CN115536554B - 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 133
- 230000007797 corrosion Effects 0.000 title claims abstract description 128
- 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 102
- 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 37
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 33
- 239000002184 metal Substances 0.000 claims abstract description 33
- 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 27
- 239000002904 solvent Substances 0.000 claims description 17
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 7
- 238000002390 rotary evaporation Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 125000005442 diisocyanate group Chemical group 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- 238000003760 magnetic stirring Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000005764 inhibitory process Effects 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 50
- 229910000831 Steel Inorganic materials 0.000 description 29
- 239000010959 steel Substances 0.000 description 29
- 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
- 239000007788 liquid Substances 0.000 description 7
- 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
- 238000007792 addition Methods 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- 238000005530 etching Methods 0.000 description 5
- 230000010287 polarization Effects 0.000 description 5
- 238000005498 polishing Methods 0.000 description 5
- 230000001681 protective effect Effects 0.000 description 5
- 238000000527 sonication Methods 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000006378 damage Effects 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000005554 pickling Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000013507 mapping Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000004210 cathodic protection Methods 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical class [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000013211 curve analysis Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
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- 230000009456 molecular mechanism Effects 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 235000021110 pickles Nutrition 0.000 description 1
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- 238000001878 scanning electron micrograph Methods 0.000 description 1
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Classifications
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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
-
- 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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- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
The invention provides a1, 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; in the invention, the 1,1'- (1, 4-phenylene) bis (3-phenylurea)/aniline corrosion inhibitor is prepared by taking aniline and paraphenylene 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 protecting a metal base material.
Description
Technical Field
The invention belongs to the technical field of metal protection and material preparation, and particularly relates to a1, 1' - (1, 4-phenylene) bis (3-phenylurea)/aniline corrosion inhibitor, and a preparation method and application thereof.
Background
Economic losses due to metal corrosion account for over 3.5% of the world GDP each year, so there is an epoch-making urgency to slow down metal corrosion. When a metal is in a corrosive medium, the metal atoms undergo oxidation-reduction reactions and are simultaneously corroded. Common solutions to metal corrosion mainly include coatings, cathodic protection, passivation layers, corrosion inhibitors, etc., where corrosion inhibitors are considered the least costly and most efficient option. In the industrial pickling process, the corrosion inhibitor can effectively reduce the secondary corrosion of the acid liquor to the metal matrix, however, a large amount of waste acid liquor can be generated in the pickling process, and the environment is also threatened greatly. Therefore, there is a need to continuously increase the corrosion protection efficiency of the corrosion inhibitor in the pickling process, thereby achieving a reduction in the production of the acid pickle.
The corrosion inhibitor with very small concentration is added into the corrosion medium to slow down the corrosion of metal, and the concentration of the corrosion inhibitor is generally considered to be less than 500 ppm, and the corrosion inhibitor can be adsorbed on the surface of the metal to form a layer of protective film. According to the mechanism of action of the corrosion inhibitor, it can be classified 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 generally influenced by the concentration of the minimum anodic corrosion inhibitor; cathode corrosion inhibitors often form a precipitation layer on the metal surface, blocking corrosive media and electron transfer; the mixed corrosion inhibitor can slow down the corrosion of the anode and the cathode. However, the classification mode classifies the corrosion inhibitor and the action result of the metal surface, and cannot effectively guide people to develop a novel efficient corrosion inhibitor. According to the components of the corrosion inhibitor, the corrosion inhibitor can be divided into an organic corrosion inhibitor and an inorganic corrosion inhibitor, and the inorganic corrosion inhibitor represented by chromates can cause pollution and harm to the environment and human bodies, so that the corrosion inhibitor is difficult to widely apply. The organic corrosion inhibitor has a planar molecular mechanism which is favorable for being adsorbed on the metal surface, contains N, S, P, O and other heteroatoms and-OH, -COOH, -NH 2 and other polar functional groups, has conjugated bonds or aromatic rings, and is more favorable for being adsorbed on the metal surface and slowing down 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 a1, 1' - (1, 4-phenylene) bis (3-phenylurea)/aniline corrosion inhibitor, and a preparation method and application thereof. In the invention, the 1,1'- (1, 4-phenylene) bis (3-phenylurea)/aniline corrosion inhibitor is prepared by taking aniline and paraphenylene 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 protecting a metal base material.
