CN113861422B - Preparation method of polythioether corrosion inhibitor containing cobaltocene cation side group and corrosion inhibitor system - Google Patents
Preparation method of polythioether corrosion inhibitor containing cobaltocene cation side group and corrosion inhibitor system Download PDFInfo
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Abstract
The invention relates to a preparation method of a polythioether corrosion inhibitor containing cobaltocene cation side groups and a corrosion inhibitor system, wherein sulfur atoms are introduced into a polymer main chain by utilizing a simple and convenient mercaptan-alkene click polymerization reaction to obtain saturated polythioethers with different numbers of sulfonate groups on side chains, and then the target polythioether corrosion inhibitor with different numbers of cobaltocene ions on side chains is prepared by high-efficiency azide and copper-catalyzed azide-alkynyl click reaction. The polymer corrosion inhibitor can further enhance the interaction between the corrosion inhibitor and the metal surface through the synergistic effect of sulfur atoms on a main chain, side group connecting groups triazole and cobaltosic chloride ions and the metal surface and the excellent film forming property of the polymer, so that the excellent corrosion inhibition effect is achieved. The final corrosion inhibition test shows that: at 25 ℃, when immersed in 5% HCl corrosion inhibition medium for 6 hours, the corrosion inhibitor with the concentration of 15ppm has the corrosion inhibition efficiency of 96% on metal.
Description
Technical Field
The invention belongs to the field of chemical corrosion prevention, and relates to a preparation method of a polythioether corrosion inhibitor containing cobaltocene cation side groups and a corrosion inhibitor system.
Background
Metal corrosion is a significant concern in most industrialized countries. The maintenance costs associated with corrosion in industrial facilities in many countries are reported to be 1-5% of the total national production. One study published by the national corrosion engineering institute 2013 showed that global corrosion costs estimated to be $ 2.5 trillion, corresponding to 3.4% of the total global domestic production in the current year. More importantly, once the infrastructure collapses, corrosion can cause loss of economic, natural resources and human life, and thus research into mature corrosion mitigation techniques is of paramount importance. Current methods of corrosion reduction include anodic protection, cathodic protection, coatings and alloying, among others, with metal corrosion inhibitors being one of the most effective and practical corrosion protection methods due to ease of use.
In recent years, corrosion inhibitors are sequentially reported to comprise organic and inorganic compounds according to chemical composition classification, wherein the inorganic corrosion inhibitors are often required to be used in actual application in large amount, the application cost is increased, and the corrosion inhibitors have certain harm to human bodies and the environment. Organic corrosion inhibitors often have the defects of low corrosion inhibition performance, poor thermal stability and the like, and are greatly limited in practical application. Therefore, polymeric corrosion inhibitors have received attention compared to organic and inorganic corrosion inhibitors because of their versatility, excellent solubility, adjustable viscosity, the presence of a large number of binding sites with metal surfaces, and the like. The polythioether polymer corrosion inhibitor is outstanding in metal corrosion inhibition, has stronger binding force with the metal surface due to sulfur-rich atoms on the polymer chain, and can better attach to the metal surface to form a compact protective film after the flexibility of the main chain is enhanced. The invention designs and prepares the polythioether corrosion inhibitor with the main chain containing sulfur atoms and the side chain containing different numbers of cobaltosic ions, the synthesis process of the corrosion inhibitor is efficient and convenient, and the effective corrosion prevention of the metal carbon steel in a weak acid environment under the low concentration of the corrosion inhibitor can be realized through the synergistic effect between various functional groups and the metal surface. Compared with the prior published patent group about the small molecule corrosion inhibitors containing different long alkyl chains of the cobaltocene cations (a cobaltocene cation-based corrosion inhibitor, a preparation method and a use method thereof, patent application number: 201910629588X) and the polyurethane corrosion inhibitor (a cobaltocene cation-based waterborne polyurethane and corrosion inhibitor system and a preparation method thereof, patent application number: 2019106295748), the polythioether corrosion inhibitor solves the defects of few adhesion sites, small adsorption force and insufficient compactness of a protective film formed on the surface of a steel sheet of the prior small molecule corrosion inhibitor, and solves the problem of insufficient chemical stability of a main chain of the polyurethane corrosion inhibitor in a strong acid environment.
Disclosure of Invention
Technical problem to be solved
In order to avoid the defects of the prior art, the invention provides a preparation method and a corrosion inhibitor system for a polythioether corrosion inhibitor containing cobaltocenium ion side groups, and aims to provide the polythioether corrosion inhibitor containing cobaltocenium ion side groups by a convenient and efficient synthesis method and a use method thereof, and the preparation method aims to solve the defects of poor film forming capability, few attachment sites and the like of a small molecular corrosion inhibitor and develop a novel polymer corrosion inhibitor. By utilizing the synergistic effect of various functional groups in the polymer corrosion inhibitor and the metal surface, excellent metal corrosion inhibition effect is expected to be achieved under the condition of low corrosion inhibitor concentration.
