CN115536554A - 1,1' - (1, 4-phenylene) bis (3-phenylurea)/aniline corrosion inhibitor and preparation method and application thereof - Google Patents
1,1' - (1, 4-phenylene) bis (3-phenylurea)/aniline corrosion inhibitor and preparation method and application thereof Download PDFInfo
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- 238000005260 corrosion Methods 0.000 title claims abstract description 147
- 230000007797 corrosion Effects 0.000 title claims abstract description 142
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 title claims abstract description 120
- 239000003112 inhibitor Substances 0.000 title claims abstract description 110
- JTBDQDFUQGNSBW-UHFFFAOYSA-N 1-phenyl-3-[4-(phenylcarbamoylamino)phenyl]urea Chemical compound C=1C=C(NC(=O)NC=2C=CC=CC=2)C=CC=1NC(=O)NC1=CC=CC=C1 JTBDQDFUQGNSBW-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title abstract description 14
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052751 metal Inorganic materials 0.000 claims abstract description 33
- 239000002184 metal Substances 0.000 claims abstract description 33
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 60
- 239000002904 solvent Substances 0.000 claims description 21
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
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- 238000003760 magnetic stirring Methods 0.000 claims description 2
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 238000002161 passivation Methods 0.000 description 7
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 6
- 238000002791 soaking Methods 0.000 description 6
- 244000137852 Petrea volubilis Species 0.000 description 5
- 230000010287 polarization Effects 0.000 description 5
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- 230000001681 protective effect Effects 0.000 description 5
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C275/00—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C275/28—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C273/00—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C273/18—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas
- C07C273/1809—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas with formation of the N-C(O)-N moiety
- C07C273/1818—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas with formation of the N-C(O)-N moiety from -N=C=O and XNR'R"
- C07C273/1827—X being H
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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
- C23F11/14—Nitrogen-containing compounds
- C23F11/147—Nitrogen-containing compounds containing a nitrogen-to-oxygen bond
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Abstract
The invention provides a 1,1' - (1, 4-phenylene) bis (3-phenylurea)/aniline corrosion inhibitor, a preparation method and application thereof, belonging to the technical field of metal protection and material preparation; according to the invention, 1'- (1, 4-phenylene) bis (3-phenylurea)/aniline corrosion inhibitor is prepared by taking aniline and p-phenylene diisocyanate as raw materials, and the 1,1' - (1, 4-phenylene) bis (3-phenylurea)/aniline corrosion inhibitor has extremely high corrosion inhibition performance, can be adsorbed on the surface of a metal base layer to slow down metal corrosion, and has good application in protection of metal base materials.
Description
Technical Field
The invention belongs to the technical field of metal protection and material preparation, and particularly relates to a 1,1' - (1, 4-phenylene) bis (3-phenylurea)/aniline corrosion inhibitor, and a preparation method and application thereof.
Background
Metal corrosion causes economic losses of more than 3.5% of the world's GDP each year, so slowing down metal corrosion has an era urgency. When the metal is in a corrosive medium, the metal atoms undergo redox reactions and are corroded. The common solutions to metal corrosion are mainly coatings, cathodic protection, passivation layers, corrosion inhibitors, etc., wherein corrosion inhibitors are considered as the least costly and most efficient choice. In the industrial pickling process, the corrosion inhibitor can effectively reduce the secondary corrosion of acid liquor on the metal matrix, however, a large amount of waste acid liquor can be generated in the pickling process, and the environmental threat is also caused. Therefore, the corrosion prevention efficiency of the corrosion inhibitor in the pickling process needs to be continuously improved, so that the generation of the waste acid solution is reduced.
