CN100441641C - Water antki-rust composition - Google Patents
Water antki-rust composition Download PDFInfo
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- CN100441641C CN100441641C CNB200410025463XA CN200410025463A CN100441641C CN 100441641 C CN100441641 C CN 100441641C CN B200410025463X A CNB200410025463X A CN B200410025463XA CN 200410025463 A CN200410025463 A CN 200410025463A CN 100441641 C CN100441641 C CN 100441641C
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Abstract
The present invention provides a water anti-rust agent which comprises a tetrazole compound expressed by the right expression, polyethylene glycol, triethanolamine and a solvent, wherein R and R' respectively represent hydrogen atoms, substituted or non-substituted alkyl with one to twenty carbon atoms, substituted or non-substituted naphthenic groups, phenyl, alkylphenyl and aralkyl and substituted or non-substituted amino groups, sulfhydryl or alkyl sulfhydryl.
Description
Technical field
The present invention relates to a kind of novel aqueous rust-proof component, be specifically related to comprise the long-acting waterborne anti-rust composition of tetrazole.
Background technology
In recent years, along with the continuous development of mechanical industry, the demand of the rust-proof component of using for mechanical means is also increasing.Simultaneously, because the global environment problem is more and more serious, so the environmental problem that rust-proof component produced has also caused people's attention.
Rust-proof component commonly used at present comprises the oiliness rust-preventive agent that contains dimethylbenzene, gasoline and nitrite.Because above-mentioned antirust agent composition comprises objectionable impuritiess such as dimethylbenzene, gasoline and nitrite, so it can cause certain infringement to environment, also there is potential safety hazard simultaneously, because dimethylbenzene and gasoline incendivity, and nitrite is a highly toxic substance.
At the problems referred to above, U.S. Pat 5744069 (people such as Maeda) discloses a kind of water-soluble metal antirusting agent composition, and it comprises tetrazotized zole compound or its water-soluble salt, and its molecular formula is:
Wherein R and R ' represent hydrogen atom separately, have alkyl, cycloalkyl, phenyl, alkyl phenyl, amino, sulfydryl or the alkyl thiol of 1-20 carbon atom.This antirust agent composition has the rust inhibiting property that conventional rust-preventive agent has, and owing to do not contain objectionable impuritiess such as dimethylbenzene, gasoline and dinitrate, so it is friendly to environment.
In addition, the open CN1035522 of Chinese patent people such as () Luo Wenyan discloses a kind of antirust agent composition, and it comprises polyoxyethylene glycol, oleic acid, barium mahogany sulfonate, trolamine, paraffin and distilled water etc.In described antirust agent composition, used polyoxyethylene glycol as membrane-forming agent, use trolamine as sustained release dosage, avoided use, and also obtained certain rust-proof effect for objectionable impuritiess such as dimethylbenzene, gasoline.
Though above-mentioned these rust-preventive agent have all been avoided objectionable impuritiess such as use dimethylbenzene, gasoline, nitrite, and all have certain rust-proof effect.But, also have the needs that further improve its rust-proof effect and stability in storage in the art.
Summary of the invention
The purpose of this invention is to provide better and more stabilized aqueous rust-preventive agent of a kind of rust-proof effect, it is friendly to environment.
The inventor finds, can reach effect of the present invention by being used in combination tetrazotized zole compound, polyoxyethylene glycol and trolamine, can obviously improve rust-proof effect, and the product stability that forms is better.
Based on above-mentioned discovery, one aspect of the present invention provides a kind of water-based antirust agent composition, and it comprises:
(1) tetrazotized zole compound represented of following formula:
Wherein R and R ' represent hydrogen atom separately, have alkyl, cycloalkyl, phenyl, alkyl phenyl, aralkyl, amino, sulfydryl or the alkyl thiol of 1-20 carbon atom;
(2) polyoxyethylene glycol;
(3) trolamine;
(4) solvent.
