CN102553501A - Method for preparing supported corrosion inhibitor - Google Patents
Method for preparing supported corrosion inhibitor Download PDFInfo
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- CN102553501A CN102553501A CN2011104519733A CN201110451973A CN102553501A CN 102553501 A CN102553501 A CN 102553501A CN 2011104519733 A CN2011104519733 A CN 2011104519733A CN 201110451973 A CN201110451973 A CN 201110451973A CN 102553501 A CN102553501 A CN 102553501A
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- water
- corrosion inhibitor
- oil emulsion
- emulsion system
- corrosion inhibiter
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Abstract
The invention relates to a method for preparing a supported corrosion inhibitor. The method comprises the following steps of: (1) dissolving an emulsifying agent in a dispersed medium; (2) dissolving ammonia water and water-soluble corrosion inhibitor in water, and dropwise adding mixed liquor to a water-in-oil emulsion system to form the water-in-oil emulsion system; and (3) dropwise adding tetraethylortho silicate to the water-in-oil emulsion system in the step 2, and reacting for a period of time under the constant temperature and forming the supported corrosion inhibitor. The supported corrosion inhibitor prepared by the method is prevented from being inactive in a corrosion environment; the effective utilization rate of the supported corrosion inhibitor is increased; and the valid period of the supported corrosion inhibitor is prolonged.
Description
Technical field
The present invention relates to a kind of preparation method of corrosion inhibiter, more specifically relate to a kind of preparation method of support type corrosion inhibiter.
Background technology
Corrosion inhibiter is meant that in medium a small amount of interpolation can reduce corrosive medium, prevent the material of metal erosion.The corrosion inhibiter technology as a kind of economy, effectively and the anti-corrosion method for metal of highly versatile occupies critical role in the metal erosion guard technology.Obtain to use widely at industrial departments such as oil, chemical industry, the energy, traffic, electromechanics, buildings, in some commercial production, become a requisite technological measure.Yet, because some problems that self can't overcome of corrosion inhibiter.For example in open system, promptly taken away before corrosion inhibiter is prone to be in full play, or the material that is extracted out carries outside by the medium that flows, cause waste.This has limited the generality that corrosion inhibiter is used greatly.
Microcapsules technology is a kind ofly to utilize natural or synthesized polymer material, and solid, liquid or even gaseous matter embedding are got up, and forms the technology of the microencapsulation with semi permeability or sealing cyst membrane.In recent years, inorganic material SiO
2Receive people and pay close attention to greatly because of having good biocompatibility, hydrophily and advantages such as extraordinary chemical stability and colloidal stability.The building-up process of most of siloxanes Capsules all is through matrix polymerization, removes center die plates with solvent or calcining method then, obtains hollow microcapsules.
Summary of the invention
The object of the present invention is to provide a kind of method for preparing the support type corrosion inhibiter,, prepare the corrosion inhibiter that microcapsules coat, can effectively overcome the deficiency in the known technology through reverse emulsion polymerization.
For realizing above-mentioned purpose, a kind of method for preparing the support type corrosion inhibiter provided by the invention the steps include:
1) emulsifying agent is dissolved in the decentralized medium;
2) ammoniacal liquor and water soluble rust inhibitor is soluble in water, and be added drop-wise in the water-in-oil emulsion system, water-in-oil emulsion system formed;
3) ethyl orthosilicate is added drop-wise in the water-in-oil emulsion system of step 2 discharging of isothermal reaction a period of time.
Described method, wherein, emulsifying agent is one or more in Span series and the OP series.
Described method, wherein, decentralized medium is cyclohexane, hexane or normal heptane.
Described method wherein, is carried out the operation of step 2 after the water-in-oil emulsion system of step 1 is heated.
Described method, wherein, water-in-oil emulsion system is heated to 35-40 ℃.
The advantage that the present invention possessed:
1) prevents corrosion inhibiter inactivation in corrosive environment, improve its effective rate of utilization, prolong the valid expiration date of corrosion inhibiter;
2) stability of raising corrosion inhibiter;
3) can effectively cover the bad smell of corrosion inhibiter, use safety and reliability;
4) the liquid corrosion inhibiter can be solidified through certain carrier, be convenient to storage and transportation, and can apply it to the anti-aging etc. of various corrosion-inhibiting coatings, plastics;
5) have slowly-releasing or controlled release characteristics.
