CN102653861A - Surface treating agent specially used for offshore drilling drill conductor and preparation method thereof - Google Patents
Surface treating agent specially used for offshore drilling drill conductor and preparation method thereof Download PDFInfo
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- CN102653861A CN102653861A CN2012101470734A CN201210147073A CN102653861A CN 102653861 A CN102653861 A CN 102653861A CN 2012101470734 A CN2012101470734 A CN 2012101470734A CN 201210147073 A CN201210147073 A CN 201210147073A CN 102653861 A CN102653861 A CN 102653861A
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Abstract
The invention discloses a surface treating agent specially used for an offshore drilling drill conductor and a preparation method thereof. The treating agent comprises the following raw materials of bis-triethoxy silanyl ethane, gamma-aminopropyl-triethoxy silane, water-dispersible silicon dioxide, a fluorine compound, a stabilizing agent, a pH regulating agent and water. According to the invention, on the basis of a silane coupling agent film formation mechanism, the surface treating agent specially used for the offshore drilling drill conductor, which takes the silane coupling agent as a main film-forming agent, is developed by screening and compounding of principal components such as a silane coupling agent, the fluorine compound and an auxiliary film-forming agent. The surface treating agent disclosed by the invention has the characteristics of no toxicity or harm, no pollution, rapid low-temperature treatment, simpleness in operation, wide raw material source, low price, cleanness in manufacture and the like.
Description
Technical field
The present invention relates to a kind of special surface treating agent that prevents the metallic corrosion of offshore drilling drill conductor and improve sticking power between metal and the coating that is exclusively used in.
Background technology
Drill conductor be under the ODP to the sleeve pipe of sea-bottom shallow, its major function is an insulating sea water, forms the circulation of drilling fluid passage, simultaneously as the power of the holding structure of offshore wellhead.In boring the completion construction process, the intensity of riser pipe and security are most important for Offshore Operation safety.
Platform at sea, drill conductor is a requisite equipment in the exploration operation, all need spend substantial contribution domestic every year from external import.Drill conductor is according to its request for utilization and site work situation, and every casing length is about about 12m, and diameter dimension has 20 inches, 24 inches, 30 inches etc.Utilize the rapid-acting coupling of its sleeve end that every pipe is coupled together during use, and according to the depth of water situation in drilling well zone, with telescopic joint, to reach water proof and the purpose of protecting the drilling well conduit when prying into well.So the pipe shaft of drill conductor and the intensity of joint will enough be born the surging force of piling, the impact force of waves of seawater, and quick-detach, connection and water-sealed effect soon each other again.
Bonderizing is one important procedure during offshore oil drilling well drill conductor joint is produced as a metallic surface rot-resistant Technology always.The drill conductor material 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 deficiency that much himself can't overcome: at first; All contain objectionable impuritiess such as phosphoric acid salt and heavy metal in the phosphatization liquid, and in treating processes, can produce a large amount of sediments and obnoxious flavour, blocking pipe; What influence was produced normally carries out, and the waste water COD of discharging and heavy metal will endanger environment as not carrying out environmental protection treatment; In addition, the most of need of bonderizing carried out under the condition of heating, and energy consumption is bigger, complex process, and operation is also inconvenient.Along with the development and the progress of society, people are also more and more high to the requirement of coated metal prefinished products, hope that not only its self performance is good, hope that more it can satisfy growing environmental protection needs, HUMAN HEALTH requires and the resources conservation requirement.These drawbacks that conventional phosphatizing is handled are just seriously restricting further developing and using of it.
Therefore, people expect to develop a kind of brand-new treatment process, and it can accomplish that again technology is simple, environmental protection when keeping conventional phosphatizing treatment process advantage, and comprehensive cost is low.
Be to guarantee metal sleeve production, make waste liquid after its surface anticorrosion is handled meet the emission standard of environmental administration, will carry out advanced treatment process research and development.
Silane coupling agent is in same molecule, to contain inorganic and silicon-based hybrid thing organic reaction property group, and basic molecular formula is: R (CH2) n Si (OR) 3, and wherein OR is hydrolyzable group, R is an organo-functional group.Be transformed into silanol behind the silane hydrolyzate, silanol can form Si-O-Me key (Me is a metal) with the oxide compound or the hydroxyl reaction of metallic surface, also can form layer protecting film in the metallic surface by condensation cross-linking between the silanol self; Silane coupling agent all has bonding strength preferably as a kind of silicon compound with unique texture to inorganics and organism; So silane can be erected " molecule bridge " between the interface of inorganic materials and organic materials; Couple together the material of two kinds of different in kinds; So just improved the consolidation strength of interfacial layer effectively, improved the bonding force of paint film, also improved the resistance to corrosion of material simultaneously matrix.