Technical proposal
A preparation method of a polythioether corrosion inhibitor containing cobaltocene cation side groups is characterized by comprising the following steps:
step 1: dissolving a diene monomer containing hydroxyl into dichloromethane, sequentially adding 1-3 parts of triethylamine, 2-6 parts of methanesulfonic anhydride and 0.5-1 part of 4-dimethylaminopyridine under the conditions of nitrogen atmosphere and ice bath, reacting for 1-4 hours at low temperature, and reacting for 24-48 hours at room temperature;
adding water for quenching reaction, adding dichloromethane for extraction and separation, removing an organic phase, and separating and purifying by a column to obtain diene monomer containing methyl sulfonate;
step 2: placing diene monomer containing methyl sulfonate and equimolar dithiol into a small bottle, adding 0.01-0.05 part of photoinitiator, and irradiating with 365nm ultraviolet light for 0.5-2h; dissolving the product obtained by the reaction with tetrahydrofuran, and precipitating twice in methanol to obtain polythioether containing methyl sulfonate side groups;
step 3: dissolving polythioether containing a methylsulfonate side group in N, N-dimethylformamide, adding 5-10 parts of sodium azide, reacting for 24-48 hours at 50-70 ℃, removing the N, N-dimethylformamide by reduced pressure distillation, adding dichloromethane to extract and separate liquid, and performing rotary evaporation on an organic phase to obtain a crude product; precipitating the crude product in water twice to obtain polythioether containing the azide side group;
step 4: dissolving polythioether containing azido side groups and 1-1.5 parts of ethynyl cobaltocene hexafluorophosphate in 15-25mL of mixed solvent of tetrahydrofuran, water and N, N-dimethylformamide, adding 1-1.5 parts of copper sulfate solution, adding 2-3 parts of 1mol/L sodium ascorbate solution, and reacting at 30-80 ℃ for 24-48 hours;
after the reaction, adding 1-3mL of ammonia water, stirring for 10-30min, removing tetrahydrofuran by rotary evaporation, removing N, N-dimethylformamide and water by reduced pressure distillation, dissolving the crude product with a small amount of acetonitrile, and precipitating twice in diethyl ether to obtain X=PF 6 - Is a corrosion inhibitor of polythioethers containing cobaltocenium ion side groups;
the volume ratio of tetrahydrofuran, water and N, N-dimethylformamide is 3:2:1.
Let x=pf 6 - Dissolving the polythioether containing the cobaltocenium ion side group in acetonitrile, stirring and dissolving thoroughly to obtain solution A, and dissolving different anions (X=Cl) - ，Br - ，I - ，OH - ) 1-5 parts of tetrabutylammonium hydrate are dissolved in acetonitrile to obtain solution B, the obtained solution A is dropwise added into the solution B, phase separation is immediately generated, precipitation is collected, acetonitrile is subjected to ultrasonic cleaning for multiple times, and the corresponding anion-countered polythioether corrosion inhibitor is obtained after drying.
When 1, 6-heptadien-4-ol is used as the hydroxyl group-containing diene monomer in step 1, x=pf obtained in step 4 6 - The structural formula of the corrosion inhibitor of the polythioether containing the cobaltocenium ion side group is as follows:
m＝20-50；
step 5, obtaining the polythioether corrosion inhibitor with different anions corresponding to the structural formula, wherein: x is X - ＝Cl - ，Br - ，I - ，OH - 。
When 1, 7-octadiene-4, 5-diol is used as the hydroxyl group-containing diene monomer in step 1, x=pf obtained in step 4 6 - The structural formula of the corrosion inhibitor of the polythioether containing the cobaltocenium ion side group is as follows:
m＝20-50；
step 5, obtaining the polythioether corrosion inhibitor with different anions corresponding to the structural formula, wherein: x is X - ＝Cl - ，Br - ，I - ，OH - 。
When diallyl propylene glycol is used as the hydroxyl group-containing diene monomer in step 1, x=pf obtained in step 4 6 - The structural formula of the corrosion inhibitor of the polythioether containing the cobaltocenium ion side group is as follows:
m＝20-50；
step 5, obtaining the polythioether corrosion inhibitor with different anions corresponding to the structural formula, wherein: x is X - ＝Cl - ，Br - ，I - ，OH - 。
The preparation method of the 1, 7-octadiene-4, 5-diol comprises the following steps: dissolving 1-3 parts of allyl bromide, 1-5 parts of potassium iodide and 1-3 parts of stannous chloride hydrate in 10-30mL of water in turn, placing the mixture in a round-bottom flask, dissolving 1-3 parts of glyoxal in 5-10mL of water, dropwise adding the mixture into the round-bottom flask, reacting at room temperature for 24-48h, adding 5-20mL of 1M HCl solution, adding ethyl acetate for extraction and separation for three times, adding a proper amount of sodium thiosulfate hydrate for decolorization, extracting and separation for one time by using ethyl acetate, removing an organic phase, and drying to obtain 1, 7-octadiene-4, 5-diol.