Description of drawings
Fig. 1 is the synthetic sketch mapes of microcapsules of the present invention.
Fig. 2 is a microcapsules particle diameter distribution schematic diagram.
Fig. 3 is a microcapsules SEM image, and wherein A amplifies 30000 times, and B amplifies 20000 times, and C amplifies 50000 times, and D amplifies 1000 times.
Fig. 4 is a microcapsules SEM/EDX image.
Fig. 5 is STEM-EDS result.
The specific embodiment
It is capsule-core with the water soluble rust inhibitor that the present invention adopts reverse microemulsion process, the product S iO of positive tetraethyl orthosilicate (TEOS) hydrolysis
2Be cyst wall, prepared the microcapsules that coat corrosion inhibiter through one-step method.
Below the present invention is described in detail.
Need to prove:
Corrosion inhibiter of the present invention is the water-soluble inorganic corrosion inhibiter, and embodiment is to be that example describes with the sodium tungstate aqueous solution.
Emulsifying agent of the present invention is one or more in Span series and the OP series, and embodiment is to be that example describes with sorbitan monooleate (Span80) and sim alkylphenol APEO-10 (OP-10).
Decentralized medium of the present invention is cyclohexane, hexane or normal heptane, and embodiment is to be that example describes with the cyclohexane.
Embodiment one
1) experimental section
1.1) raw material
Cyclohexane is analyzed purely, and chemical industry Co., Ltd is risen by Beijing China; Sodium tungstate, analyze pure, Gansu Province, Shantou City west chemical industry Co., Ltd; Sorbitan monooleate (Span80), chemical pure, Tianjin recovery fine chemistry industry research institute; Sim alkylphenol APEO-10 (OP-10), chemical pure, Tianjin recovery fine chemistry industry research institute; Ethyl orthosilicate (TEOS) is analyzed purely, and benefit sharp fine chemicals in Beijing is limited; Ammoniacal liquor (mass fraction is 25%), analyze pure, the Beijing Chemical Plant.
1.2) method of operating
With Span80, the OP-10 emulsifying agent is dissolved in the cyclohexane, and magnet rotor stirs; Fully change over to after the dissolving in the four-hole reaction bulb of band condenser pipe, stirring, constant pressure funnel, stir (approximately 200r/min) 1h and also be heated to 35 ℃, with ammoniacal liquor and sodium tungstate is soluble in water and slowly be added drop-wise to (0.02ml/min) in the reaction bulb; The dropping time is 6h, afterwards TEOS is added drop-wise to (0.2ml/min) in the reaction bulb, and the dropping time is 1h; Drip and finish back isothermal reaction 48h, analysis and characterization is carried out in discharging.Experimental formula such as table 1 are the tabulation of corrosion inhibiter different content.
1.3) pattern of capsule particle characterizes
The morphology analysis of polysiloxanes hollow microcapsules adopts SEM (SEM) to observe, and the capsule size distribution is measured (DLS) through 200-SM type dynamic light scattering, and sealing through scanning transmission electron microscope-energy disperse spectroscopy (STEM/EDX) of corrosion inhibiter measured.
2) result and discussion
2.1) synthesis mechanism of microcapsules
Synthetic reaction equation such as Fig. 1:
The first step be with aqueous dispersion in the oil phase that contains emulsifying agent.The emulsifying agent Molecular Adsorption forms stable little water droplet at the W/O interface, and the emulsifying agent molecule plays a part this " microreactor " water droplet of protection in whole polymerization process.Second step was that reaction monomers TEOS is dissolved in the continuous phase oil phase, because the catalytic action of alkali, the hydrolysis-condensation reaction will take place at the oil-water interfaces place TEOS, form a highly cross-linked macromolecule shell of Si-O-Si at last, and stratum nucleare is the microcapsules that contain corrosion inhibiter.