The corrosion inhibitor is added into the corrosion medium in a very small concentration to slow down the corrosion of the metal, and the concentration of the corrosion inhibitor is generally considered to be less than 500 ppm, so that the corrosion inhibitor can be adsorbed on the surface of the metal to form a protective film. According to the mechanism of action of the corrosion inhibitor, the corrosion inhibitor can be divided into an anodic corrosion inhibitor, a cathodic corrosion inhibitor and a mixed corrosion inhibitor. Wherein, the anodic corrosion inhibitor forms a passivation layer on the metal surface to slow down corrosion, and is usually influenced by the lowest anodic corrosion inhibitor concentration; the cathodic corrosion inhibitor usually forms a precipitation layer on the surface of the metal to block the transfer of corrosive media and electrons; the mixed corrosion inhibitor can slow down the corrosion of the anode and the cathode. However, the classification method is based on the results of the action of the corrosion inhibitor and the metal surface, and cannot effectively guide people to develop a novel high-efficiency corrosion inhibitor. The corrosion inhibitor can be divided into an organic corrosion inhibitor and an inorganic corrosion inhibitor according to the components of the corrosion inhibitor, and the inorganic corrosion inhibitor represented by chromate causes pollution and harm to the environment and human bodies and is difficult to be widely applied. The molecular mechanism of the organic corrosion inhibitor is favorable for being adsorbed on the metal surface, and the organic corrosion inhibitor contains heteroatoms such as N, S, P, O and the like, and-OH, -COOH and-NH 2 The isopolar functional groups have conjugated bonds or aromatic rings, and are more favorable for being adsorbed on the metal surface and retarding corrosion. Therefore, the development of organic corrosion inhibitors with N, S, P, O, polar groups and planarity has important academic and practical significance.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a 1,1' - (1, 4-phenylene) bis (3-phenylurea)/aniline corrosion inhibitor, and a preparation method and application thereof. According to the invention, 1'- (1, 4-phenylene) bis (3-phenylurea)/aniline corrosion inhibitor is prepared by taking aniline and p-phenylene diisocyanate as raw materials, and the 1,1' - (1, 4-phenylene) bis (3-phenylurea)/aniline corrosion inhibitor has extremely high corrosion inhibition performance, can be adsorbed on the surface of a metal base layer to slow down metal corrosion, and has good application in protection of metal base materials.
The invention firstly provides a 1,1' - (1, 4-phenylene) bis (3-phenylurea)/aniline corrosion inhibitor which takes ethylene glycol dimethyl ether (DME) as An organic solvent and-NH in aniline (An) molecules 2 and-OCN group of p-phenylene diisocyanate (PPDI),
the structural formula of the 1,1' - (1, 4-phenylene) bis (3-phenylurea)/aniline corrosion inhibitor is as follows:
the invention also provides a preparation method of the 1,1' - (1, 4-phenylene) bis (3-phenylurea)/aniline corrosion inhibitor, which comprises the following steps:
(1) Dissolving aniline (An) in a solvent ethylene glycol dimethyl ether (DME), and uniformly mixing to obtain a solution A; dissolving p-phenylene diisocyanate (PPDI) in a solvent DME, and uniformly dispersing by ultrasonic to obtain a solution B;
(2) And adding the solution B into the solution A, magnetically stirring at room temperature to react, and performing rotary evaporation to remove the solvent after the reaction is finished to obtain the 1,1' - (1, 4-phenylene) bis (3-phenylurea)/aniline corrosion inhibitor.
Further, in the step (1), the volume ratio of aniline (An) to ethylene glycol dimethyl ether (DME) in the solution A is 0.5.
Further, in the step (1), the volume ratio of PPDI to DME in the solution B is 0.01:10 to 0.17:10.
further, in the step (2), the volume ratio of the solution B to the solution A is 1.
Further, in the step (2), the reaction time is 1-2 h by magnetic stirring.
The invention also provides the application of the 1,1' - (1, 4-phenylene) bis (3-phenylurea)/aniline corrosion inhibitor in metal protection.
Further, the metal protection is corrosion protection, and the metal is stainless steel.