The invention firstly provides a1, 1' - (1, 4-phenylene) bis (3-phenylurea)/aniline corrosion inhibitor which is prepared by taking ethylene glycol dimethyl ether (DME) as An organic solvent, reacting-NH 2 in aniline (An) molecules with-OCN groups of terephthalyl 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 specifically 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 terephthalyl diisocyanate (PPDI) in a solvent DME, and uniformly dispersing by ultrasonic waves to obtain a solution B;
(2) And adding the solution B into the solution A, magnetically stirring at room temperature for reaction, and removing the solvent by rotary evaporation after the reaction is finished to obtain the 1,1' - (1, 4-phenylene) bis (3-phenylurea)/aniline corrosion inhibitor.
Further, in the step (1), in the solution A, the volume ratio of the aniline (An) to the ethylene glycol dimethyl ether (DME) is 0.5:20-1.0:20.
Further, in the step (1), in the solution B, the volume ratio of PPDI to DME 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 1:1-1:3.
In the step (2), the magnetic stirring reaction time is 1-2 h.
The invention also provides 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 to adsorb a 1,1' - (1, 4-phenylene) bis (3-phenylurea)/aniline corrosion inhibitor on a metal surface.
Compared with the prior art, the invention has the beneficial effects that:
the invention prepares the 1,1' - (1, 4-phenylene) bis (3-phenylurea)/aniline corrosion inhibitor (AP/An) by a one-pot method, researches the composition of the corrosion inhibitor and the microscopic morphology of a formed film layer by means of FTIR, EDS, SEM, MAPPING, and evaluates the protective performance of the corrosion inhibitor by adopting Tafel and EIS.
SEM and MAPPING researches show that the 1,1'- (1, 4-phenylene) bis (3-phenylurea)/aniline corrosion inhibitor film has good compactness and uniformity, and the anti-corrosion performance of the 1,1' - (1, 4-phenylene) bis (3-phenylurea)/aniline corrosion inhibitor film in 1mol/L HCl is researched by Tafel polarization curve and EIS curve, so 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 enables the impedance of the AP/An5 to reach 450.2 Ω cm -2.
The 1,1' - (1, 4-phenylene) bis (3-phenylurea)/aniline corrosion inhibitor disclosed by the invention has the advantages of simple preparation process, excellent protection efficiency on metal substrates, low cost and good application in the field of metal protection.
Drawings
FIG. 1 is a FTIR spectrum of 1,1' - (1, 4-phenylene) bis (3-phenylurea)/aniline corrosion inhibitor AP/An.
FIG. 2 is an EDS picture of a1, 1' - (1, 4-phenylene) bis (3-phenylurea)/aniline corrosion inhibitor film in 1mol/L HCl corrosion medium.
FIG. 3 is an SEM image of bare Q235 (a, b) and corrosion inhibitor treated Q235 (c, d) after 0.5h immersion in 1mol/L HCl, where a and c are magnified 3000 times and b and d are magnified 10000 times.
FIG. 4 is a Tafel plot of bare Q235 and corrosion inhibitor AP/An5 in 1mol/L HCl.
Fig. 5 is An impedance curve and a corresponding fitting curve of the bare Q235 and AP/An5, fig. 5a is An impedance curve of the bare Q235, and fig. 5b is An R (QR) equivalent circuit schematic diagram.
FIG. 6 shows BODE curves (FIG. 6 a) and impedance mode curves (FIG. 6 b) for bare Q235 and AP/An 5.
Detailed Description
The invention will be further described with reference to the drawings and the specific embodiments, but the scope of the invention is not limited thereto. In the following examples, the Q235 steel sheet was used as a substrate to adsorb a1, 1' - (1, 4-phenylene) bis (3-phenylurea)/aniline corrosion inhibitor (abbreviated as AP/An corrosion inhibitor) and examined correspondingly, but the scope of the present invention is not limited to Q235 steel sheets.
Example 1:
(1) Pretreatment of Q235 steel sheet:
polishing the surface of the Q235 steel sheet by using 800# to 1000# water-phase sand paper, removing a passivation layer on the surface, sequentially ultrasonically cleaning in acetone and ethanol solution for 10 minutes, and volatilizing at room temperature for later use.
