CN105603437A - Low-pH controllable-release intelligent corrosion inhibitor preparation method - Google Patents
Low-pH controllable-release intelligent corrosion inhibitor preparation method Download PDFInfo
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- CN105603437A CN105603437A CN201610019344.6A CN201610019344A CN105603437A CN 105603437 A CN105603437 A CN 105603437A CN 201610019344 A CN201610019344 A CN 201610019344A CN 105603437 A CN105603437 A CN 105603437A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/173—Macromolecular compounds
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Abstract
The invention belongs to the field of preparation of intelligent corrosion inhibitors and particularly relates to a low-pH controllable-release intelligent corrosion inhibitor preparation method. Most metals are prone to corrosion in low-pH environments, and waste and environment damage are caused due to the fact that use concentrations of traditional corrosion inhibitors in use cannot be adjusted timely according to pH environmental changes. A low-pH controllable-release intelligent corrosion inhibitor is composed of hydrogel with pH responsiveness and a corrosion inhibitor with a corrosion inhibition function, and the corrosion inhibitor is coated with the low-pH-sensitivity hydrogel. The low-pH controllable-release intelligent corrosion inhibitor preparation method has the advantages that 1) control of corrosion inhibitor release speeds on the basis of pH can be realized, and the corrosion inhibitor is released quickly under low-pH conditions and released slowly or even not released under high-pH conditions; 2) long-acting effects of the corrosion inhibitor can be realized, and high corrosion inhibition efficiency is achieved; 3) the wide applicability is realized.
Description
Technical field
The invention belongs to the preparation field of intelligent corrosion inhibiter, particularly a kind of preparation method of intelligent corrosion inhibiter of low pH controllable release.
Background technology
The etching problem of metal material spreads all overNationalEconomic every field, most metals material is more easily corrosion under acid condition. Existing metallic material corrosion safeguard procedures mainly comprise: 1) correct selection and appropriate design, the corrosion stability of raising material itself; 2) change environment: change pH, change stress state, add corrosion inhibiter etc. to change environment; 3) electrochemical protection: cathodic protection, anodic protection; 4) adopt coated layer and surface modification, material and corrosive medium are separated: chemical composition coating, metal electroplating layer, nonmetallic coating, anti-tarnish paper etc.; 5) management of corrosion and protection and education. Wherein, corrosion inhibiter has that using method is easy, applicability extensively, strong adaptability (in use need not Special Equipment, need not change the character of hardware), technology of the package is simple, cost is low, rust-proof life is long, the multiple advantage such as energy-conservation, be now widely used. But, the occupation mode that traditional corrosion inhibiter conventionally adopts disposable input or throws in continuously. At the use initial stage, corrosion inhibiter dense, may cause the waste of corrosion inhibiter; As time goes on, the problems such as corrosion inhibiter is hydrolyzed in environment under arms, degrades, inefficacy, cause its corrosion mitigating effect to decline. Therefore, recent domestic scholar is devoted to research and develop a kind of intelligent long-acting corrosion inhibiter always, wishes that it can control automatically according to the variation of surrounding environment the burst size of corrosion inhibiter. Environmental sound, the hydrogel with pH sensitiveness are prepared to intelligent corrosion inhibiter as the carrier of corrosion inhibiter, are one of research and development directions of intelligent corrosion inhibiter.
The sensitiveness of pH sensitive aqueous gel conventionally derive from its strand with ionogen, as carboxylic group or amino group etc., mostly therefore be polyelectrolyte hydrogel. Polyelectrolyte hydrogel swelling is to be mainly present in the electrostatic repulsion in polymer chain due to electric charge wherein, and its swelling degree is subject to as the impact of any conditions such as the type of Coulomb repulsion, pH, ionic strength and counter ion. For the responsive aqueous gel of pH with alkalescent group (being generally amino), in the time that the pH of surrounding medium value reaches a certain particular value, the charged cation of the protonated formation of alkalescent group on hydrogel molecular side chain, Coulomb repulsion occurs between like charges, thereby it is swelling that hydrogel is occurred. For the pH sensitive aquagel with faintly acid group, in the time that the pH of surrounding medium value is greater than a certain particular value, hydrogel occurs swelling.