In a preferred embodiments of the present invention, described rust-preventive agent also comprises one or more materials that are selected from thiocarbamide, sodium bicarbonate, the sodium phosphate
In another preferred embodiments of the present invention, described tetrazotized zole compound is expressed from the next:
Wherein R and R ' represent hydrogen atom separately, have the alkyl of 1-4 carbon atom, the replacement with 3-6 carbon atom or unsubstituted cycloalkyl, phenyl, are had the sulfydryl of phenyl, benzyl, amino, sulfydryl that the alkyl of 1-4 carbon atom replaces or the alkyl replacement with 1-4 carbon atom.
In another preferred embodiments of the present invention, described tetrazotized zole compound is 5-benzyl-tetrazole.
In another preferred embodiments of the present invention, the molecular weight of described polyoxyethylene glycol is 200-600.
In another preferred embodiments of the present invention, described solvent comprises water.
In another preferred embodiments of the present invention, described rust-preventive agent comprises:
(1) the described tetrazotized zole compound of 10-15 weight %;
(2) the described trolamine of 3-7 weight %;
(3) polyoxyethylene glycol of 2-8 weight %;
(4) solvent of 70-85 weight %.
In another preferred embodiments of the present invention, described rust-preventive agent comprises:
(1) the described tetrazotized zole compound of 10-15 weight %;
(2) the described trolamine of 3-7 weight %;
(3) polyoxyethylene glycol of 2-8 weight %;
(4) thiocarbamide of 0.2-2 weight %;
(5) sodium bicarbonate of 1-5 weight %;
The sodium phosphate of (6) 3 weight %;
(7) water of 60-80.8 weight %.
The present invention provides a kind of water-based antirust agent composition on the other hand, and it comprises 5-benzyl-tetrazole and solvent.
Antirust agent composition of the present invention can be applicable to the vehicles, bridge, and storage, pipeline, facility spares such as mechanical means steel antirust provides good guarantee to environment protection and factory mass production again simultaneously.It is-the long-acting stabilized aqueous rust-preventive agent of kind of environmental type.
Embodiment
The invention provides a kind of novel water-based antirust agent, it comprises:
(1) tetrazotized zole compound represented of following formula:
Wherein R and R ' represent hydrogen atom separately, have the replacement of 1-20 carbon atom or the alkyl that does not replace, replacement or cycloalkyl, phenyl, alkyl phenyl, aralkyl, replacement or unsubstituted amino, sulfydryl or alkyl thiol for replacing;
(2) polyoxyethylene glycol;
(3) trolamine;
(4) solvent.
Effects such as that tetrazole and derivative thereof have is antibiotic, anti-inflammatory and plant growth regulating are a kind of strong antifoggant and anti-bronze agent, so it is extensively applied to a plurality of fields, as sensitive materials, and biological medicine, a plurality of fields such as chemical industry and machinery.And described compound can both carry out chelatropic reaction to many metal ions, and the insoluble inner complex of formation is deposited on and forms protective membrane on the metallic surface, makes the metallic surface be converted into " passivation attitude " by " activated state ", thereby has reached antirust effect.The tetrazotized zole compound that the present invention relates to is shown below:
Wherein R and R ' represent hydrogen atom separately, have the replacement of 1-20 carbon atom or the alkyl that does not replace, replacement or cycloalkyl, phenyl, alkyl phenyl, aralkyl, replacement or unsubstituted amino, sulfydryl or alkyl thiol for replacing.The example of these tetrazotized zole compounds can be specifically referring to U.S. Pat 5744069 people such as () Maeda, it is in full with reference to being incorporated into this.
In the present invention, R and R ' preferably represent hydrogen atom separately, have 1-4 carbon atom alkyl (for example methyl, ethyl, n-propyl and normal-butyl), have the replacement of 3-6 carbon atom or do not replace (preferred substituted is the alkyl with 1-4 carbon atom) cycloalkyl (for example cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl), phenyl, had 1-4 carbon atom the alkyl replacement phenyl (for example ethylbenzene base, propyl phenyl, butylbenzene base), benzyl, amino, sulfydryl or had the sulfydryl of the alkyl replacement of 1-4 carbon atom.