Further, the application is that 1,1' - (1, 4-phenylene) bis (3-phenylurea)/aniline corrosion inhibitor is adsorbed on the metal surface.
Compared with the prior art, the invention has the beneficial effects that:
in the invention, 1' - (1, 4-phenylene) bis (3-phenylurea)/aniline corrosion inhibitor (AP/An) is prepared by a one-pot method, the composition of the corrosion inhibitor and the microscopic morphology of a formed film layer are researched by means of FTIR, EDS, SEM and MAPPING, and the protective performance of the corrosion inhibitor is evaluated by adopting Tafel and EIS.
According to the invention, SEM and MAPPING researches show that the 1,1'- (1, 4-phenylene) bis (3-phenylurea)/aniline corrosion inhibitor film has good compactness and uniformity, corrosion resistance of the 1,1' - (1, 4-phenylene) bis (3-phenylurea)/aniline corrosion inhibitor film in 1mol/L HCl is researched through a Tafel polarization curve and An EIS curve, and the researches show that the self-corrosion current of AP/An5 is reduced by two orders of magnitude, and the protection efficiency reaches 98.59%. Meanwhile, the 1,1' - (1, 4-phenylene) bis (3-phenylurea)/aniline corrosion inhibitor film with good compactness and uniformity ensures that the impedance of AP/An5 reaches 450.2 omega cm -2 。
The 1,1' - (1, 4-phenylene) bis (3-phenylurea)/aniline corrosion inhibitor disclosed by the invention is simple in preparation process, excellent in metal substrate protection efficiency, low in cost and very good in application in the field of metal protection.
Drawings
FIG. 1 is An FTIR spectrum of 1,1' - (1, 4-phenylene) bis (3-phenylurea)/aniline corrosion inhibitor AP/An.
FIG. 2 is an EDS picture of a 1,1' - (1, 4-phenylene) bis (3-phenylurea)/aniline corrosion inhibitor film in a 1mol/L HCl corrosion medium.
FIG. 3 is an SEM image of bare Q235 (a, b) and resist treated Q235 (c, d) after soaking in 1mol/L HCl for 0.5h, where a and c are 3000 times larger and b and d are 10000 times larger.
FIG. 4 is a Tafel plot of bare Q235 and corrosion inhibitors AP/An5 in 1mol/L HCl.
FIG. 5 is a graph showing the impedance curves and corresponding fitting curves of the bare Q235 and AP/An5, FIG. 5a is a graph showing the impedance curve of the bare Q235, and FIG. 5b is a schematic diagram showing the equivalent circuit of R (QR).
FIG. 6 is a BODE curve (FIG. 6 a) and An impedance mode curve (FIG. 6 b) for bare Q235 and AP/An5.
Detailed Description
The invention will be further described with reference to the following figures and specific examples, but the scope of the invention is not limited thereto. In the following examples, a steel sheet of Q235 was used as a substrate to adsorb a 1,1' - (1, 4-phenylene) bis (3-phenylurea)/aniline corrosion inhibitor (AP/An corrosion inhibitor for short) and the corresponding examination was made, but the scope of the present invention is not limited to the steel sheet of Q235.
Example 1:
(1) Pretreatment of Q235 steel sheets:
and (3) polishing the surface of the Q235 steel sheet by using 800# to 1000# water phase sand paper, removing a passivation layer on the surface, then sequentially ultrasonically cleaning in an acetone and ethanol solution for 10 minutes, and volatilizing at room temperature for later use.
(2) Preparing An AP/An corrosion inhibitor:
adding 20mL of DME and 0.5mol/L aniline solution into a 50mL beaker, taking the DME as a solvent, uniformly mixing, and marking as solution A for later use;
10mL of DME and 0.2g of PPDI were added to a 25mL beaker, and after sonication for 5min, the PPDI was sufficiently dissolved and uniformly dispersed in the DME solvent, and the solution B was marked for use.