Because most metals material more easily corrodes under acid condition, therefore, developmental research can be under acid condition fast, discharge in a large number, and under neutrality or alkali condition slowly, a small amount of intelligent corrosion inhibiter discharging is very important. Because synthetic pH sensitive aquagel is high molecular polymer, environmental sound, therefore can be used as the carrier of intelligent corrosion inhibiter. The pH sensitiveness of pH sensitive aquagel, i.e. swellbility size and difference under varying environment pH condition, is the important performance indexes of intelligent corrosion inhibiter. PH sensitiveness is stronger, and this pH sensitive aquagel is more suitable as the intelligent carrier of corrosion inhibiter.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of preparation method of intelligent corrosion inhibiter of low pH controllable release, and the method technique is simple, and cost is low, is widely used. The long-acting intelligent corrosion inhibiter corrosion mitigating effect of preparation is good, has a good application prospect.
In order to solve existing issue, technical scheme provided by the invention is:
A kind of preparation method of intelligent corrosion inhibiter of low pH controllable release, it is characterized in that: comprise that mass fraction is the monomer of 40%-60%, mass fraction is the crosslinking agent of 0.2%-1.0%, mass fraction is the initator of 0.3-0.7%, all the other are the corrosion inhibiter aqueous solution and deionized water, described monomer is dimethylaminoethyl methacrylate, described crosslinking agent is methylene-bisacrylamide, described initator is 2-hydroxy-2-methyl-1-[4-(2-hydroxyl-oxethyl) phenyl]-1-acetone, described corrosion inhibiter is benzotriazole, its preparation method comprises the following steps:
1) preparation of pH sensitive aquagel
A) described monomer, crosslinking agent, initator are added in dried and clean beaker, add above-mentioned deionized water, lucifuge stirs certain hour, until solution homogeneous transparent;
B) with syringe, solution is injected from molding jig, fix and be placed under uviol lamp;
C) after reaction finishes, remove mould, take out hydrogel, use card punch that hydrogel is cut into sequin;
D) disk gel is put into the culture dish that contains deionized water, soak to remove the raw material of unreacted minute quantity;
E) gel is put into freezer compartment of refrigerator freezing after, be transferred in vacuum freeze drier, vacuum freeze drying is to constant weight, obtains pH sensitive aquagel.
2) preparation of the intelligent corrosion inhibiter that low pH discharges fast
Described pH sensitive aquagel is soaked in the corrosion inhibiter aqueous solution, soaks after 20-28h and put into freezer compartment of refrigerator, be transferred in freeze drier after freezing, vacuum freeze drying, to constant weight, can obtain controlling the long-acting intelligent corrosion inhibiter discharging by pH.
Another technical scheme of the present invention is that the mass fraction of described monomer is 49.6%, the mass fraction of crosslinking agent is 0.33%, the mass fraction of initator optimum while being 0.5%.
Another technical scheme of the present invention is described corrosion inhibitor solution, and its optimal concentration is saturated concentration.
Principle: dimethylaminoethyl methacrylate molecule is with the characteristic group with pH sensitiveness, be the amino on side chain, and contain a carbon-carbon double bond, can with two carbon-carbon double bond polymerization reaction take places at crosslinking agent methylene-bisacrylamide molecule two ends, be cross-linked to form the three-dimensional netted polyalcohol hydrogel of pH sensitiveness. End group-the amino of hydrogel can be protonated under acid condition, thereby swelling. In the process of coated BTA corrosion inhibiter, the pH sensitive aqueous gel absorption BTA aqueous solution occurs swelling, and the BTA being absorbed by pH sensitive aqueous gel is retained in xerogel structure after freeze drying, becomes intelligent corrosion inhibiter.
The type intelligence corrosion inhibiter of low pH controllable release prepared by the present invention can regulate the swellbility size of pH sensitive aquagel by the pH value that changes the concentration of monomer, crosslinking agent and ratio, surrounding medium, thereby can control embedding amount and the burst size of corrosion inhibiter.
Beneficial effect of the present invention:
(1) technique of the present invention is simple, and cost is low, adopts and use water as reaction medium in preparation process, produces without poisonous and hazardous accessory substance, environmentally friendly.