In recent years, very active for the research of phosphatization alternative techniques both at home and abroad.
Chromium-free metal surface treatment agent (the patent number of patent application: 200510127048.X) of the rattan Kang Yan far away of Inst. of Technology Precision Electrical Discharge Work's, the rich man's invention of wine well; Provide a kind of can be used for metal product especially the surface-treated of galvanized metal product have the chromium-free metal surface treatment agent of excellent rustless property; This metal conditioner basically by comprise water and/or alcohol form as the siliceous binder solution of solvent; And the concentration of silica component is 8-25% weight; Especially; But the metal conditioner long term inhibition that comprises the alcoholic solution of the alkoxysilane oligomer with weight-average molecular weight 1000-10000 that obtains through the organoalkoxysilane hydrolysis condensation reaction is given birth to the appearance of white rust; Preferably; Per 100 weight part silica component; The average primary particle size of 3-25 weight part is no more than the dispersing nanometer grade titanium dioxide powder suspension of 70nm in siliceous binder solution, and the rustless property of metal conditioner can be through using pure dissolubility polyvinyl butyral resin and have vinyl or the epoxide group silane coupling agent as functional group through adding, and combines the nanoscale powder of dispersed titanium dioxide and further improve;
The pretty bright non-chromate metal surface treatment agent that waits people's invention in storehouse, Nippon Paint Co., Ltd island and uses thereof (patent number of patent application: 01108890.7); The non-chromate metal surface treatment agent that is used for PCM is provided; It every liter contain (a) silane coupling agent and/or its amount and be the hydrolysis condensation product of 0.01-100g/l; (b) its amount is the water-dispersible silica of 0.05-100g/l (solid); (c) the zirconium ion amount is the zirconium compounds of 0.01-50g/l, and/or the titanium ion amount is the titanium compound of 0.01-50g/l;
The metal conditioner of people such as the imperial palace Gao Zhi of Nikko Materials Co. Ltd invention and metallic substance (the patent number of patent application: 01801289.X) that applies with it; It is a kind of metal conditioner that contains following component (A) to (D); It is firmly adhered to metal substrate for example on the aluminium; Even there is very thin thickness to still have fabulous Corrosion Protection, and fabulous plasticity-arranged and, (A) be at least a silicoorganic compound that contain 3 carbonyls and at least 1 alkoxysilyl ADHESION OF PAINTS power; When the total amount of component (A) to (D) was 100, its wt ratio was 5-15; (B) be the epoxy resin of at least a alkanolamine modification, with respect to above-mentioned total amount, its wt ratio is 10-30; (C) be at least a end capped POLYMETHYLENE POLYPHENYLISOCYANATE, with respect to total amount, its wt ratio is 50-70; And (D) be at least a aminoresin, with respect to above-mentioned total amount, its wt ratio is 5-15;
Pretty bright non-chromate metal surface treatment agent and surface treatment method (the patent number of patent application: 01801232.X) that waits people's invention in storehouse, Nippon Paint Co., Ltd island; It every liter contain (a) 0.01-100 grams per liter silane coupling agent and/or its hydrolysis condensation product; (b) 0.05-100 grams per liter water-dispersible silica (solid-state); (c) the zirconium ion amount is the zirconium compounds of 0.01-50g/l; And/or the titanium ion amount is the titanium compound of 0.01-50g/l, and/or (d) the 0.01-100 grams per liter contains the compound of sulfo-carbonyl and/or (e) 0.1-100 grams per liter water soluble acrylic resin.
Summary of the invention
The present invention aims to provide a kind of nontoxic, harmless, free of contamination surface treatment agent that is exclusively used in the offshore drilling drill conductor and preparation method thereof.
Concrete technical scheme of the present invention is following:
Be exclusively used in the surface treatment agent of offshore drilling drill conductor, form by following materials of weight proportions:
1, two (triethoxy is silica-based) ethane 3-5% of 2-
γ-An Bingjisanyiyangjiguiwan 2-4%
Water-dispersible silica 6-8%
Fluorine cpd 1-1.5%
Stablizer 5-6%
PH adjustment agent 0.5-0.8%
Water surplus.
Be exclusively used in the surface treatment agent of offshore drilling drill conductor, described fluorine cpd are a kind of or mixture in Zirconium tetrafluoride and the titanium fluoride.
Be exclusively used in the surface treatment agent of offshore drilling drill conductor, described stablizer is selected any in methyl alcohol, ethanol, propyl alcohol, the Virahol for use, or its mixture.
Be exclusively used in the surface treatment agent of offshore drilling drill conductor, described pH adjustment agent is a kind of in formic acid, acetate and the sulfuric acid.