And adding the solution B into the solution A, fully magnetically stirring at room temperature for reaction for 2 hours, removing the solvent by rotary evaporation to obtain the 1,1' - (1, 4-phenylene) bis (3-phenylurea)/aniline corrosion inhibitor, and marking as AP/An1 according to the different dosage of PPDI.
(3) The AP/An1 corrosion inhibitor is adsorbed on the surface of the Q235 steel sheet:
soaking the Q235 steel sheet in the AP/An1 corrosion inhibitor corrosion solution for 0.5h, so that the AP/An1 corrosion inhibitor can be adsorbed on the surface of the Q235 steel sheet.
Example 2:
(1) Pretreatment of a Q235 steel sheet:
and (3) polishing the surface of the Q235 steel sheet by using 800# to 1000# water phase sand paper, removing a passivation layer on the surface, then sequentially ultrasonically cleaning in an acetone and ethanol solution for 10 minutes, and volatilizing at room temperature for later use.
(2) Preparation of 1,1' - (1, 4-phenylene) bis (3-phenylurea)/aniline corrosion inhibitor:
adding 20mL of DME and 0.5mol/L aniline into a 50mL beaker, taking the DME as a solvent, uniformly mixing, and marking as solution A for later use;
10mL of DME and 0.1g of PPDI were added into a 25mL beaker, and after 5min of sonication, the PPDI was dissolved and dispersed in the DME solvent sufficiently and uniformly, and the solution B was marked for use.
And adding the solution B into the solution A, fully and magnetically stirring at room temperature for reaction for 2 hours, wherein the solution is in a white turbid state after the reaction is finished, and removing the solvent by rotary evaporation to obtain the 1,1' - (1, 4-phenylene) bis (3-phenylurea)/aniline corrosion inhibitor which is marked as AP/An2 according to the different dosage of PPDI.
(3) The AP/An2 corrosion inhibitor is adsorbed on the surface of the Q235 steel sheet:
soaking the Q235 steel sheet in the AP/An2 corrosion inhibitor corrosion solution for 0.5h, so that the AP/An2 corrosion inhibitor can be adsorbed on the surface of the Q235 steel sheet.
Example 3:
(1) Pretreatment of a Q235 steel sheet:
and (3) polishing the surface of the Q235 steel sheet by using 800# to 1000# water phase sand paper, removing a passivation layer on the surface, then sequentially ultrasonically cleaning in an acetone and ethanol solution for 10 minutes, and volatilizing at room temperature for later use.
(2) Preparation of 1,1' - (1, 4-phenylene) bis (3-phenylurea)/aniline corrosion inhibitor:
adding 20mL of DME and 0.5mol/L aniline into a 50mL beaker, taking the DME as a solvent, uniformly mixing, and marking as a solution A for later use;
10mL of DME and 0.05g of PPDI were added to a 25mL beaker, and after sonication for 5min, the PPDI was sufficiently dissolved and uniformly dispersed in the DME solvent, and the solution was marked as solution B for use.
And adding the solution B into the solution A, fully and magnetically stirring at room temperature for reaction for 2 hours, removing the solvent by rotary evaporation to obtain a 1,1' - (1, 4-phenylene) bis (3-phenylurea)/aniline corrosion inhibitor after the reaction is finished, and marking as AP/An3 according to the different dosage of PPDI.
(3) The AP/An3 corrosion inhibitor is adsorbed on the surface of the Q235 steel sheet:
soaking the Q235 steel sheet in the AP/An3 corrosion inhibitor corrosion solution for 0.5h, so that the AP/An3 corrosion inhibitor can be adsorbed on the surface of the Q235 steel sheet.
Example 4:
(1) Pretreatment of a Q235 steel sheet:
and (3) polishing the surface of the Q235 steel sheet by using 800# to 1000# water phase sand paper, removing a passivation layer on the surface, then sequentially carrying out ultrasonic cleaning in an acetone and ethanol solution for 10 minutes, and volatilizing at room temperature for later use.