The object lesson of described tetrazotized zole compound can be 1H-tetrazole, 5-amino-1H-tetrazole, 5-methyl isophthalic acid H-tetrazole, 1-methyl-5-ethyl-tetrazole, 1-methyl-5-sulfydryl-tetrazole, 5-(2-aminophenyl)-1H-tetrazole, 1-cyclohexyl-5-sulfydryl-tetrazole, 1-phenyl-5-sulfydryl-tetrazole, 1-carboxymethyl-5-sulfydryl-tetrazole, 5-phenyl-1H-tetrazole and 5-benzyl-tetrazole etc.
In a preferred embodiment of the present invention, the content of described tetrazotized zole compound is 10-15 weight %, more preferably 11-13 weight %.
In the present invention, trolamine is the inhibiter that helps of ferrous metal, and iron and steel is had the corrosive of inhibition effect, and it has good synergistic, can strengthen the corrosion mitigating effect of other reagent.In a preferred embodiment of the present invention, the content of described trolamine is 3-7 weight %, more preferably 4-6%.
In the present invention, polyoxyethylene glycol is a colourless viscous liquid, can be made by the ethylene glycol condensation.It is the macromolecule filming material, can form water white film with other auxiliary agents are common, thereby separate iron and steel and corrosive atmosphere etc., has reached antirust purpose.The mean number average molecular weight of preferred polyoxyethylene glycol is about 200-600.In a preferred embodiment of the present invention, the content of described polyoxyethylene glycol is 2-8 weight %, more preferably 4-6%.
In the present invention, do not have concrete restriction, as long as the component that it can dissolve among the present invention is just passable for solvent.Consider influence, organic compound or its mixture that preferred solvent is water, can dissolve each other with water for environment.Preferred solvent is the mixed solvent of second alcohol and water, because it can accelerate the rate of drying of anti-rust film.In a preferred embodiment of the present invention, the content of described solvent is 70-85 weight %, more preferably 75-80%.
Antirust agent composition of the present invention also can comprise auxiliary agent commonly used in other this areas, for example rust-preventive agent, sustained release dosage, emulsifying agent, fusing assistant, tensio-active agent, filler, clean-out system, water-softening chemicals, digestive pharmaceutical, antacid, fire-fighting medium etc.Preferably, antirust agent composition of the present invention can comprise one or more materials that are selected from thiocarbamide, sodium bicarbonate and the sodium phosphate.
In another preferred embodiment of the present invention, antirust agent composition of the present invention comprises the described tetrazotized zole compound of 10-15 weight %, the described trolamine of 3-7 weight %, the polyoxyethylene glycol of 2-8 weight %, the thiocarbamide of 0.2-2 weight %, the sodium bicarbonate of 1-5 weight %, the sodium phosphate of 3 weight %, the water of 60-80.8 weight %.Preferably, described antirust agent composition comprises the described tetrazotized zole compound of 11-13 weight %, the described trolamine of 4-6 weight %, the polyoxyethylene glycol of 4-6 weight %, the thiocarbamide of 1-1.5 weight %, the sodium bicarbonate of 2-4 weight %, the sodium phosphate of 3 weight %, the water of 66.5-75 weight %.
Another aspect of the present invention provides a kind of novel antirust agent composition, and it comprises 5-benzyl-tetrazole and solvent.Described solvent is identical with aforementioned solvents.
Describe the present invention in detail below in conjunction with embodiment, these embodiment just are used for illustration purpose, do not limit the scope of the invention.In an embodiment of the present invention, raw materials usedly all adopt chemical pure reagent, component concentration all by weight.