The preparation method of the diallyl propylene glycol comprises the following steps: 1 part of diethyl diallylmalonate was dissolved in 5-15mL of diethyl ether and placed in a round-bottomed flask, 1-3 parts of lithium aluminum hydride was dispersed in 10-20mL of diethyl ether and slowly added to the above round-bottomed flask under ice-bath conditions, and stirred at room temperature for 12-24 hours. Adding a proper amount of water for quenching reaction, filtering to remove sediment, adding a proper amount of dichloromethane for extraction for multiple times, removing an organic phase, and drying to obtain the diallyl propylene glycol.
The method for preparing the polythioether corrosion inhibitor containing the cobaltocene cation side group by using any one of the prepared polythioether corrosion inhibitors as a corrosion inhibitor system is characterized in that: the concentration of the polydiene sulfide containing the cobaltocene cation side group in each 160mL of hydrochloric acid solution is 0-25mg/L; the concentration of the hydrochloric acid solution is 1.4mol/L.
Advantageous effects
According to the preparation method of the polythioether corrosion inhibitor containing the cobaltocene cation side group and the corrosion inhibitor system, sulfur atoms are introduced into a polymer main chain through a simple and convenient mercaptan-alkene clicking polymerization reaction to obtain saturated polythioether with different numbers of sulfonate groups on the side chain, and the target polythioether corrosion inhibitor with different numbers of cobaltocene ions on the side chain is prepared through efficient azide and copper-catalyzed azide-alkynyl clicking reaction. The polymer corrosion inhibitor can further enhance the interaction between the corrosion inhibitor and the metal surface through the synergistic effect of sulfur atoms on a main chain, side group connecting groups triazole and cobaltosic chloride ions and the metal surface and the excellent film forming property of the polymer, so that the excellent corrosion inhibition effect is achieved. The final corrosion inhibition test shows that: at 25 ℃, when immersed in 5% HCl corrosion inhibition medium for 6 hours, the corrosion inhibitor with the concentration of 15ppm has the corrosion inhibition efficiency of 96% on metal.
The polymer corrosion inhibitor provided by the invention is polythioether containing cobaltocene cation side groups, and the corrosion inhibitor is composed of a saturated alkane main chain containing sulfur atoms and a cobaltocene ion side chain. According to the metal corrosion inhibition mechanism of the corrosion inhibitor, the polymer corrosion inhibitor generally forms a layer of protective film on the surface of metal through physical or chemical action to achieve the effect of inhibiting corrosion. The polymer corrosion inhibitor provided by the patent can isolate the mutual contact between metal and corrosive medium through the coordination effect formed by sulfur atoms on a main chain and triazole as a connecting group and the surface of a steel sheet, the electrostatic interaction formed by cobaltocene cations and the surface of the steel sheet, the hydrophilic and hydrophobic properties of the polymer, the characteristic of easy film formation and the like, and the effect of effectively inhibiting metal corrosion is achieved.
Drawings
FIG. 1 is a digital photograph of three polycyclopentadienyl cationic pendant polythioether corrosion inhibitors;
FIG. 2 is a Fourier transform infrared spectrum of three cobalt-containing cationic pendant polythioether corrosion inhibitors;
FIG. 3 is a nuclear magnetic resonance hydrogen spectrum of three cobalt-containing cationic pendant polythioether corrosion inhibitors;
FIG. 4 is a schematic illustration of a 10# steel without the addition of a cobalt dicyclopentadienyl cation pendant-containing polythioether corrosion inhibitor (formula 2, X=Cl) - ) Then immersing the optical photo in weak acid environment at a certain temperature for a certain time;
FIG. 5 is a schematic illustration of a 10# steel without the addition of a cobalt dicyclopentadienyl cation pendant-containing polythioether corrosion inhibitor (formula 2, X=Cl) - ) And then immersing the scanning electron microscope photo in a weak acid environment at a certain temperature for a certain time.