(2) Preparation of 1,1' - (1, 4-phenylene) bis (3-phenylurea)/aniline corrosion inhibitor:
adding 20mL of DME and 0.5mol/L aniline into a 50mL beaker, taking the DME as a solvent, uniformly mixing, and marking as solution A for later use;
10mL of DME and 0.025g of PPDI were added to a 25mL beaker, and after sonication for 5min, the PPDI was dissolved and dispersed in the DME solvent sufficiently and uniformly, and the solution was marked as solution B for use.
And adding the solution B into the solution A, fully and magnetically stirring at room temperature for reaction for 2 hours, wherein the solution is in a white turbid state after the reaction is finished, and removing the solvent by rotary evaporation to obtain the 1,1' - (1, 4-phenylene) bis (3-phenylurea)/aniline corrosion inhibitor which is marked as AP/An4 according to the different dosage of PPDI.
(3) The AP/An4 corrosion inhibitor is adsorbed on the surface of the Q235 steel sheet:
soaking the Q235 steel sheet in the AP/An4 corrosion inhibitor corrosion solution for 0.5h, so that the AP/An4 corrosion inhibitor can be adsorbed on the surface of the Q235 steel sheet.
Example 5:
(1) Pretreatment of Q235 steel sheets:
and (3) polishing the surface of the Q235 steel sheet by using 800# to 1000# water phase sand paper, removing a passivation layer on the surface, then sequentially carrying out ultrasonic cleaning in an acetone and ethanol solution for 10 minutes, and volatilizing at room temperature for later use.
(2) Preparation of 1,1' - (1, 4-phenylene) bis (3-phenylurea)/aniline corrosion inhibitor:
adding 20mL of DME and 0.5mol/L aniline into a 50mL beaker, taking the DME as a solvent, uniformly mixing, and marking as solution A for later use;
10mL of DME and 0.0125g of PPDI was added to a 25mL beaker, and after 5min of sonication, the PPDI was dissolved and dispersed in the DME solvent sufficiently and uniformly, and the solution B was labeled for use.
And adding the solution B into the solution A, fully and magnetically stirring at room temperature for reaction for 2 hours, removing the solvent by rotary evaporation to obtain a 1,1' - (1, 4-phenylene) bis (3-phenylurea)/aniline corrosion inhibitor after the reaction is finished, and marking as AP/An5 according to the different dosage of PPDI.
(3) The AP/An5 corrosion inhibitor is adsorbed on the surface of the Q235 steel sheet:
soaking the Q235 steel sheet in the AP/An5 corrosion inhibitor corrosion solution for 0.5h, so that the AP/An4 corrosion inhibitor can be adsorbed on the surface of the Q235 steel sheet.
FIG. 1 is An FTIR spectrum of AP/An5 corrosion inhibitor, wherein, 3445cm -1 ～3145cm -1 The absorption band belongs to-NH stretching vibration and H in AP/An5 molecule 2 Stretching vibration of O-H in O molecule and-NH in unreacted An molecule 2 And (5) stretching and vibrating. 3045 cm of -1 Nearby absorption peaks are attributed to stretching vibration of the benzene ring C-H in the AP/An5 molecule and the unreacted An molecule. 1690cm -1 The absorption peak of (2) is attributed to C = O stretching vibration of AP/An5, 1632cm -1 、1560cm -1 、1509cm -1 、1439cm -1 The absorption peaks of (a) are attributed to the vibration of the backbone of the benzene ring in AP/An5 and unreacted An molecules. FTIR spectrum research shows that the AP/An5 corrosion inhibitor is successfully prepared.
FIG. 2 is An EDS picture of AP/An5 corrosion inhibitor films in 1mol/L HCl. The main elements comprise C, N, O, cl and Fe, wherein the Fe element mainly comes from Q235, the C, N and O mainly come from AP/An5 and unreacted An molecules, and the mol ratio of the Cl element is only 0.42 percent, which shows that the formed corrosion inhibitor film is extremely compact and can effectively slow down the damage of HCl corrosion medium to the surface of Q235.