Embodiment
In an embodiment of the present invention, concrete used reagent is as follows:
Thiocarbamide: (Shanghai reagent one factory)
Sodium bicarbonate: (comprehensive management portion of Shanghai reagent one factory)
Sodium phosphate: (Shanghai Xinhua chemical plant)
5-phenyl-tetrazole: (the photochemical factory of Yixing City)
5-chloro-tetrazole: (the photochemical factory of Yixing City)
5-benzyl-tetrazole: (the photochemical factory of Yixing City)
Trolamine: content 80 (the photochemical factory of Yixing City)
Polyoxyethylene glycol: 400 molecules (the photochemical factory of Yixing City)
Sodium Benzoate: (Shanghai Xinhua chemical plant)
Sodium Nitrite: (Shanghai reagent one factory)
Benzotriazole: (Shanghai Xinhua chemical plant)
Dicyclohexyl amine nitrite: (Shanghai Xinhua chemical plant)
Zinc phosphate: (Shanghai Xinhua chemical plant)
Preparation example 1
In 500 liters reactor, add the component of amount shown in the table 1 and 2, at room temperature evenly stir, obtain rust-preventive agent.Except as otherwise noted, listed component all is a weight part otherwise in table 1 and 2.
Table 1
| Embodiment | 1 | 2 | 3 | 4 | 5 | 6 |
| Thiocarbamide | 1 | 2 | 0.5 | 0.5 | 0.5 | 1 |
| Sodium bicarbonate | 2 | 4 | 1.5 | 1.5 | 1.5 | 1 |
| Sodium phosphate | 3 | 3 | 3 | 3 | 3 | 3 |
| 5-benzyl-tetrazole | 11 | 10 | 15 | 12 | 10 | 12 |
| Trolamine | 3 | 4 | 5 | 6 | 3 | 2 |
| Polyoxyethylene glycol | 3 | 2 | 5 | 2 | 2 | 2 |
| Water | 77 | 75 | 70 | 70 | 80 | 79 |
Table 2
Evaluation for rust-preventive agent
Resulting rust-preventive agent in the preparation example 1 is placed a week, estimate its package stability by observing outward appearance then, the results are shown in the table 3.
Resulting rust-preventive agent in the preparation example 1 is heated to 90 ℃ then by observing its outward appearance, estimates the high-temperature stability of described rust-preventive agent, the results are shown in the table 3.
Resulting rust-preventive agent in the preparation example 1 is cooled to 10 ℃, by observing its outward appearance, estimates the low-temperature stability of described rust-preventive agent then, the results are shown in the table 3.
Resulting rust-preventive agent in the preparation example 1 is coated in sample (A-3 soft steel small column, 1.5 centimetres of diameters, 0.5 centimetre of thickness)) on.Described sample is placed on outdoor, observes its outward appearance respectively after 3 months, 6 months, 9 months and 12 months, estimates rust-proof effect, and outcome record is in table 3.
Table 3
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 |
| Outward appearance | Evenly, not stratified, nothing precipitation | Evenly, not stratified, nothing precipitation | Evenly, not stratified, nothing precipitation | Evenly, not stratified, nothing precipitation | Evenly, not stratified, nothing precipitation | Evenly, not stratified, nothing precipitation |
| The pH value | 8-9 | 8-9 | 8-9 | 8-9 | 8-9 | 8-9 |
| High-temperature stability | Evenly, not stratified | Evenly, not stratified | Evenly, not stratified | Evenly, not stratified | Evenly, not stratified | Evenly, not stratified |
| Low-temperature stability | Evenly, not stratified | Evenly, not stratified | Evenly, not stratified | Evenly, not stratified | Evenly, not stratified | Evenly, not stratified |
| Sample was placed after 3 months | The surface is rustless, and light as before | The surface is rustless, and light as before | The surface is rustless, and light as before | The surface is rustless, and light as before | The surface is rustless, and light as before | The surface is rustless, and light as before |
| Sample was placed after 6 months | The surface is rustless, and light as before | The surface is rustless, and light as before | The surface is rustless, and light as before | The surface is rustless, and light as before | The surface is rustless, and light as before | The surface is rustless, and light as before |
| Sample was placed after 9 months | The surface is rustless, and light as before | The surface is rustless, and light as before | The surface is rustless, and light as before | The surface is rustless, and light as before | The surface is rustless, and light as before | The surface is rustless, and light as before |
