CN105887102A - Phosphate ester functionalized quaternary ammonium salt corrosion inhibitor and preparation method thereof - Google Patents
Phosphate ester functionalized quaternary ammonium salt corrosion inhibitor and preparation method thereof Download PDFInfo
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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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/04—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors
- C23G1/06—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors
- C23G1/066—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors phosphorus-containing compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se)
- C07F9/40—Esters thereof
- C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4006—Esters of acyclic acids which can have further substituents on alkyl
- C07F9/4009—Esters containing the structure (RX)2P(=X)-alk-N...P (X = O, S, Se)
Abstract
The invention discloses a phosphate ester functionalized quaternary ammonium salt corrosion inhibitor. Please see the general structure of the corrosion inhibitor in the description, wherein, R represents alkyl groups with the number of carbon atoms ranging from 8 to 18; and n represents 2 or 3. The invention further discloses a preparation method of the corrosion inhibitor. The phosphate ester functionalized quaternary ammonium salt corrosion inhibitor has very high corrosion inhibiting performance.
Description
Technical field
The present invention relates to quaternary ammonium salt corrosion inhibitor of phosphate ester functionalization and preparation method thereof.
Background technology
Pickling of metal is widely present in different industrial processes production processes, such as in the mechanical industry acid pickling and rust removing of canister, plate and goods, scale removal in the boiler of large enterprise, power and transportation industry medium-and-large-sized device outer surface rust cleaning, surface clean of marine vessel etc..Common mineral acid such as sulphuric acid, nitric acid, hydrochloric acid and Fluohydric acid. and part organic acid all can be as pickles.Generally, being frequently accompanied by the etching problem of metal self during using these pickle pickling, in order to reduce the pickle corrosion to metal self as far as possible, different types of corrosion inhibiter has been developed and has been widely used.Therefore, the performance quality of corrosion inhibiter is directly becoming the key problem in technology determining pickling success or failure.
At present in the different types of restrainer of report, organic inhibitor is because preparation is simple, corrosion mitigating effect significantly becomes a most commonly seen class in dissimilar corrosion inhibiter.Generally speaking, when organic inhibitor refers to add extremely low concentration in acid solution, protective action can be played in metal surface and slow down the chemical substance of corrosion, it is typically containing O, N, P, S etc. are with the organic compound of lone electron pair, they can be by the Specific Interactions (electrostatic interaction between metal surface, π-π interacts, Coordination interaction, hydrophobic interaction etc.) and stable adsorbing on the surface of metallic substrates, form one layer of stable physical absorption or chemisorbed film, thus play and intercept contacting with each other of corrosive medium and metal surface, play inhibition purpose.
In numerous organic inhibition agent molecules, quaternary ammonium salt corrosion inhibiter because of its simple synthesis step, relatively low cost and efficient antiseptic property by extensive concern (Yu, Q.; Jiang, X.; Zhou,
L.; Liao, Y.; etal. Synthesis and Anticorrosion for X70 Steel of Propynol
Derivatives in Acid. J. Mater. Environ. Sci 2014, 5 (1), 13-32; Yu, Q.; Jiang,
X.; Zhou, L.; Xia, G., Preparation and inhibition of 2-methyl cetyl pyridine
bromide for X70 steel in 5M HCl. Materials Research Innovations 2013, 17 (S1),
166-171.).Phosphate ester and derivant thereof are widely used as the preservative of metal always, are primarily due to phosphate functional group and can form stable coordinate bond with metal surface and assemble one layer of stable adsorbed film of formation, so just having excellent antiseptic effect (Gao, X., Liu, S., Lu, H.
Gao, F., Ma, H. Corrosion Inhibition of Iron in Acidic Solutions by Monoalkyl
Phosphate Esters with Different Chain Lengths. Ind. Eng. Chem. Res. 2015, 54,
1941 1952).It is combined in same molecule it is contemplated that these two parts can be rolled into a ball for quaternary ammonium salt and phosphate functional by MOLECULE DESIGN, is improved the inhibition efficiency of noval chemical compound by intramolecular cooperative effect.Document and patent investigation show also do not have the quaternary ammonium salt corrosion inhibitor application report about phosphate ester functionalization.
Summary of the invention
It is an object of the invention to provide the quaternary ammonium salt corrosion inhibitor of a series of phosphate ester functionalization.
Another object of the present invention is to provide the preparation method of the quaternary ammonium salt corrosion inhibitor of a series of phosphate ester functionalization.
The quaternary ammonium salt corrosion inhibitor of phosphate ester functionalization, it is characterised in that the general structure of this corrosion inhibiter is as follows:
Wherein, R represents the alkyl that carbon number is 8 to 18；N represents 2 or 3.
The preparation method of the quaternary ammonium salt corrosion inhibitor of phosphate ester functionalization as mentioned above, it is characterised in that concretely comprising the following steps of this preparation method:
By in O, O '-diethyl phosphonic acid ethyl bromide ester or O, O '-diethyl bromopropyl phosphonate ester and N, N-dimethyl alkylamine addition acetonitrile, being stirred at reflux 8 ~ 12 hours under inert gas shielding, then decompression steams solvent, residue from dichloromethane and normal hexane recrystallization.