FIG. 3 is An SEM image of bare Q235 and Q235 after being treated by a corrosion inhibitor after being soaked in 1mol/L HCl for 0.5h, wherein FIGS. 3a and 3b show that no corrosion inhibitor is added in the etching medium, and FIGS. 3c and 3d show that a corrosion inhibitor AP/An5 is added in the etching medium. From the SEM pictures, a small amount of grinding marks exist on the surface of Q235, and from comparison of 3000 times of SEM pictures 3a and 3c and 10000 times of SEM pictures 3b and 3d, the surface of the pictures 3a and 3b is severely corroded, which shows that the corrosion inhibitor AP/An5 can effectively slow down the corrosion rate of HCl on the surface of the steel sheet.
Example 6:
in this example, the corrosion inhibiting properties of the 1,1'- (1, 4-phenylene) bis (3-phenylurea)/aniline corrosion inhibitors prepared in examples 1-5 at different PPDI addition levels and the densification of the films formed from the 1,1' - (1, 4-phenylene) bis (3-phenylurea)/aniline corrosion inhibitors were examined.
The Tafel polarization curve is an important method for researching the protective performance of the corrosion inhibitor, namely the self-corrosion current I corr The smaller the corrosion inhibitor, the better the corrosion inhibition performance is, the better the corrosion inhibition performance can be expressed by the protection efficiency, and the protection efficiency eta = (I) corr a-I corr b)/I corr a, wherein I corr a represents the self-corrosion current of bare Q235 in the corrosive medium, and I corr b represents the self-corrosion current obtained by adding a 1,1' - (1, 4-phenylene) bis (3-phenylurea)/aniline corrosion inhibitor into a corrosion medium.
The method specifically comprises the steps of taking a saturated calomel electrode as a reference electrode, a platinum wire as a counter electrode, a Q235 stainless steel sheet as a working electrode and mixing 1cm in a three-electrode electrochemical system 2 Exposed in 1mol/L HCl corrosive liquid to carry out Tafel polarization curve test.
TABLE 1 Tafel polarization curve data table with different PPDI addition and AP/An addition
Table 1 is a table of Tafel polarization curves for 1,1' - (1, 4-phenylene) bis (3-phenylurea)/aniline corrosion inhibitors prepared at different PPDI addition levels. As can be seen from Table 1 and FIG. 4, the self-etching current decreased and then increased with the decrease in the amount of PPDI added, and the self-etching current reached the minimum value (3.742X 10) at the addition amount of PPDI of 0.0125g -5 A) The self-corrosion current of AP/An5 is reduced by two orders of magnitude, the corresponding protection efficiency reaches 98.59 percent, and the protection efficiency is equivalent to that of a common resin coating.
An Electrochemical Impedance Spectroscopy (EIS) curve is an important method for researching the compactness of a film, the higher the impedance value is, the better the compactness of the film is, the better the protective performance of the corrosion inhibitor film on a Q235 matrix is, the specific steps are that in a three-electrode electrochemical system, a saturated calomel electrode is taken as a reference electrode, a platinum wire is taken as a counter electrode, a Q235 stainless steel sheet is taken as a working electrode, and 1cm of the corrosion inhibitor film is subjected to electrochemical reaction 2 The Q235 is exposed in 1mol/L HCl corrosive liquid, and after the open circuit potential is stable, namely the third digit is kept constant within 3 minutes after the open circuit potential is a decimal point, an EIS curve test is carried out.
FIG. 5 is An impedance spectrum of a bare Q235 steel sheet and AP/An5, actual measurement data are fitted in ZSimDemo3.30d according to equivalent circuit R (QR), the fitting data are shown in Table 2, and the impedance value of the bare Q235 is 15.21 omega cm -2 And the impedance value of AP/An5 is 450.20. Omega. Cm -2 The results show that the AP/An5 corrosion inhibitor film has excellent compactness and can effectively slow down the corrosion damage of a corrosion medium HCl to Q235.
