CN102993870A - 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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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 the metal conditioner technology, be specifically related to a kind of modified silicon alkanisation metallic surface pretreating reagent that contains the oleic acid polyoxyethylene ester and preparation method thereof.
Background technology
The corrosion of metallic substance all occurs around us all the time.Annual according to statistics have 10% metallic substance can't reclaim for corrosion approximately, this not only causes the huge waste of metals resources, also normal production and personnel safety are brought serious threat, it is a kind of anti-corrosion method commonly used that metallic substance is carried out surface treatment, and being used for coated metal pre-treatment main method at present is parco-lubrizing.Environment there are the problems such as pollution but traditional metal surface treating method exists because containing hazardous and noxious substances, have been not suitable for the more and more higher environmental requirement of human society.
Metallic substance can strengthen the sticking power between metallic matrix and the coating after phosphatization, improve corrosion resistance nature.Bonderizing no doubt has plurality of advantages, but also there is the drawback that much himself can't overcome: all contain the objectionable impuritiess such as phosphoric acid salt and heavy metal in the etching solution, 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 discharging and heavy metal will endanger environment as not advancing environmental protection treatment; In addition, the most of need of bonderizing carried out under the condition of heating, and energy consumption is larger, complex process, and operation is also inconvenient.Along with development and the progress of society, people are also more and more high to the requirement of coated metal prefinished products, wish that not only its self performance is good, wish that more it can satisfy growing environmental protection needs, HUMAN HEALTH requires and the resources conservation requirement.These drawbacks that conventional phosphatizing is processed are just seriously restricting further developing and using 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.
The silanization processing is compared with conventional phosphatizing has following a plurality of advantage: not phosphorous without the harmful heavy metal ion, need not to heat.The silane treatment process does not produce sediment, and the treatment time is short, controls easy.Treatment step is few, can save table and transfer operation, and tank liquor is reusable.Effective Raise paint is to the sticking power of base material.But the multiple base materials such as collineation processing iron plate, galvanized sheet, aluminium sheet.But with regard to present domestic technique, not very ripe, especially on the type selecting of silane and auxiliary agent, also have a lot of not enough places.
Metallic surface silanization is processed and is had broad application prospects, and corrosion resistance is not strong, film forming is inhomogeneous, do not possess the defectives such as " selfreparing " performance or " selfreparing " poor performance, has limited its development but the silane film that prior art becomes exists.
Summary of the invention
The invention discloses a kind of modified silicon alkanisation metallic surface pretreating reagent that contains the oleic acid polyoxyethylene 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 that contains the oleic acid polyoxyethylene ester, it is characterized in that, made by the feed composition of following weight part: 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 that contains the oleic acid polyoxyethylene 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 described preparation method who contains the modified silicon alkanisation metallic surface pretreating reagent of oleic acid polyoxyethylene ester is characterized in that, may further comprise the steps:
(1) modification coupling agent preparation
The water-soluble nano grade silica sol is added 4-5% nano zinc powder, 3-5% ferric oxide, 4-6%2-aminoethyl 17 alkenyl imidazolines, be mixed and heated to 100-120 ℃, cool off after 20-30 minute and get final product;
(2) in stirring tank, add first silane coupling agent KH-69 by the formula rate amount, then add dicumyl peroxide, after stirring 3-4 minute with the speed of 300-400rpm, add again silane coupling agent KH-912, after stirring 3-5 minute with the speed of 300-400rpm, Sodium perfluorooctanoate and monobutyl-tin-trichloride are added wherein, at room temperature with the condition of protection of inert gas under, speed with 350-450rpm stirred 30-40 minute again, obtained built up silane couple A;
(3) by formula rate deionized water is injected stirring tank, the modification coupling agent that under the whipped state step (1) is made adds in the still, stir after 1-2 minute, add again propyl alcohol, continue to stir after 2-3 minute, add again ACRYLIC EMULSION, stirred 5-6 minute, obtain mixing solutions B, stirring velocity is 2000～2500rpm;
(4) A and B are mixed, add successively Xylo-Mucine, sorbester p18, polyoxyethylene oleic acid ester, phytic acid again, under the whipped state, isothermal reaction under 50-60 ℃ of condition obtains mixed solution C;
(5) add at last 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 the 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 agent of resulting modified silicon alkanisation surface pretreatment has characteristics nontoxic, environmental protection, formed silane film corrosion resistance is strong in the metallic surface, film is fine and close evenly, strong adhesion produces without the dust phenomenon, is widely used in the pre-treatment of the spraying paint that dusts of various metallic surfaces.