Shell siloxanes hydrolysis formula is suc as formula 1:
R-Si(OC
2H
5)
3+H
2O→R-Si(OH)
3+C
2H
5OH
or?R-Si(OH)
3+R-Si(OC
2H
5)
3→
Formula 1
2.2) pattern of capsule particle and size distribution characterize
Fig. 2 is that the nucleocapsid structure polysiloxanes microcapsules reversed-phase emulsion that synthesizes is diluted to clarification after the measured particle size distribution figure of DLS through cyclohexane.As can be seen from the figure particle diameter distributes and presents single peak; Its average grain diameter is 616nm, also can find out from the particle diameter distribution map, and system particle diameter major part is all in the 1000nm; There is the particle of a small amount of greater particle size to occur; This might be in the polymerization process, siloxanes generation polycondensation reaction between two or more capsules, and coalescence becomes macroparticle.
Fig. 3 drops on the sheet glass that cleans up after cyclohexane dilution for reversed-phase emulsion, the air dry of spending the night under the room temperature, metal spraying after SEM (ESEM) observation post get.Can find out that from photo the microcapsule particle particle diameter is approximately 1000nm; Also roughly the same with the light scattering particle size distribution results; From figure, it can also be seen that the wall of capsule is very thin; All capsule collapses after dried, this possibly be because the microcapsules particle diameter is big, polysiloxanes shell itself causes without causes such as calcining curing.But can find out that from Electronic Speculum figure the microcapsules spheroidal particle forms, and can find out and formed Capsules.
Adopt ESEM-energy spectrum method to analyze the surface of microcapsule element and form, the result sees Fig. 4 and table 2.Can know that by the result composition on silicon dioxide microsphere surface is C, O, Si, does not have W elements.
The polymer that prescription in the table 11 reversed-phase emulsion is obtained is added on the copper mesh of 200 orders plating carbon film through drop after the cyclohexane dilution; Air dry is crossed ight STEM (scanning transmission microscope) and is observed in air; And sample is carried out elementary analysis with EDS (X-ray energy spectrometer), see Fig. 5.From EDS result, can find out, tangible W elements power spectrum characteristic peak occur.What ESEM-power spectrum characterized is that the microsphere surface element is formed, and scanning transmission electron microscope-power spectrum sign is that the microballoon inner element is formed.In conjunction with the result of ESEM and scanning transmission electron microscope, explain that the sustained release agent sodium tungstate successfully is encapsulated in the silica microcapsules, rather than attached to the surface of silicon dioxide microsphere.
Adopt EDS that element is formed and carry out quantitative analysis, the result sees table 3.
Sodium tungstate (Na
2WO
42H
2O), molecular weight 329.86; Positive tetraethyl orthosilicate (C
8H
20O
4Si), molecular weight: 208.33, density 0.9356g/mL
Calculate the clad ratio of sodium tungstate in two prescription polymerization gained microcapsules by table 2 result and see table 4.
Show that the sodium tungstate that is added on the emulsion aqueous phase is covered by in the silicon dioxide granule, and increase that clad ratio increases with the addition of sodium tungstate.
3) conclusion
Utilize reversed emulsion polymerization to synthesize the microcapsules of the nucleocapsid structure that is coated with the sodium tungstate corrosion inhibiter.Can composite structure complete, Size Distribution is the polysiloxanes hollow microcapsules comparatively uniformly; And can realize that in conjunction with the inverse emulsion polymerization principle one-step method preparation coats the microcapsules of corrosion inhibiter; Along with the increase of aqueous phase corrosion inhibiter addition, the clad ratio of corrosion inhibiter increases.