Be exclusively used in the preparation method of the surface treatment agent of offshore drilling drill conductor, comprise the steps:
(1) get in the above-mentioned prescription 1, two (triethoxy the is silica-based) ethane of 2-add in 2/3rds the water, fully stir and treat to add γ-An Bingjisanyiyangjiguiwan more therein after its intact dissolving, make work in-process A after fully stirring;
(2) the dispersed silicon-dioxide of water intaking adds in the remaining water, fully stirs and treats to add fluorine cpd more therein after its intact dissolving, and it is for use to make work in-process B after fully stirring again;
(3) work in-process B is added among the work in-process A, add stablizer and fully stir its pH value of back measurement, the pH value is adjusted between the 1-3, make the surface treatment agent that is exclusively used in the offshore drilling drill conductor with pH adjustment agent.
(γ-APS) is a main film forming substance, and their effects of being cross-linked with each other can form the silane adsorption film of one deck densification in the metallic surface for wherein two triethoxysilicane alkyl ethane (BTSE) and γ-An Bingjisanyiyangjiguiwan; Water-dispersible silica is a secondary film formers; Fluorine cpd mainly are that the density that is used for increasing the silane adsorption film is improved quality of forming film; PH adjustment agent is used for promoting the hydrolysis of silane and then quickens its film process.
Beneficial effect of the present invention: the present invention is on the basis of silane coupling agent membrane formation mechanism; (major ingredient screenings and composite such as BTSE, γ-APS), fluorine cpd, secondary film formers, working out with silane coupling agent is the special surface treating agent of the offshore drilling drill conductor of main membrane-forming agent through silane coupling agent.That product of the present invention has is nontoxic, harmless, pollution-free, low temperature fast processing, simple to operate, characteristics such as raw material sources are extensive, price is low, cleaner production.
Embodiment
Through embodiment the present invention is done to describe further below.
Embodiment 1:
Being used for the metallic surface pretreated is that the metal conditioner of staple is made up of following raw materials according with the silane coupling agent:
Two triethoxysilicane alkyl ethane (BTSE) 3%
(γ-APS) 4% for γ-An Bingjisanyiyangjiguiwan
Water-dispersible silica 5.8%
Zirconium tetrafluoride 1%
Ethanol 5%
Acetate 0.5%
Water surplus.
It is described that to be used for the metallic surface pretreated be that the metal conditioner preparation method of staple comprises the steps: with the silane coupling agent
(1) gets in the water of two triethoxysilicane alkyl ethane (BTSE) addings 2/3rds in the above-mentioned prescription, fully stir and treat to add γ-An Bingjisanyiyangjiguiwan (γ-APS), make work in-process A after abundant the stirring more therein after its intact dissolving;
(2) the dispersed silicon-dioxide of water intaking adds in the remaining water, fully stirs to treat to add therein after its intact dissolving that to make work in-process B after fluorine cpd fully stir again for use again;
(3) work in-process B is added among the work in-process A, add stablizer and fully stir its pH value of back measurement, the pH value is adjusted between 1 ~ 3, make the special surface treating agent that is used for the offshore drilling drill conductor with pH adjustment agent.
Embodiment 2:
Being used for the metallic surface pretreated is that the metal conditioner of staple is made up of following raw materials according with the silane coupling agent:
Two triethoxysilicane alkyl ethane (BTSE) 3.5%
(γ-APS) 5% for γ-An Bingjisanyiyangjiguiwan
Water-dispersible silica 7%
Zirconium tetrafluoride 1.5%
Methyl alcohol 5%
Sulfuric acid 0.5%
Water surplus.
The preparation method is with embodiment 1.
Embodiment 3:
Being used for the metallic surface pretreated is that the metal conditioner of staple is made up of following raw materials according with the silane coupling agent:
Two triethoxysilicane alkyl ethane (BTSE) 3%
(γ-APS) 4.4% for γ-An Bingjisanyiyangjiguiwan
Water-dispersible silica 7%
Titanium fluoride 1.5%
Ethanol 5.5%
Sulfuric acid 0.5%
Water surplus.
The preparation method is with embodiment 1.
Embodiment 4:
Being used for the metallic surface pretreated is that the metal conditioner of staple is made up of following raw materials according with the silane coupling agent:
Two triethoxysilicane alkyl ethane (BTSE) 5%
(γ-APS) 4% for γ-An Bingjisanyiyangjiguiwan
Water-dispersible silica 7.5%
Titanium fluoride 1.5%
Virahol 5%
Acetate 0.8%
Water surplus.
The preparation method is with embodiment 1.
Test-results:
Before utilizing this treatment agent that the metallic surface is handled, at first pending workpiece is cleaned completely with alkaline cleaner; And soaking fully with the clear water rinsing and by water immediately after the alkali cleaning promptly to carry out the silylanization processing after forming seamless moisture film.
