after 3-4 minute with the speed of 300-400rpm, add again silane coupling agent KH-912, stir after 3-5 minute with the speed of 300-400rpm, Sodium perfluorooctanoate and monobutyl-tin-trichloride added wherein, at room temperature with the condition of protection of inert gas under, stir 30-40 minute with the speed of 350-450rpm again, obtain built up silane couple A;
(3) by formula rate, deionized water is injected to stirring tank, the modification coupling agent under whipped state, step (1) being made adds in still, stir after 1-2 minute, add again propyl alcohol, continue to stir after 2-3 minute, then add ACRYLIC EMULSION, stir 5-6 minute, obtain mixing solutions B, stirring velocity is 2000～2500rpm;
(4) A and B are mixed, then add successively Xylo-Mucine, sorbester p18, polyoxyethylene oleic acid ester, phytic acid, under whipped state, isothermal reaction under 50-60 DEG C of condition, obtains mixed solution C;
(5) finally add lanthanum acetate, stir after 10-15 minute, obtain the finished product.
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| CN103468129A (en) * | 2013-08-29 | 2013-12-25 | 安徽省宿州市龙华机械制造有限公司 | Urea-containing modified silanization surface treatment and pretreatment agent and preparation method thereof |
| CN103450799A (en) * | 2013-08-29 | 2013-12-18 | 安徽省宿州市龙华机械制造有限公司 | Modified silanized metal surface pretreatment agent containing sodium carboxymethyl cellulose and preparation method thereof |
| CN103451641A (en) * | 2013-08-29 | 2013-12-18 | 安徽省宿州市龙华机械制造有限公司 | Modified silanized metal surface pretreatment agent containing diphenylethyl diphenol polyoxyethylene ether and preparation method thereof |
| CN103451642A (en) * | 2013-08-29 | 2013-12-18 | 安徽省宿州市龙华机械制造有限公司 | Modified silanized metal surface pretreatment agent containing fatty alcohol-polyoxyethylene ether and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0694593A1 (en) * | 1994-07-29 | 1996-01-31 | Procoat, S.L. | Anticorrosive composition free from sexvalent chromium |
| CN102146560A (en) * | 2011-03-18 | 2011-08-10 | 蚌埠市钰诚五金工贸有限公司 | Rare earth-silanization treatment agent used before metal cathode electrophoresis and preparation method of rare earth-silanization treatment agent |
| CN102337532A (en) * | 2011-07-11 | 2012-02-01 | 武汉迪赛高科技研究发展有限公司 | Chromium-free passivation liquid applied to surface of zinc-coated layer |
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| JP5112783B2 (en) * | 2007-08-09 | 2013-01-09 | 株式会社ケミコート | Solution composition and surface treatment method of metal surface treatment agent based on zirconium |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0694593A1 (en) * | 1994-07-29 | 1996-01-31 | Procoat, S.L. | Anticorrosive composition free from sexvalent chromium |
| CN102146560A (en) * | 2011-03-18 | 2011-08-10 | 蚌埠市钰诚五金工贸有限公司 | Rare earth-silanization treatment agent used before metal cathode electrophoresis and preparation method of rare earth-silanization treatment agent |
| CN102337532A (en) * | 2011-07-11 | 2012-02-01 | 武汉迪赛高科技研究发展有限公司 | Chromium-free passivation liquid applied to surface of zinc-coated layer |
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| JP特开2009-41077A 2009.02.26 * |
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