| Sample was placed after 12 months | The surface is rustless, and light as before | The surface is rustless, and light as before | The surface is rustless, and light as before | The surface is rustless, and light as before | The surface is rustless, and light as before | The surface is rustless, and light as before |
Table 3 (continuing)
| Project | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 |
| Outward appearance | Evenly, not stratified, nothing precipitation | There is precipitation placement for some time | There is precipitation placement for some time | Evenly, not stratified, nothing precipitation | Evenly, not stratified, nothing precipitation | Evenly, not stratified, nothing precipitation |
| The pH value | 9-10 | 9-10 | 7-8 | 7-8 | 7-8 | 7-8 |
| High-temperature stability | Evenly, not stratified | There is precipitation placement for some time | There is precipitation placement for some time | Evenly, not stratified | Evenly, not stratified | Evenly, not stratified |
| Low-temperature stability | Slightly precipitate | There is precipitation placement for some time | There is precipitation placement for some time | Slightly precipitate | Slightly precipitate | Slightly precipitate |
| Sample was placed after 3 months | The surface is rustless, and light as before | The surface is rustless, and light as before | The surface is rustless, and light as before | The surface is rustless, and light as before | The surface is rustless, and light as before | The surface is rustless, and light as before |
| Sample was placed after 6 months | The surface is rustless, and light as before | The surface is rustless, and light as before | The surface is rustless, and light as before | The surface is rustless, and light as before | The surface is rustless, and light as before | The surface is rustless, and light as before |
| Sample was placed after 9 months | The surface is rustless, and light as before | The surface is rustless, and light as before | The light rust in surface, not loss of gloss | The light rust in surface, not loss of gloss | The light rust in surface, not loss of gloss | The surface is rustless, and light as before |
| Sample was placed after 12 months | The surface is rustless, and light as before | The light rust in surface, not loss of gloss | The surface is speckle slightly | The surface is speckle slightly | The surface is speckle slightly | The light rust in surface, not loss of gloss |
As can be seen from Table 3, the outward appearance of rust-preventive agent of the present invention, low-temperature stability and high-temperature stability all are better than comparative example.And the sample of handling with rust-preventive agent of the present invention also can keep rust-proof effect after placing 1 year, and its performance obviously is better than comparative example.
The evaluation of the antirust efficient of 5-benzyl-tetrazole
The antirust efficient of rust-preventive agent can be estimated with weight-loss method.In weight-loss method is measured, can record weight loss Δ w, obtain inhibition efficiency P according to following calculating formula then:
P=[Δ w
0(no inhibiter)-Δ w (inhibiter is arranged)]/Δ w
0(no inhibiter).
In test, the instrument that uses is TG328B type photoelectric analytical balance.Used sample is an A-3 soft steel small column (diameter 1.5cm, thickness 0.5cm) (commercially available little iron nail).
The at first accurate weight of weighing sample immerses in 200 milliliter 3.5% the sodium-chlor corrosive fluid then, takes out after soaking certain hour, and drying, weightless Δ w is calculated in weighing
0The results are shown in the table 4.
Sample is placed on various rust-preventive agent soaked 3 minutes, take out drying, weighing.Immerse then in 200 milliliter 3.5% the sodium-chlor corrosive fluid, take out after soaking certain hour, drying, weightless Δ w is calculated in weighing.The results are shown in the table 4.
Can find out that by last table the rust-proof effect of 5-benzyl-tetrazole is better than other tetrazotized zole compounds.
Claims (7)
1. water-based antirust agent, it comprises:
(1) tetrazotized zole compound represented of the following formula of 10-15 weight %:
Wherein R and R ' represent hydrogen atom separately, have the alkyl of 1-20 carbon atom, cycloalkyl, phenyl, alkyl phenyl, aralkyl, amino or sulfydryl;
(2) polyoxyethylene glycol of 2-8 weight %;
(3) trolamine of 3-7 weight %;
(4) solvent of 70-85 weight %.