Detailed Description
The invention will now be further described with reference to examples, figures:
in order to make the technical problems, technical solutions and advantages to be solved by the present invention more apparent, the following detailed description will be made with reference to specific embodiments. The structural formula of the cobaltocene cation side group-containing polythioether provided by the patent is shown as follows:
wherein: x is X - ＝PF 6 - ，Cl - ，Br - ，I - ，OH - ；m＝20-50。
Example 1: when X is - ＝Cl - Preparation of time Structure 1
Dissolving 1, 6-heptadiene-4-alcohol in a proper amount of dichloromethane, sequentially adding 1-3 parts of triethylamine, 2-6 parts of methanesulfonic anhydride and 0.5-1 part of 4-dimethylaminopyridine under the conditions of nitrogen atmosphere and ice bath, reacting for 1-4 hours at low temperature, and reacting for 24-48 hours at room temperature. Adding water to quench the reaction, adding an equal amount of dichloromethane to extract the separated liquid, removing the organic phase, and separating and purifying by a column to obtain the 1, 6-heptadiene-4-methylsulfonate.
1 part of 1, 6-heptadiene-4-methylsulfonate and 1 part of octadithiol are placed in a small bottle, 0.01-0.05 part of photoinitiator is added, and 365nm ultraviolet light is irradiated for 0.5-2 hours. Precipitation twice with tetrahydrofuran dissolution in methanol gives polythioethers containing pendant methylsulfonate groups.
Dissolving the polythioether containing the methyl sulfonate side group in a small amount of N, N-dimethylformamide, adding 5-10 parts of sodium azide, reacting for 24-48 hours at 50-70 ℃, removing the N, N-dimethylformamide by reduced pressure distillation, adding dichloromethane for extraction and separation, rotary evaporating an organic phase, and precipitating the crude product in water twice to obtain the polythioether containing the azide side group.
Polythioether containing pendant azide groups and 1-1.5 parts of ethynylcobaltocene hexafluorophosphate are dissolved in 25mL of mixed solvent of tetrahydrofuran/water/N, N-dimethylformamide (3:2:1) and placed in a round-bottom flask, 1-1.5 parts of freshly prepared copper sulfate solution is added, then 2-3 parts of 1mol/L sodium ascorbate solution is added, and the mixture is reacted for 24-48 hours at 30-80 ℃. Adding 1-3mL of ammonia water solution, stirring for 10-30min, removing tetrahydrofuran by rotary evaporation, removing N, N-dimethylformamide and water by reduced pressure distillation, dissolving the crude product with a small amount of acetonitrile, and precipitating twice in diethyl ether to obtain the polythioether containing the cobaltosic ion side group.
Dissolving the polythioether containing the cobaltosic ion side groups in a small amount of acetonitrile, fully stirring and dissolving to obtain a solution A, dissolving tetrabutylammonium chloride hydrate in a proper amount of acetonitrile to obtain a solution B, dropwise adding the obtained solution A into the solution B, immediately generating phase separation, collecting precipitate, ultrasonically cleaning the acetonitrile for multiple times, and drying to obtain the polythioether corrosion inhibitor containing the cobaltosic ion side groups.
Example 2: when X is - ＝Cl - Preparation of time Structure 2
Dissolving 1-3 parts of allyl bromide, 1-5 parts of potassium iodide and 1-3 parts of stannous chloride hydrate in 10-30mL of water in turn, placing the mixture in a round-bottom flask, dissolving 1-3 parts of glyoxal in 5-10mL of water, dropwise adding the mixture into the round-bottom flask, reacting at room temperature for 24-48h, adding 5-20mL of 1M HCl solution, adding ethyl acetate for extraction and separation for three times, adding a proper amount of sodium thiosulfate hydrate for decolorization, extracting and separation for one time by using ethyl acetate, removing an organic phase, and drying to obtain 1, 7-octadiene-4, 5-diol.
1, 7-octadiene-4, 5-diol is dissolved in a proper amount of methylene dichloride, 1 to 3 parts of triethylamine, 2 to 6 parts of methanesulfonic anhydride and 0.5 to 1 part of 4-dimethylaminopyridine are sequentially added under the conditions of nitrogen atmosphere and ice bath, the reaction is carried out for 1 to 4 hours at low temperature, and the reaction is carried out for 24 to 48 hours at room temperature. Adding water to quench reaction, adding equal amount of dichloromethane to extract and separate liquid, steaming organic phase, and separating and purifying by column to obtain 1, 7-octadiene-4, 5-dimethyl sulfonate.
1 part of 1, 7-octadiene-4, 5-dimethyl sulfonate and 1 part of octadithiol are placed in a small bottle, 0.01-0.05 part of photoinitiator is added, and 365nm ultraviolet light irradiates for 0.5-2 hours. The polymer was precipitated twice in methanol with dichloromethane as a dissolution product to give a polythioether having uniformly distributed pendant methylsulfonate groups on both sides of the polymer backbone.