(2) the intelligent corrosion inhibiter of the low pH controllable release that prepared by the present invention is good to the pH sensitiveness of surrounding medium, inhibition efficiency is high, has a good application prospect.
Brief description of the drawings
Fig. 1For the theoretical synthetic route of pH sensitive aqueous gel in the intelligent corrosion inhibiter of low pH controllable release of preparation.
Fig. 2For the swelling curve of the low pH sensitive aquagel of A3B1 type of preparationFigure。
Fig. 3For the swelling curve of the low pH sensitive aquagel of A3B2 type of preparationFigure。
Fig. 4For the swelling curve of the low pH sensitive aquagel of A3B3 type of preparationFigure。
Fig. 5For the swelling curve of the low pH sensitive aquagel of A3B4 type of preparationFigure。
Fig. 6For the swelling curve of the low pH sensitive aquagel of A1.5B1 type of preparationFigure。
Fig. 7For the swelling curve of the low pH sensitive aquagel of A4.5B3 type of preparationFigure。
Fig. 8For the corrosion inhibiter release kinetics profile of intelligent corrosion inhibiter of the low pH controllable release of preparation.
Fig. 9For throwing in low pH controllable release intelligence corrosion inhibiter after one hour, the polarization curve of copper.
Figure 10For throwing in low pH controllable release intelligence corrosion inhibiter after six hours, the polarization curve of copper.
Figure 11For throwing in after low pH controllable release intelligence corrosion inhibiter, the ac impedance spectroscopy of copper.
Detailed description of the invention
Below in conjunction with specific embodiment, further set forth the present invention. Should be understood that these embodiment are only not used in and limit the scope of the invention for the present invention is described. In addition should be understood that those skilled in the art can make various changes or modifications the present invention after having read the content that the present invention tells about, that these equivalent form of values fall within the application is equally appendedClaimBook limited range.
Embodiment 1
1) preparation of the hydrogel of pH sensitivity
A) take 3g monomer, 0.02g crosslinking agent, 0.03g initator and add in dried and clean beaker, and measure 3mL deionized water and add wherein, lucifuge stirs certain hour, until solution homogeneous transparent;
B) two clean sheet glass of folder silicone rubber plate are fixed, solution is injected from molding jig and fix with syringe;
C), after uviol lamp preheating 10min, mould is placed on to (between sheet glass and uviol lamp, distance is about 3cm) room temperature under uviol lamp and irradiates 1h;
D) close uviol lamp, remove mould, take out prepared hydrogel, hydrogel is cut into diameter 1cm circular shaped patches with card punch, put it in the culture dish that contains deionized water, soak 2 days (changing water one time every 6h) to remove unreacted raw material;
E) by circular gel sheet freezing 24h in freezer compartment of refrigerator, will freeze rear circular gel sheet and in freeze drier, be dried to constant weight, obtain pH sensitive aquagel.
2) preparation of the intelligent corrosion inhibiter of low pH controllable release
Getting above-mentioned xerogel is soaked in the aqueous solution that contains BTA corrosion inhibiter, average every be immersed in 20mL solution (to ensure gel can be not overlapped and affect solute exchange cause the medicine carrying inhomogeneous), BTA concentration is 4g/L, leave standstill 24h, remove the unnecessary BTA aqueous solution and carry the hydrogel of corrosion inhibiter with deionized water rinsing. Put it in freezer compartment of refrigerator, after freezing 24h, be transferred to immediately vacuum freeze drying in vacuum freezing drying oven and, to constant weight, seal and preserve.
Prepared pH sensitive aquagel has been carried out to pH sensitivity tests,As Fig. 3Shown in, its pH sensitiveness optimum, is the suitable carrier of corrosion inhibiter. The intelligent corrosion inhibiter of preparing based on A3B2 hydrogel, its Drug Release Kinetics curveAs Fig. 8Shown in, it can discharge corrosion inhibiter according to the control of pH environment, discharges fast and in a large number, and slowly discharge in pH=8 cushioning liquid in pH=2 cushioning liquid, has significant pH sensitiveness. This intelligence corrosion inhibiter has been carried out to corrosion inhibition test,As Fig. 9～11Shown in, it not only shows efficient corrosion inhibition, has also shown obvious long-acting performance, has good application prospect.