(2) Preparation of AP/An corrosion inhibitor:
adding 20mL of DME and 0.5mol/L aniline solution into a 50mL beaker, uniformly mixing the DME and the aniline solution serving as a solvent, and marking the mixture as solution A for later use;
10mL of DME and 0.2g of PPDI were added to a 25mL beaker, and after 5min of sonication, the PPDI was well dissolved and dispersed in DME solvent, labeled as B solution, for use.
Adding the solution B into the solution A, fully magnetically stirring at room temperature for reaction for 2 hours, and after the reaction is finished, taking the solution as a white turbidity state, 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 different PPDI consumption.
(3) The AP/An1 corrosion inhibitor is adsorbed on the surface of the Q235 steel sheet:
And soaking the Q235 steel sheet in the AP/An1 corrosion inhibitor corrosive liquid 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 Q235 steel sheet:
polishing the surface of the Q235 steel sheet by using 800# to 1000# water-phase sand paper, removing a passivation layer on the surface, sequentially ultrasonically cleaning in 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 of aniline into a 50mL beaker, uniformly mixing the DME and the aniline to obtain a solution A for later use;
10mL of DME and 0.1g of PPDI were added to a 25mL beaker, and after 5 minutes of sonication, the PPDI was allowed to fully dissolve and disperse uniformly in the DME solvent, labeled as B solution, ready for use.
Adding the solution B into the solution A, fully magnetically stirring at room temperature for reaction for 2 hours, and after the reaction is finished, taking the solution as a white turbidity state, removing the solvent by rotary evaporation to obtain the 1,1' - (1, 4-phenylene) bis (3-phenylurea)/aniline corrosion inhibitor, and marking as AP/An2 according to different PPDI consumption.
(3) The AP/An2 corrosion inhibitor is adsorbed on the surface of the Q235 steel sheet:
and soaking the Q235 steel sheet in the AP/An2 corrosion inhibitor corrosive liquid 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 Q235 steel sheet:
polishing the surface of the Q235 steel sheet by using 800# to 1000# water-phase sand paper, removing a passivation layer on the surface, sequentially ultrasonically cleaning in 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 of aniline into a 50mL beaker, uniformly mixing the DME and the aniline to obtain a solution A for later use;
10mL of DME and 0.05g of PPDI were added to a 25mL beaker, and after 5 minutes of sonication, the PPDI was well dissolved and dispersed uniformly in the DME solvent, labeled as B solution, for use.
Adding the solution B into the solution A, fully magnetically stirring at room temperature for reaction for 2 hours, and after the reaction is finished, taking the solution as a white turbidity state, removing the solvent by rotary evaporation to obtain the 1,1' - (1, 4-phenylene) bis (3-phenylurea)/aniline corrosion inhibitor, and marking as AP/An3 according to different PPDI consumption.
(3) The AP/An3 corrosion inhibitor is adsorbed on the surface of the Q235 steel sheet:
And soaking the Q235 steel sheet in the AP/An3 corrosion inhibitor corrosive liquid 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 Q235 steel sheet:
polishing the surface of the Q235 steel sheet by using 800# to 1000# water-phase sand paper, removing a passivation layer on the surface, sequentially ultrasonically cleaning in 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 of aniline into a 50mL beaker, uniformly mixing the DME and the aniline to obtain a solution A for later use;
10mL of DME and 0.025g of PPDI were added to a 25mL beaker, and after 5 minutes of sonication, the PPDI was well dissolved and dispersed in the DME solvent, labeled as B solution, for use.
Adding the solution B into the solution A, fully magnetically stirring at room temperature for reaction for 2 hours, and after the reaction is finished, taking the solution as a white turbidity state, removing the solvent by rotary evaporation to obtain the 1,1' - (1, 4-phenylene) bis (3-phenylurea)/aniline corrosion inhibitor, and marking as AP/An4 according to different PPDI consumption.
(3) The AP/An4 corrosion inhibitor is adsorbed on the surface of the Q235 steel sheet:
and soaking the Q235 steel sheet in the AP/An4 corrosion inhibitor corrosive liquid 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 sheet:
polishing the surface of the Q235 steel sheet by using 800# to 1000# water-phase sand paper, removing a passivation layer on the surface, sequentially ultrasonically cleaning in 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 of aniline into a 50mL beaker, uniformly mixing the DME and the aniline to obtain a solution A for later use;
10mL of DME and 0.0125g of PPDI were added to a 25mL beaker, and after 5min of sonication, the PPDI was well dissolved and dispersed in the DME solvent, and labeled as B solution for use.