Dissolving polythioether with evenly distributed methyl sulfonate side groups on two sides of a polymer main chain in a small amount of N, N-dimethylformamide, adding 5-10 parts of sodium azide, reacting for 24-48 hours at 50-70 ℃, removing the N, N-dimethylformamide by reduced pressure distillation, adding dichloromethane to extract and separate liquid, rotary evaporating an organic phase, and respectively precipitating a crude product on water and methanol once to obtain the polythioether with evenly distributed azide side groups on two sides of the polymer main chain.
Polythioether with azide side groups uniformly distributed on two sides of a polymer main chain and 2-3 parts of ethynyl cobaltocene hexafluorophosphate are dissolved in 25mL of mixed solvent of tetrahydrofuran/water/N, N-dimethylformamide (3:2:1), 2-3 parts of freshly prepared copper sulfate solution is added, 4-6 parts of 1mol/L sodium ascorbate solution is added, and the mixture is reacted for 24-48 hours at 30-80 v. Adding 1-3mL of ammonia water solution, stirring for 10-30min, removing tetrahydrofuran by rotary evaporation, removing N, N-dimethylformamide and water by reduced pressure distillation, dissolving the crude product in a small amount of acetonitrile, and precipitating twice in diethyl ether to obtain the polythioether with the two sides of the main chain of the polymer containing cobaltocenium ions uniformly distributed.
Dissolving polythioether with evenly distributed cobaltosic ions at two sides of a polymer main chain in a small amount of acetonitrile, fully stirring and dissolving to obtain a solution A, dissolving tetrabutylammonium chloride hydrate in a proper amount of acetonitrile to obtain a solution B, dropwise adding the obtained solution A into the solution B, immediately generating phase separation, collecting precipitate, ultrasonically cleaning acetonitrile for multiple times, and drying to obtain the polythioether corrosion inhibitor with evenly distributed cobaltosic ions at two sides of the polymer main chain.
Example 3: when X is - ＝Cl - Preparation of time Structure 3
1 part of diethyl diallylmalonate was dissolved in 5-15mL of diethyl ether and placed in a round-bottomed flask, 1-3 parts of lithium aluminum hydride was dispersed in 10-20mL of diethyl ether and slowly added to the above round-bottomed flask under ice-bath conditions, and stirred at room temperature for 12-24 hours. Adding a proper amount of water for quenching reaction, filtering to remove sediment, adding a proper amount of dichloromethane for extraction for multiple times, removing an organic phase, and drying to obtain the diallyl propylene glycol.
Dissolving diallyl propylene glycol in a proper amount of dichloromethane, sequentially adding 1-3 parts of triethylamine, 2-6 parts of methanesulfonic anhydride and 0.5-1 part of 4-dimethylaminopyridine under the conditions of nitrogen atmosphere and ice bath, and reacting for 1-4 hours at low temperature and 24-48 hours at room temperature. Adding water to quench the reaction, adding an equal amount of dichloromethane to extract and separate liquid, steaming the organic phase in a rotary way, and separating and purifying by a column to obtain diallyl dimethyl sulfonate propylene diester.
1 part of diallyl dimethyl sulfonate propylene glycol and 1 part of octanedithiol are placed in a small bottle, 0.01-0.05 part of photoinitiator is added, and 365nm ultraviolet light is irradiated for 0.5-2 hours. Precipitation of the methylene chloride solution twice in methanol gives polythioethers containing pendant methylsulfonate groups.
Dissolving the polythioether containing the methyl sulfonate side group in a small amount of N, N-dimethylformamide, adding 5-10 parts of sodium azide, reacting for 24-48 hours at 70-110 ℃, removing the N, N-dimethylformamide by reduced pressure distillation, adding dichloromethane for extraction and separation, rotationally steaming an organic phase, and respectively precipitating the crude product in water and methanol once to obtain the polythioether containing the azide side group.
Polythioether containing methyl sulfonate side group and 2-3 parts of ethynyl cobaltocene hexafluorophosphate are dissolved in 25mL of mixed solvent of tetrahydrofuran/water/N, N-dimethylformamide (3:2:1), and the mixture is placed in a round-bottom flask, 2-3 parts of freshly prepared copper sulfate solution is added, 4-6 parts of 1mol/L sodium ascorbate solution is added, and the mixture is reacted for 24-48 hours at 30-80 ℃. Adding 1-3mL of ammonia water solution, stirring for 10-30min, removing tetrahydrofuran by rotary evaporation, removing N, N-dimethylformamide and water by reduced pressure distillation, dissolving the crude product with a small amount of acetonitrile, and precipitating twice in diethyl ether to obtain the polythioether containing the cobaltosic ion side group.