TABLE 2 data of the fitting of bare Q235 to different AP/An corrosion inhibitors based on equivalent circuit diagram R (QR)
FIG. 6 is a BODE curve of bare Q235 and AP/An5, and it can be seen from the graph that the time constant of AP/An5 is 1, the inside and outside uniformity compactness of the corrosion inhibitor film formed on the surface, and the impedance mode of AP/An5 is obviously increased compared with bare Q235. EIS curve analysis shows that AP/An5 forms a good corrosion inhibitor protective film layer on the surface of Q235, and can effectively slow down the corrosion damage of a corrosion medium HCl to Q235.
The 1,1' - (1, 4-phenylene) bis (3-phenylurea)/aniline corrosion inhibitor disclosed by the invention is simple in preparation process, excellent in metal substrate protection efficiency, low in cost and very good in application in the field of metal protection.
The present invention is not limited to the above-described embodiments, and any obvious improvements, substitutions or modifications can be made by those skilled in the art without departing from the spirit of the present invention.
Claims (10)
1. The 1,1' - (1, 4-phenylene) bis (3-phenylurea)/aniline corrosion inhibitor is characterized in that the corrosion inhibitor takes ethylene glycol dimethyl ether (DME) as An organic solvent, and-NH in aniline An molecules 2 and-OCN groups of p-phenylene diisocyanate PPDI, said
The structural formula of the 1,1' - (1, 4-phenylene) bis (3-phenylurea)/aniline corrosion inhibitor is as follows:
2. a process for preparing the 1,1' - (1, 4-phenylene) bis (3-phenylurea)/aniline corrosion inhibitor of claim 1, comprising:
(1) Dissolving aniline An in a solvent glycol dimethyl ether DME, and uniformly mixing to obtain a solution A; dissolving p-phenylene diisocyanate (PPDI) in a solvent ethylene glycol dimethyl ether (DME), and uniformly dispersing by ultrasonic to obtain a solution B;
(2) And adding the solution B into the solution A, magnetically stirring at room temperature to react, and performing rotary evaporation to remove the solvent after the reaction is finished to obtain the 1,1' - (1, 4-phenylene) bis (3-phenylurea)/aniline corrosion inhibitor.
3. The method for preparing the 1,1' - (1, 4-phenylene) bis (3-phenylurea)/aniline corrosion inhibitor according to claim 2, wherein in the step (1), the volume ratio of aniline An to ethylene glycol dimethyl ether DME in the solution A is 0.5.
4. The method for preparing the 1,1' - (1, 4-phenylene) bis (3-phenylurea)/aniline corrosion inhibitor according to the claim 2, wherein in the step (1), the volume ratio of p-phenylene diisocyanate (PPDI) and ethylene glycol dimethyl ether (DME) in the solution B is 0.01:10 to 0.17:10.
5. the method for preparing the 1,1' - (1, 4-phenylene) bis (3-phenylurea)/aniline corrosion inhibitor according to claim 2, wherein in the step (2), the volume ratio of the solution B to the solution A is 1.
6. The method for preparing the 1,1' - (1, 4-phenylene) bis (3-phenylurea)/aniline corrosion inhibitor according to claim 2, wherein in the step (2), the reaction time is 1-2 h under magnetic stirring.
7. Use of the 1,1' - (1, 4-phenylene) bis (3-phenylurea)/aniline corrosion inhibitor of claim 1 for metal protection.
8. Use according to claim 7, wherein the metal protection is corrosion protection.
9. The use of claim 7 wherein the use is the adsorption of a 1,1' - (1, 4-phenylene) bis (3-phenylurea)/aniline corrosion inhibitor onto a metal surface.
10. Use according to claim 9, wherein the metal is stainless steel.
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