Adding the solution B into the solution A, fully magnetically stirring at room temperature for reaction for 2 hours, and after the reaction is finished, taking the solution as a white turbidity state, removing the solvent by rotary evaporation to obtain the 1,1' - (1, 4-phenylene) bis (3-phenylurea)/aniline corrosion inhibitor, and marking as AP/An5 according to different PPDI consumption.
(3) The AP/An5 corrosion inhibitor is adsorbed on the surface of the Q235 steel sheet:
And soaking the Q235 steel sheet in the AP/An5 corrosion inhibitor corrosive liquid for 0.5h, so that the AP/An4 corrosion inhibitor can be adsorbed on the surface of the Q235 steel sheet.
FIG. 1 is a FTIR spectrum of An AP/An5 corrosion inhibitor, wherein the 3445cm -1～3145cm-1 absorption band is attributed to-NH stretching vibration in the AP/An5 molecule, O-H stretching vibration in the H 2 O molecule, and-NH 2 stretching vibration in the unreacted An molecule. 3045 The absorption peak around cm -1 is attributed to the stretching vibration of the benzene ring C-H in the AP/An5 molecule and unreacted An molecule. The absorption peak of 1690cm -1 is assigned to the stretching vibration of c=o in AP/An5, and the absorption peak of 1632cm -1、1560cm-1、1509cm-1、1439cm-1 is assigned to the skeletal vibration of the benzene ring in AP/An5 and unreacted An molecules. FTIR spectrogram researches show that the AP/An5 corrosion inhibitor is successfully prepared.
FIG. 2 is An EDS picture of An AP/An5 corrosion inhibitor film in 1mol/L HCl. The main elements are C, N, O, cl, fe, wherein the Fe element is mainly derived from Q235, the C, N, O is mainly derived from AP/An5 and unreacted An molecules, and the molar ratio of Cl element is only 0.42%, so that the formed corrosion inhibitor film is extremely compact, and the damage of HCl corrosive medium to the surface of the Q235 can be effectively slowed down.
FIG. 3 is An SEM photograph of bare Q235 and treated Q235 after soaking in 1mol/L HCl for 0.5h, wherein FIGS. 3a and 3b show no corrosion inhibitor added to the etching medium, and FIGS. 3c and 3d show the addition of corrosion inhibitor AP/An5 to the etching medium. As can be seen from SEM pictures, small grinding marks exist on the surface of Q235, and comparison of SEM pictures 3a and 3c of 3000 times and SEM pictures 3b and 3d of 10000 times shows that the surfaces of the pictures 3a and 3b are severely corroded, which indicates that the corrosion inhibitor AP/An5 can effectively slow down the corrosion rate of HCl on the surface of the steel sheet.
Example 6:
The corrosion resistance of the 1,1'- (1, 4-phenylene) bis (3-phenylurea)/aniline corrosion inhibitors and the compactness of the films formed by the 1,1' - (1, 4-phenylene) bis (3-phenylurea)/aniline corrosion inhibitors prepared in examples 1-5 at different PPDI additions were examined in this example.
Tafel polarization curve is an important method for researching the protective performance of the corrosion inhibitor, the smaller the self-corrosion current I corr is, the better the corrosion inhibition performance is shown, the better the corrosion inhibition performance can be expressed by the protection efficiency, namely, the protection efficiency eta= (I corra-Icorrb)/Icorr a, wherein I corr a represents the self-corrosion current of bare Q235 in a corrosion medium, and I corr b represents the self-corrosion current obtained by adding 1,1' - (1, 4-phenylene) bis (3-phenylurea)/aniline corrosion inhibitor in the corrosion medium.
In a three-electrode electrochemical system, a saturated calomel electrode is used as a reference electrode, a platinum wire is used as a counter electrode, a Q235 stainless steel sheet is used as a working electrode, and Q235 of 1cm 2 is exposed in 1mol/L HCl corrosive liquid to carry out Tafel polarization curve test.
TABLE 1 Tafel polarization Curve data sheet with varying PPDI and AP/An additions
Table 1 is a table of Tafel polarization curve data for 1,1' - (1, 4-phenylene) bis (3-phenylurea)/aniline corrosion inhibitors prepared at various PPDI loadings. As can be seen from table 1 and fig. 4, as the PPDI addition amount decreases, the self-etching current decreases and increases, and when the PPDI addition amount is 0.0125g, the self-etching current reaches the minimum value (3.742 × -5 a), the self-etching current of AP/An5 decreases by two orders of magnitude, the corresponding protection efficiency reaches 98.59%, and the protection efficiency is equivalent to that of the common resin coating.