The technical process that we handle by alkaline degreasing → washing → silylanization to cold-reduced sheet test block handle.Silylanization treatment time 3min wherein, temperature normal temperature.
To test the processing of prepared sample and conventional phosphatizing (iron is phosphatization, Zinc phosphating) and chromating compares; The coating that test is adopted is polyester-triglycidyl isocyanurate (TGIC) powder coating, tests by the salt air corrosion of ASTM B-117.Test sample is made comparisons through measuring etched width (the corrosion spread scenarios after coatingsurface is with the miter angle delineation).In test, sealed with wax in three limits of sample, and light is cutd open on the 4th limit.Result who obtains such as following table:
The etching width of cold drawing
| Treatment process | Etching width (mm) |
| Alkali cleaning | 60±2 |
| Iron is phosphatization | 22±2 |
| Zinc phosphating | 17±2 |
| Iron is phosphatization+chromating | 12±3 |
| Silylanization is handled | 3±0.5 |
Can find out from last table, film and base material combine effect and preservative effect, its antiseptic property reaches or is superior to phosphatize phosphate coat and contrasts index accordingly.
Can draw to draw a conclusion through test: silane coupling agent is as a kind of silicon compound with unique texture; Erected the bridge between inorganics and the organism; Adopt silane coupled technology that metal is carried out surface treatment; The conversion film of good application and corrosion protection result be can on metal, obtain to have, metallic substance and adhesive force of coatings and resistance to corrosion significantly improved.The composite use of BTSE and γ-APS can obtain respond well silane film.Can't form utilizable conversion film but silane coupling agent is used in the metallic surface separately, must be used with other auxiliary agent and could obtain good result.
Claims (5)
1. surface treatment agent that is exclusively used in the offshore drilling drill conductor is characterized in that: be made up of following materials of weight proportions:
1, two (triethoxy is silica-based) ethane 3-5% of 2-
γ-An Bingjisanyiyangjiguiwan 2-4%
Water-dispersible silica 6-8%
Fluorine cpd 1-1.5%
Stablizer 5-6%
PH adjustment agent 0.5-0.8%
Water surplus.
2. the surface treatment agent that is exclusively used in the offshore drilling drill conductor according to claim 1 is characterized in that: described fluorine cpd are a kind of or mixture in Zirconium tetrafluoride and the titanium fluoride.
3. the surface treatment agent that is exclusively used in the offshore drilling drill conductor according to claim 1 is characterized in that: described stablizer is selected any in methyl alcohol, ethanol, propyl alcohol, the Virahol for use, or its mixture.
4. the surface treatment agent that is exclusively used in the offshore drilling drill conductor according to claim 1 is characterized in that: described pH adjustment agent is a kind of in formic acid, acetate and the sulfuric acid.
5. a preparation method who is exclusively used in the surface treatment agent of offshore drilling drill conductor as claimed in claim 1 is characterized in that comprising the steps:
(1) get in the above-mentioned prescription 1, two (triethoxy the is silica-based) ethane of 2-add in 2/3rds the water, fully stir and treat to add γ-An Bingjisanyiyangjiguiwan more therein after its intact dissolving, make work in-process A after fully stirring;
(2) the dispersed silicon-dioxide of water intaking adds in the remaining water, fully stirs and treats to add fluorine cpd more therein after its intact dissolving, and it is for use to make work in-process B after fully stirring again;
(3) work in-process B is added among the work in-process A, add stablizer and fully stir its pH value of back measurement, the pH value is adjusted between the 1-3, make the surface treatment agent that is exclusively used in the offshore drilling drill conductor with pH adjustment agent.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103834208A (en) * | 2012-11-22 | 2014-06-04 | 汉达精密电子(昆山)有限公司 | Environment-friendly type magnesium alloy skin membrane treatment solution and its preparation method |
| CN103897584A (en) * | 2014-04-11 | 2014-07-02 | 中国海洋石油总公司 | Surface silane treatment agent of offshore drilling tool joint |
| CN104846359A (en) * | 2014-02-17 | 2015-08-19 | 广州中国科学院工业技术研究院 | Composite treatment agent for metal surface pretreatment, preparation method and applications thereof |
| CN105400239A (en) * | 2015-12-18 | 2016-03-16 | 北京航天赛德科技发展有限公司 | Preparation method of modified silicon dioxide obtained via super-hydrophobic modification |
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| CN105400239A (en) * | 2015-12-18 | 2016-03-16 | 北京航天赛德科技发展有限公司 | Preparation method of modified silicon dioxide obtained via super-hydrophobic modification |
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Application publication date: 20120905 |