Dissolving the polythioether containing the cobaltosic ion side group in a small amount of acetonitrile, fully stirring and dissolving to obtain a solution A, dissolving tetrabutylammonium chloride hydrate in a proper amount of acetonitrile to obtain a solution B, dropwise adding the obtained solution A into the solution B, immediately generating phase separation, collecting precipitate, ultrasonically cleaning the acetonitrile for multiple times, and drying to obtain the polythioether corrosion inhibitor containing the cobaltosic ion side group.
The using method of the polymer corrosion inhibitor provided by the invention is used for carrying out an anti-corrosion weightlessness experiment according to an acidulation corrosion inhibitor performance test method and an evaluation index SY/T5405-2019. And respectively examining the corrosion of the time, the temperature and the corrosion inhibitor concentration to the steel sheet in a weak acid environment. The steel sheet material used in the experiment is 10# steel processed according to the chemical industry standard, and the size is 50mm multiplied by 10mm multiplied by 3mm; the hanging piece area is 1360cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The corrosion inhibitor performance is evaluated by calculating the corrosion rate and the corrosion inhibition rate, wherein the calculation formula of the corrosion rate V and the corrosion inhibition rate eta is as follows:
corrosion rate v=Δw/(s×t) (g·m -2 ·h -1 ) The method comprises the steps of carrying out a first treatment on the surface of the Corrosion inhibition rate η= (V 0 -V)/V 0 ×100％
Wherein Deltaw is the weight difference (g) between the test coupon before and after pickling;
V、V 0 corrosion rates (g.m) with and without corrosion inhibitors -2 ·h -1 )；
S-surface area of test coupon (m 2 ) The method comprises the steps of carrying out a first treatment on the surface of the t-etching time (h).
Specific examples of methods of using the polythioether corrosion inhibitor containing cobaltocene cationic side groups are as follows:
example 4:
the concentration of the hydrochloric acid solution is 1.4mol/L, the consumption of the hydrochloric acid solution is 160mL, the consumption of the cobaltocene cationic polythioether corrosion inhibitor is 0, 5, 10, 15, 20 and 25mg/L, and 10# steel is immersed in acid liquor for 2, 4 and 6 hours at 25 ℃.
Example 5:
the concentration of hydrochloric acid is 1.4mol/L, the consumption of hydrochloric acid solution is 160mL, the consumption of the cobaltocene cationic polythioether corrosion inhibitor is 15mg/L, and 10# steel is immersed in acid liquor for 4h at 25, 35, 45 and 55 ℃.
Corrosion inhibition rate data (structural formula 2, X=Cl) corresponding to examples 4 and 5 - ) The results were as follows:
comparing the previously published patent application number of the group of the problems with the small molecular corrosion inhibitors containing different long alkyl chains of cobaltocene cations (a cobaltocene cation based corrosion inhibitor, a preparation method and a use method: 201910629588X) and a polyurethane corrosion inhibitor (a cobaltocene cation-containing waterborne polyurethane and corrosion inhibitor system and a preparation method, patent application number: 2019106295748), the corrosion inhibition rate of the cobaltocene cation-containing polythioether type corrosion inhibitor reported by the invention can reach more than 70% at low concentration, and the effect of the micromolecular corrosion inhibitor is difficult to reach at low concentration. And the corrosion inhibitor gradually increases along with the increase of temperature, and finally tends to be stable, which shows that the corrosion inhibitor has better adsorption stability and chemical stability at high temperature. The corrosion inhibition result also proves that the polythioether corrosion inhibitor has stronger adhesive force and excellent film forming property on the metal surface. Meanwhile, the polythioether main chain structure also endows the corrosion inhibitor with better acid and alkali resistance than the polyurethane corrosion inhibitor.
With the cobaltocene cation-containing pendant polythioether (formula 2, x=cl) - ) The test scheme as a corrosion inhibitor is as follows:
scheme 1: testing of different concentrations
The metal is immersed in acid liquor with the temperature of 25 ℃ and the corrosion inhibitor concentration of 0, 5, 10, 15, 20 and 25mg/L for 4 hours.
Scheme 2: different time tests
Immersing the metal in acid solution with the temperature of 25 ℃ and the corrosion inhibitor concentration of 15mg/L for 2, 4 and 6 hours.
Scheme 3: testing at different temperatures
The metal is immersed in acid liquor with the temperature of 25, 35, 45 and 55 ℃ and the corrosion inhibitor concentration of 15mg/L for 4 hours.