Embodiment 2
1) preparation of the hydrogel of pH sensitivity
A) take 3g monomer, a certain amount of crosslinking agent, 0.03g initator and add in dried and clean beaker, and measure 3mL deionized water and add wherein, lucifuge stirs certain hour, until solution homogeneous transparent, concrete preparation parameterAs table 1Shown in;
Table 1The preparation parameter of A3 series polymethylacrylic acid dimethylaminoethyl hydrogel
* sheet of water gel use mg monomer and nx0.01g crosslinking agent are prepared in AmBn representative.
B) two clean sheet glass of folder silicone rubber plate are fixed, solution is injected from molding jig and fix with syringe;
C), after uviol lamp preheating 10min, mould is placed on to (between sheet glass and uviol lamp, distance is about 3cm) room temperature under uviol lamp and irradiates 1h;
D) close uviol lamp, remove mould, take out prepared hydrogel, hydrogel is cut into diameter 1cm circular shaped patches with card punch, put it in the culture dish that contains deionized water, soak 2 days (changing water one time every 6h) to remove unreacted raw material;
E) by circular gel sheet freezing 24h in freezer compartment of refrigerator, will freeze rear circular gel sheet and in freeze drier, be dried to constant weight, obtain pH sensitive aquagel.
2) preparation of the intelligent corrosion inhibiter of low pH controllable release
Getting above-mentioned xerogel is soaked in the aqueous solution that contains BTA corrosion inhibiter, average every be immersed in 20mL solution (to ensure gel can be not overlapped and affect solute exchange cause the medicine carrying inhomogeneous), BTA concentration is 4g/L, leave standstill 24h, remove the unnecessary BTA aqueous solution and carry the hydrogel of corrosion inhibiter with deionized water rinsing. Put it in freezer compartment of refrigerator, after freezing 24h, be transferred to immediately vacuum freeze drying in vacuum freezing drying oven and, to constant weight, seal and preserve.
Prepared pH sensitive aquagel has been carried out to pH sensitivity tests,As Fig. 2～7Shown in, these a series of hydrogels all show pH sensitiveness. Except A3B5, A3B6 very easily cracked and can not reversibly reusing in pH=2 cushioning liquid, other the suitable carrier that can serve as corrosion inhibiter. Wherein A3B2 hydrogel is optimum carrier.
Embodiment 3
1) preparation of the hydrogel of pH sensitivity
A) take a certain amount of monomer, a certain amount of crosslinking agent, 0.03g initator and add in dried and clean beaker, and measure 3mL deionized water and add wherein, lucifuge stirs certain hour, until solution homogeneous transparent, concrete preparation parameterAs table 2Shown in;
B) two clean sheet glass of folder silicone rubber plate are fixed, solution is injected from molding jig and fix with syringe;
C), after uviol lamp preheating 10min, mould is placed on to (between sheet glass and uviol lamp, distance is about 3cm) room temperature under uviol lamp and irradiates 1h;
D) close uviol lamp, remove mould, take out prepared hydrogel, hydrogel is cut into diameter 1cm circular shaped patches with card punch, put it in the culture dish that contains deionized water, soak 2 days (changing water one time every 6h) to remove unreacted raw material;
E) by circular gel sheet freezing 24h in freezer compartment of refrigerator, will freeze rear circular gel sheet and in freeze drier, be dried to constant weight, obtain pH sensitive aquagel.
Table 2Monomer/crosslinking agent ratio is the preparation parameter of the polymethylacrylic acid dimethylaminoethyl hydrogel of 3:2 series
* sheet of water gel use mg monomer and nx0.01g crosslinking agent are prepared in AmBn representative.