Embodiment
Embodiment 1
Take by weighing 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
The preparation method:
(1) modification coupling agent preparation
The water-soluble nano grade silica sol is added 4-5% nano zinc powder, 3-5% ferric oxide, 4-6%2-aminoethyl 17 alkenyl imidazolines, be mixed and heated to 110 ℃, cool off after 20-30 minute and get final product;
(2) in stirring tank, add first silane coupling agent KH-69 by the formula rate amount, then add dicumyl peroxide, after stirring 3-4 minute with the speed of 300-400rpm, add again silane coupling agent KH-912, after stirring 3-5 minute with the speed of 300-400rpm, Sodium perfluorooctanoate and monobutyl-tin-trichloride are added wherein, at room temperature with the condition of protection of inert gas under, speed with 350-450rpm stirred 30-40 minute again, obtained built up silane couple A;
(3) by formula rate deionized water is injected stirring tank, the modification coupling agent that under the whipped state step (1) is made adds in the still, stir after 1-2 minute, add again propyl alcohol, continue to stir after 2-3 minute, add again ACRYLIC EMULSION, stirred 5-6 minute, obtain mixing solutions B, stirring velocity is 2000～2500rpm;
(4) A and B are mixed, add successively Xylo-Mucine, sorbester p18, polyoxyethylene oleic acid ester, phytic acid again, under the whipped state, isothermal reaction under 55 ℃ of conditions obtains mixed solution C;
(5) add at last 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 such as following table:
| Project | Implement 1 | Prior art |
| Treatment time min | 5 | 20 |
| Treatment temp ℃ | Normal temperature | 140 |
| Post-treatment condition | Pure water is washed | Elder generation's pickling is washing with water |
| Tank liquor pH value | 4.5 | 9.0 |
| Silane film | Evenly fine and close | Rete is inhomogeneous |
Have energy-saving and environmental protection when silanization protective agent for surface treatment of the present invention is processed metal works as can be seen from the table, the characteristics that effect is high, silane film is evenly fine and close simultaneously.
Claims (3)
1. modified silicon alkanisation metallic surface pretreating reagent that contains the oleic acid polyoxyethylene ester, it is characterized in that, made by the feed composition of following weight part: deionized water 100, modification coupling agent 10-15, propyl alcohol 11-14, 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.
2. a kind of modified silicon alkanisation metallic surface pretreating reagent that contains the oleic acid polyoxyethylene ester according to claim 1, 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.
3. the preparation method who contains the modified silicon alkanisation metallic surface pretreating reagent of oleic acid polyoxyethylene ester as claimed in claim 1 or 2 is characterized in that, may further comprise the steps:
(1) modification coupling agent preparation
The water-soluble nano grade silica sol is added 4-5% nano zinc powder, 3-5% ferric oxide, 4-6%2-aminoethyl 17 alkenyl imidazolines, be mixed and heated to 100-120 ℃, cool off after 20-30 minute and get final product;
(2) in stirring tank, add first silane coupling agent KH-69 by the formula rate amount, then add dicumyl peroxide, after stirring 3-4 minute with the speed of 300-400rpm, add again silane coupling agent KH-912, after stirring 3-5 minute with the speed of 300-400rpm, Sodium perfluorooctanoate and monobutyl-tin-trichloride are added wherein, at room temperature with the condition of protection of inert gas under, speed with 350-450rpm stirred 30-40 minute again, obtained built up silane couple A;
(3) by formula rate deionized water is injected stirring tank, the modification coupling agent that under the whipped state step (1) is made adds in the still, stir after 1-2 minute, add again propyl alcohol, continue to stir after 2-3 minute, add again ACRYLIC EMULSION, stirred 5-6 minute, obtain mixing solutions B, stirring velocity is 2000～2500rpm;
(4) A and B are mixed, add successively Xylo-Mucine, sorbester p18, polyoxyethylene oleic acid ester, phytic acid again, under the whipped state, isothermal reaction under 50-60 ℃ of condition obtains mixed solution C;
(5) add at last lanthanum acetate, stir after 10-15 minute, obtain the finished product.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| 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 |
| 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 |
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| EP0694593A1 (en) * | 1994-07-29 | 1996-01-31 | Procoat, S.L. | Anticorrosive composition free from sexvalent chromium |
| JP2009041077A (en) * | 2007-08-09 | 2009-02-26 | Chemicoat & Co Ltd | Solution composition of metal surface-treatment agent containing zirconium as main component, and surface-treatment method |
| 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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2012
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| EP0694593A1 (en) * | 1994-07-29 | 1996-01-31 | Procoat, S.L. | Anticorrosive composition free from sexvalent chromium |
| JP2009041077A (en) * | 2007-08-09 | 2009-02-26 | Chemicoat & Co Ltd | Solution composition of metal surface-treatment agent containing zirconium as main component, and surface-treatment method |
| 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 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| 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 |
| 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 |
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