Claims (4)
1. A preparation method of a polythioether corrosion inhibitor containing cobaltocene cation side groups is characterized by comprising the following steps:
step 1: dissolving a diene monomer containing hydroxyl into dichloromethane, sequentially adding 1-3 parts of triethylamine, 2-6 parts of methanesulfonic anhydride and 0.5-1 part of 4-dimethylaminopyridine under the conditions of nitrogen atmosphere and ice bath, reacting for 1-4 hours at low temperature, and reacting for 24-48 hours at room temperature;
adding water for quenching reaction, adding dichloromethane for extraction and separation, removing an organic phase, and separating and purifying by a column to obtain diene monomer containing methyl sulfonate;
step 2: placing diene monomer containing methyl sulfonate and equimolar dithiol into a small bottle, adding 0.01-0.05 part of photoinitiator, and irradiating with 365nm ultraviolet light for 0.5-2h; dissolving the product obtained by the reaction with tetrahydrofuran, and precipitating twice in methanol to obtain polythioether containing methyl sulfonate side groups;
step 3: dissolving polythioether containing a methylsulfonate side group in N, N-dimethylformamide, adding 5-10 parts of sodium azide, reacting for 24-48 hours at 50-70 ℃, removing the N, N-dimethylformamide by reduced pressure distillation, adding dichloromethane to extract and separate liquid, and performing rotary evaporation on an organic phase to obtain a crude product; precipitating the crude product in water twice to obtain polythioether containing the azide side group;
step 4: dissolving polythioether containing azido side groups and 1-1.5 parts of ethynyl cobaltocene hexafluorophosphate in 15-25mL of mixed solvent of tetrahydrofuran, water and N, N-dimethylformamide, adding 1-1.5 parts of copper sulfate solution, adding 2-3 parts of 1mol/L sodium ascorbate solution, and reacting at 30-80 ℃ for 24-48 hours;
after the reaction is finished, adding 1-3mL of ammonia water, stirring for 10-30min, and removing the tetrahydro by rotary evaporationRemoving N, N-dimethylformamide and water by distillation under reduced pressure, dissolving the crude product with a small amount of acetonitrile, and precipitating twice in diethyl ether to obtain X - ＝PF 6 - Is a corrosion inhibitor of polythioethers containing cobaltocenium ion side groups;
the volume ratio of the tetrahydrofuran, the water and the N, N-dimethylformamide is 3:2:1;
step 5: x is to be - ＝PF 6 - Dissolving the polythioether containing the cobaltosic ion side group in acetonitrile, fully stirring and dissolving to obtain a solution A, dissolving 1-5 parts of tetrabutylammonium hydrate with different anions in acetonitrile to obtain a solution B, dropwise adding the obtained solution A into the solution B, immediately generating phase separation, collecting precipitate, ultrasonically cleaning the acetonitrile for multiple times, and drying to obtain the corresponding anion-countered polythioether corrosion inhibitor;
when the hydroxy-containing diene monomer of step 1 is 1, 6-heptadien-4-ol, X obtained in step 4 - ＝PF 6 - The structural formula of the corrosion inhibitor of the polythioether containing the cobaltocenium ion side group is as follows:
m＝20-50；
step 5, obtaining the polythioether corrosion inhibitor with different anions corresponding to the structural formula, wherein: x is X - ＝Cl - ，Br - ，I - ，OH - ；
When 1, 7-octadiene-4, 5-diol is used as the hydroxyl group-containing diene monomer in step 1, X obtained in step 4 - ＝PF 6 - The structural formula of the corrosion inhibitor of the polythioether containing the cobaltocenium ion side group is as follows:
m＝20-50；
in step 5, the polythioether type slow with different anions corresponding to the structural formula is obtainedAn etchant, wherein: x is X - ＝Cl-，Br - ，I - ，OH - ；
When diallyl propylene glycol is used as the hydroxy-containing diene monomer in step 1, X is obtained in step 4 - ＝PF 6 - The structural formula of the corrosion inhibitor of the polythioether containing the cobaltocenium ion side group is as follows:
m＝20-50；
step 5, obtaining the polythioether corrosion inhibitor with different anions corresponding to the structural formula, wherein: x is X - ＝Cl - ，Br - ，I - ，OH - 。
2. The method for preparing the polythioether corrosion inhibitor containing cobaltocene cation side groups, according to claim 1, wherein the method comprises the following steps: the preparation method of the 1, 7-octadiene-4, 5-diol comprises the following steps: dissolving 1-3 parts of allyl bromide, 1-5 parts of potassium iodide and 1-3 parts of stannous chloride hydrate in 10-30mL of water in turn, placing the mixture in a round-bottom flask, dissolving 1-3 parts of glyoxal in 5-10mL of water, dropwise adding the mixture into the round-bottom flask, reacting at room temperature for 24-48h, adding 5-20mL of 1M HCl solution, adding ethyl acetate for extraction and separation for three times, adding a proper amount of sodium thiosulfate hydrate for decolorization, extracting and separation for one time by using ethyl acetate, removing an organic phase, and drying to obtain 1, 7-octadiene-4, 5-diol.