2) preparation of the intelligent corrosion inhibiter of low pH controllable release
Getting above-mentioned xerogel is soaked in the aqueous solution that contains BTA corrosion inhibiter, average every be immersed in 20mL solution (to ensure gel can be not overlapped and affect solute exchange cause the medicine carrying inhomogeneous), BTA concentration is 4g/L, leave standstill 24h, remove the unnecessary BTA aqueous solution and carry the hydrogel of corrosion inhibiter with deionized water rinsing. Put it in freezer compartment of refrigerator, after freezing 24h, be transferred to immediately vacuum freeze drying in vacuum freezing drying oven and, to constant weight, seal and preserve.
Prepared pH sensitive aquagel has been carried out to pH sensitivity tests,As Fig. 2～7Shown in, these a series of hydrogels all show pH sensitiveness. Except A1.5B1 is because of the loose especially solution of cross-linked structure breaks, other the suitable carrier that can serve as corrosion inhibiter. Wherein A3B2 hydrogel is optimum carrier.
Claims (3)
1. the preparation method of the intelligent corrosion inhibiter of a low pH controllable release, it is characterized in that: comprise that mass fraction is the monomer of 40%-60%, mass fraction is the crosslinking agent of 0.2%-1.0%, mass fraction is the initator of 0.3-0.7%, all the other are the corrosion inhibiter aqueous solution and deionized water, described monomer is dimethylaminoethyl methacrylate, described crosslinking agent is methylene-bisacrylamide, described initator is 2-hydroxy-2-methyl-1-[4-(2-hydroxyl-oxethyl) phenyl]-1-acetone, described corrosion inhibiter is benzotriazole, its preparation method comprises the following steps:
1) preparation of pH sensitive aquagel
Described monomer, crosslinking agent, initator are added in dried and clean beaker, add above-mentioned deionized water, lucifuge stirs certain hour, until solution homogeneous transparent;
Solution is injected from molding jig with syringe, fix and be placed under uviol lamp;
After reaction finishes, remove mould, take out hydrogel, use card punch that hydrogel is cut into sequin;
Disk gel is put into the culture dish that contains deionized water, soaked to remove the raw material of unreacted minute quantity;
By gel put into freezer compartment of refrigerator freezing after, be transferred in vacuum freeze drier, vacuum freeze drying is to constant weight, obtains pH sensitive aquagel;
2) preparation of the intelligent corrosion inhibiter that low pH discharges fast
Described pH sensitive aquagel is soaked in the corrosion inhibiter aqueous solution, soaks after 20-28h and put into freezer compartment of refrigerator, be transferred in freeze drier after freezing, vacuum freeze drying, to constant weight, can obtain controlling the long-acting intelligent corrosion inhibiter discharging by pH.
2. the preparation scheme of the sensitive aquagel of pH described in claim 1, the mass fraction that it is characterized in that described monomer is 49.6%, the mass fraction of crosslinking agent is 0.33%, the mass fraction of initator optimum while being 0.5%.
3. the preparation method of the responsive intelligent corrosion inhibiter of pH described in claim 1, is characterized in that described corrosion inhibitor solution, and optimal concentration is saturated concentration.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108914190A (en) * | 2018-08-03 | 2018-11-30 | 中国科学院金属研究所 | A kind of preparation method of magnesium alloy surface micro-arc oxidation/intelligence release structures integration composite coating |
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| CN102258498A (en) * | 2011-07-14 | 2011-11-30 | 四川大学 | Release mass transfer rate adjustable and controllable intelligent drug delivery carrier and preparation method thereof |
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- 2016-01-12 CN CN201610019344.6A patent/CN105603437A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US20100062054A1 (en) * | 2001-08-16 | 2010-03-11 | Sergey Kazakov | Lipobeads and their production |
| CN102258498A (en) * | 2011-07-14 | 2011-11-30 | 四川大学 | Release mass transfer rate adjustable and controllable intelligent drug delivery carrier and preparation method thereof |
| CN103145914A (en) * | 2013-03-25 | 2013-06-12 | 湖南工业大学 | Preparation method of high-strength nano-composite hydrogel with rapid dual responses of pH and temperature |
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Non-Patent Citations (1)
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| CN108914190A (en) * | 2018-08-03 | 2018-11-30 | 中国科学院金属研究所 | A kind of preparation method of magnesium alloy surface micro-arc oxidation/intelligence release structures integration composite coating |
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Application publication date: 20160525 |