The Electrochemical Impedance Spectroscopy (EIS) curve is an important method for researching the compactness of the 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 to a Q235 matrix is, and the specific steps are that in a three-electrode electrochemical system, a saturated calomel electrode is used as a reference electrode, a platinum wire is used as a counter electrode, a Q235 stainless steel sheet is used as a working electrode, Q235 of 1cm 2 is exposed in 1mol/L HCl corrosive liquid, and after the open circuit potential is stable, namely the third digit after the open circuit potential decimal point is kept constant, and EIS curve test is carried out.
FIG. 5 is An impedance spectrum of a bare Q235 steel sheet and AP/An5, wherein measured data is fitted in ZSimDemo3.30d according to An equivalent circuit R (QR), the fitted data is shown in Table 2, the impedance value of the bare Q235 is 15.21Ω -cm -2, and the impedance value of the AP/An5 is 450.20 Ω -cm -2, which shows that the AP/An5 corrosion inhibitor film has excellent compactness and can effectively slow down corrosion damage of corrosive medium HCl to Q235.
TABLE 2 fitting data of bare Q235 with different AP/An Corrosion inhibitors based on equivalent Circuit Board R (QR)
FIG. 6 shows BODE curves of bare Q235 and AP/An 5. As can be seen from the graph, the time constant of AP/An5 is 1, the inner and outer uniform compactness of the corrosion inhibitor film formed on the surface is improved, and meanwhile, the impedance mode of AP/An5 is obviously increased compared with that of bare Q235. EIS curve analysis shows that the AP/An5 forms a good corrosion inhibitor protective film layer on the surface of the Q235, so that corrosion damage of corrosion medium HCl to the Q235 can be effectively slowed down.
The 1,1' - (1, 4-phenylene) bis (3-phenylurea)/aniline corrosion inhibitor disclosed by the invention has the advantages of simple preparation process, excellent protection efficiency on metal substrates, low cost and good application in the field of metal protection.
The examples are preferred embodiments of the present invention, but the present invention is not limited to the above-described embodiments, and any obvious modifications, substitutions or variations that can be made by one skilled in the art without departing from the spirit of the present invention are within the scope of the present invention.
Claims (7)
1. A method for preparing a 1,1' - (1, 4-phenylene) bis (3-phenylurea)/aniline corrosion inhibitor, comprising the steps of:
(1) Dissolving aniline An in a solvent ethylene glycol dimethyl ether DME, and uniformly mixing to obtain a solution A; dissolving terephthalyl diisocyanate PPDI in a solvent ethylene glycol dimethyl ether DME, and uniformly dispersing by ultrasonic to obtain a solution B;
In the solution A, the final concentration of aniline An is 0.5mol/L;
in the solution B, the dosage ratio of the terephthalyl diisocyanate PPDI to the ethylene glycol dimethyl ether DME is 0.01-0.17 g:10mL;
(2) Adding the solution B into the solution A, magnetically stirring at room temperature for reaction, and removing the solvent by rotary evaporation after the reaction is finished to obtain the 1,1' - (1, 4-phenylene) bis (3-phenylurea)/aniline corrosion inhibitor;
The volume ratio of the solution B to the solution A is 1:1-1:3;
the structural formula of the 1,1' - (1, 4-phenylene) bis (3-phenylurea) is as follows:
。
2. The method for preparing a 1,1' - (1, 4-phenylene) bis (3-phenylurea)/aniline corrosion inhibitor according to claim 1, wherein in the step (2), the magnetic stirring reaction time is 1-2 h.
3. A1, 1' - (1, 4-phenylene) bis (3-phenylurea)/aniline corrosion inhibitor prepared by the process of any one of claims 1 or 2.
4. Use of the 1,1' - (1, 4-phenylene) bis (3-phenylurea)/aniline corrosion inhibitor of claim 3 in metal protection.
5. The use according to claim 4, wherein the metal protection is corrosion protection.
6. The use according to claim 4, wherein the use is to adsorb a 1,1' - (1, 4-phenylene) bis (3-phenylurea)/aniline corrosion inhibitor on a metal surface.
7. The use according to claim 6, wherein the metal is stainless steel.
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