3. The method for preparing the polythioether corrosion inhibitor containing cobaltocene cation side groups, according to claim 1, wherein the method comprises the following steps: the preparation method of the diallyl propylene glycol comprises the following steps: 1 part of diethyl diallyl malonate is dissolved in 5-15mL of diethyl ether, the diethyl diallyl malonate is placed in a round-bottom flask, 1-3 parts of lithium aluminum hydride is dispersed in 10-20mL of diethyl ether and is slowly added into the round-bottom flask under ice bath condition, the mixture is stirred for 12-24 hours at room temperature, a proper amount of water is added for quenching reaction, the precipitate is filtered, a proper amount of dichloromethane is added for multiple extraction, an organic phase is removed, and the diallyl propylene glycol is obtained after drying.
4. Use of a polythioether corrosion inhibitor comprising pendant cobaltocene cations prepared by the method of any one of claims 1-3 as a corrosion inhibitor system, characterized in that: the concentration of the polydiene sulfide containing the cobaltocene cation side group in each 160mL of hydrochloric acid solution is 0-25mg/L; the concentration of the cobaltocene cation side group polythioether is not zero;
the concentration of the hydrochloric acid solution is 1.4mol/L.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104725637A (en) * | 2013-12-20 | 2015-06-24 | 中国科学院宁波材料技术与工程研究所 | Polythioether-base polymercaptan, and synthesis method and application thereof |
| CN105837820A (en) * | 2015-01-16 | 2016-08-10 | 中国科学院宁波材料技术与工程研究所 | Latent type polythioether based polymercaptan, synthesis method and application thereof |
| JP2018505925A (en) * | 2014-12-15 | 2018-03-01 | ザ・ボーイング・カンパニーＴｈｅ Ｂｏｅｉｎｇ Ｃｏｍｐａｎｙ | Polyvinyl butyral coating with thiol corrosion inhibitor |
| CN110565100A (en) * | 2019-07-12 | 2019-12-13 | 西北工业大学 | cobaltocene cation-based corrosion inhibitor and preparation method and use method thereof |
| CN110577626A (en) * | 2019-07-12 | 2019-12-17 | 西北工业大学太仓长三角研究院 | cobaltocene cation-based waterborne polyurethane and corrosion inhibitor system and preparation method thereof |
| WO2020060690A1 (en) * | 2018-09-17 | 2020-03-26 | Exxonmobil Chemical Patents Inc. | Metallocene dimer selective catalysts and processes to produce poly alpha-olefin dimers |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10053606B2 (en) * | 2015-10-26 | 2018-08-21 | Prc-Desoto International, Inc. | Non-chromate corrosion inhibiting polythioether sealants |
-
2021
- 2021-11-15 CN CN202111350308.5A patent/CN113861422B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104725637A (en) * | 2013-12-20 | 2015-06-24 | 中国科学院宁波材料技术与工程研究所 | Polythioether-base polymercaptan, and synthesis method and application thereof |
| JP2018505925A (en) * | 2014-12-15 | 2018-03-01 | ザ・ボーイング・カンパニーＴｈｅ Ｂｏｅｉｎｇ Ｃｏｍｐａｎｙ | Polyvinyl butyral coating with thiol corrosion inhibitor |
| CN105837820A (en) * | 2015-01-16 | 2016-08-10 | 中国科学院宁波材料技术与工程研究所 | Latent type polythioether based polymercaptan, synthesis method and application thereof |
| WO2020060690A1 (en) * | 2018-09-17 | 2020-03-26 | Exxonmobil Chemical Patents Inc. | Metallocene dimer selective catalysts and processes to produce poly alpha-olefin dimers |
| CN110565100A (en) * | 2019-07-12 | 2019-12-13 | 西北工业大学 | cobaltocene cation-based corrosion inhibitor and preparation method and use method thereof |
| CN110577626A (en) * | 2019-07-12 | 2019-12-17 | 西北工业大学太仓长三角研究院 | cobaltocene cation-based waterborne polyurethane and corrosion inhibitor system and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| Ze Zhang,et al..Recyclable cobalt-molybdenum bimetallic carbide modified separator boosts the polysulfide adsorption-catalysis of lithium sulfur battery.《SCIENCE CHINA Materials》.2020,第63卷(第12期),第2443-2455页. * |
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