Table 1: experimental formula
Table 2:SEM-EDS method test surface of microcapsule elemental composition
| Element | Weight % | Mole % |
| C | 31.09 | 48.45 |
| O | 11.15 | 13.04 |
| Si | 57.77 | 38.50 |
| Amount to | 100.00 | 100.00 |
Table 3: the content of element silicon and W elements in the power spectrum mensuration microcapsules
Table 4: sodium tungstate clad ratio
| Prescription 1 | Prescription 2 | |
| Clad ratio | 15％ | 67％ |
Claims (5)
1. a method for preparing the support type corrosion inhibiter the steps include:
1) emulsifying agent is dissolved in the decentralized medium;
2) ammoniacal liquor and water soluble rust inhibitor is soluble in water, and be added drop-wise in the water-in-oil emulsion system, water-in-oil emulsion system formed;
3) ethyl orthosilicate is added drop-wise in the water-in-oil emulsion system of step 2 discharging of isothermal reaction a period of time.
2. method according to claim 1, wherein, emulsifying agent is one or more in Span series and the OP series.
3. method according to claim 1, wherein, decentralized medium is cyclohexane, hexane or normal heptane.
4. method according to claim 1 wherein, is carried out the operation of step 2 after the water-in-oil emulsion system of step 1 is heated.
5. method according to claim 4, wherein, water-in-oil emulsion system is heated to 35-40 ℃.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103225085A (en) * | 2013-04-25 | 2013-07-31 | 中国科学院海洋研究所 | Application of triazole compound containing salicylaldehyde as high efficiency corrosion inhibitor |
| CN108425119A (en) * | 2018-04-09 | 2018-08-21 | 翟琳 | A kind of preparation method of metal inhibitor |
| CN109762546A (en) * | 2019-01-28 | 2019-05-17 | 西南科技大学 | A kind of preparation method of the acrylamide being loaded with corrosion inhibiter-bentonite capsule |
| CN112662300A (en) * | 2020-12-26 | 2021-04-16 | 武汉中科先进技术研究院有限公司 | Long-acting wear-resistant slow-release antiviral coating and preparation |
| CN114643027A (en) * | 2022-03-28 | 2022-06-21 | 国网江苏省电力有限公司电力科学研究院 | Composite graphene microcapsule and preparation method and application thereof |
| CN116913397A (en) * | 2023-07-17 | 2023-10-20 | 四川冠山科技有限公司 | Development method of green corrosion inhibitor system with core-shell structure |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103225085A (en) * | 2013-04-25 | 2013-07-31 | 中国科学院海洋研究所 | Application of triazole compound containing salicylaldehyde as high efficiency corrosion inhibitor |
| CN108425119A (en) * | 2018-04-09 | 2018-08-21 | 翟琳 | A kind of preparation method of metal inhibitor |
| CN109762546A (en) * | 2019-01-28 | 2019-05-17 | 西南科技大学 | A kind of preparation method of the acrylamide being loaded with corrosion inhibiter-bentonite capsule |
| CN109762546B (en) * | 2019-01-28 | 2021-06-25 | 西南科技大学 | Preparation method of corrosion inhibitor-loaded acrylamide-bentonite capsule |
| CN112662300A (en) * | 2020-12-26 | 2021-04-16 | 武汉中科先进技术研究院有限公司 | Long-acting wear-resistant slow-release antiviral coating and preparation |
| CN114643027A (en) * | 2022-03-28 | 2022-06-21 | 国网江苏省电力有限公司电力科学研究院 | Composite graphene microcapsule and preparation method and application thereof |
| CN116913397A (en) * | 2023-07-17 | 2023-10-20 | 四川冠山科技有限公司 | Development method of green corrosion inhibitor system with core-shell structure |
| CN116913397B (en) * | 2023-07-17 | 2024-02-02 | 四川冠山科技有限公司 | Development method of green corrosion inhibitor system with core-shell structure |
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Inventor after: Li Ye Inventor after: Shen Dawa Inventor after: Zhang Zhiguo Inventor after: Tian Xingling Inventor after: Ma Qinglin Inventor before: Li Na Inventor before: Shen Dawa Inventor before: Zhang Zhiguo Inventor before: Tian Xingling Inventor before: Ma Qinglin |
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Free format text: CORRECT: INVENTOR; FROM: LI NA SHEN DAWA ZHANG ZHIGUO TIAN XINGLING MA QINGLIN TO: LI YE SHEN DAWA ZHANG ZHIGUO TIAN XINGLING MA QINGLIN |
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Application publication date: 20120711 |