2. rust-preventive agent as claimed in claim 1, it also comprises one or more materials that are selected from thiocarbamide, sodium bicarbonate, the sodium phosphate.
3. rust-preventive agent as claimed in claim 1 is characterized in that described tetrazotized zole compound is expressed from the next:
Wherein R and R ' represent hydrogen atom separately, have the alkyl of 1-4 carbon atom, have the cycloalkyl of 3-6 carbon atom, phenyl, benzyl, amino or sulfydryl.
4. as claim 1 or 3 described rust-preventive agent, it is characterized in that described tetrazotized zole compound is 5-benzyl-tetrazole.
5. rust-preventive agent as claimed in claim 1, the molecular weight that it is characterized in that described polyoxyethylene glycol is 200-600.
6. rust-preventive agent as claimed in claim 1 is characterized in that described solvent comprises water.
7. rust-preventive agent as claimed in claim 2 is characterized in that described rust-preventive agent comprises:
(1) the described tetrazotized zole compound of 10-15 weight %;
(2) the described trolamine of 3-7 weight %;
(3) polyoxyethylene glycol of 2-8 weight %;
(4) thiocarbamide of 0.2-2 weight %;
(5) sodium bicarbonate of 1-5 weight %;
The sodium phosphate of (6) 3 weight %;
(7) water of 60-80.8 weight %.
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| CNB200410025463XA CN100441641C (en) | 2004-06-25 | 2004-06-25 | Water antki-rust composition |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200410025463XA CN100441641C (en) | 2004-06-25 | 2004-06-25 | Water antki-rust composition |
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| CN100441641C true CN100441641C (en) | 2008-12-10 |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102634804A (en) * | 2012-04-27 | 2012-08-15 | 湘潭大学 | Nickel plated battery steel casing organic antirust agent and use method thereof |
| CN103451001A (en) * | 2013-08-23 | 2013-12-18 | 吴江龙硕金属制品有限公司 | Machine tool cutting fluid and preparation method thereof |
| CN104649991A (en) * | 2013-11-25 | 2015-05-27 | 刘现梅 | Water-soluble 1-phenyl-5-mercaptotetrazole derivative and preparation method thereof |
| CN104649992A (en) * | 2013-11-26 | 2015-05-27 | 刘现梅 | 1-phenyl-5-(N, N-dihydroxyl amino methyne thio)-tetrazole and preparation method thereof |
| CN103820795B (en) * | 2014-01-22 | 2016-03-30 | 西南林业大学 | A kind of compound corrosion inhibitor and preparation method thereof and application |
| CN104562033A (en) * | 2014-09-30 | 2015-04-29 | 金寨县宏拓机电有限责任公司 | Antirust agent and preparation method thereof |
| CN111662582A (en) * | 2019-03-06 | 2020-09-15 | 中核华兴达丰机械工程有限公司 | Wear-resistant antirust paint for crane and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1035522A (en) * | 1988-03-01 | 1989-09-13 | 上海工业大学 | Rust preventing emulsion |
| CN1140189A (en) * | 1996-03-14 | 1997-01-15 | 吴镛俊 | Water anti-rust agent |
| US5744069A (en) * | 1993-11-24 | 1998-04-28 | Chiyoda Chemical Kabushiki Kaisha | Water soluable metal anticorrosive |
-
2004
- 2004-06-25 CN CNB200410025463XA patent/CN100441641C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1035522A (en) * | 1988-03-01 | 1989-09-13 | 上海工业大学 | Rust preventing emulsion |
| US5744069A (en) * | 1993-11-24 | 1998-04-28 | Chiyoda Chemical Kabushiki Kaisha | Water soluable metal anticorrosive |
| CN1140189A (en) * | 1996-03-14 | 1997-01-15 | 吴镛俊 | Water anti-rust agent |
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