The mol ratio of described O, O '-diethyl phosphonic acid ethyl bromide ester or O, O '-diethyl bromopropyl phosphonate ester and N, N-dimethyl alkylamine is 1:1.0 ~ 1.5.
Described N, N-dimethyl alkylamine is N, N-dimethyl octylame, N, N-dimethyl lauryl amine, N, N-dimethyl tetradecy lamine, N, N-dimethyl cetylamine or N, Dymanthine.
The volume ratio of described dichloromethane and normal hexane is 1:10-15.
O, O '-diethyl phosphonic acid ethyl bromide ester or O, O '-diethyl bromopropyl phosphonate ester synthesized reference document: (Z. G. Mu, W. M. Liu, S. X. Zhang, F. Zhou. Chemistry Letters
33 (2004) 524-525.)。
The quaternary ammonium salt corrosion inhibitor weight-loss method analysis result of phosphate ester functionalization of the present invention shows that it has higher corrosion inhibition in the hydrochloric acid solution of 1 mol/L.
The quaternary ammonium salt corrosion inhibitor of phosphate ester functionalization of the present invention is as mild steel corrosion inhibiter in 1 mol/L hydrochloric acid solution, can be obtained by electrochemical impedance spectrometry analysis, the quaternary ammonium salt of this series phosphate ester functionalization can effectively adsorb at steel surface, the adsorbed film forming stable coordinate bond with iron surface and form densification is rolled into a ball by season atom N or phosphate functional, simultaneously, hydrophobic chain long in this series quaternary ammonium salt molecule can reversely stretch in water and mutually be wound around and form the hydrophobic membrane of densification, can effectively intercept the erosion to substrate of corrosive chloride ion, thus play effective antiseptic property.
The quaternary ammonium salt corrosion inhibitor of phosphate ester functionalization of the present invention, is measured by dynamic potential polarization curve, and the quaternary ammonium salt of the phosphate ester functionalization of this series has the highest corrosion inhibition, and main inhibition mechanism is based on the hybrid corrosion inhibitor of anode suppression.
Detailed description of the invention
In order to be better understood from synthesis and the corrosion inhibition of series corrosion inhibiter of the present invention, we are with bromododecane base (O, O '-diethylpropyl phosphonate ester) N, N-Dimethyl Ammonium (NP-12), bromotetradecane base (O, O '-diethylpropyl phosphonate ester N, specifically it is illustrated as a example by N-Dimethyl Ammonium (NP-14), bromohexadecane base (O, O '-diethylpropyl phosphonate ester) N, N-Dimethyl Ammonium (NP-16).
Embodiment 1
The preparation of bromododecane base (O, O '-diethylpropyl phosphonate ester) N, N-Dimethyl Ammonium (NP-12) corrosion inhibiter
Preparation process:
250 milliliters of round-bottomed flasks add 0.05 mole of N, N-dimethyl dodecylamine, 0.05 mole of O, O '-diethyl bromopropyl phosphonate ester, adds the acetonitrile of 100 milliliters as solvent, the lower 80 degrees Celsius of reactions of inert gas shielding 8 hours.After reaction terminates, decompression steams solvent, obtains oily residue and repeatedly washs with normal hexane in refrigerating process.Afterwards, the residual solid obtained is dissolved in and carries out recrystallization by dichloromethane and ethyl acetate volume ratio 1:10, obtains white solid and is bromododecane base (O, O '-diethylpropyl phosphonate ester) N, N-Dimethyl Ammonium (NP-12).
NP-12 inhibitor structure formula is:
NP-12. Yield: 72%.1H
NMR (400 MHz, CDCl3)
δ
: 4.24 – 3.94 (m, 4H), 3.98 – 3.60 (m, 3H), 3.57 – 3.08 (m, 8H), 1.86 (dd,J
= 74.1, 57.7 Hz, 7H), 1.50 – 1.03 (m, 25H), 1.00 – 0.65 (m, 3H). 13C NMR (100 MHz, CDCl3) δ: 64.31, 62.13,
62.07,51.21, 31.87, 29.56, 29.43, 29.38, 29.30, 29.21, 26.28, 22.74, 22.66,
22.58, 21.16, 16.72, 16.68, 16.51, 16.45, 14.10.
Embodiment 2
The preparation of bromotetradecane base (O, O '-diethylpropyl phosphonate ester) N, N-Dimethyl Ammonium (NP-14) corrosion inhibiter
Preparation process:
250 milliliters of round-bottomed flasks add 0.05 mole of N, N-dimethyl tetradecyl amine, 0.05 mole of O, O '-diethyl bromopropyl phosphonate ester, adds the acetonitrile of 100 milliliters as solvent, the lower 80 degrees Celsius of reactions of inert gas shielding 8 hours.After reaction terminates, decompression steams solvent, obtains oily residue and repeatedly washs with normal hexane in refrigerating process.Afterwards, the residual solid obtained is dissolved in and carries out recrystallization by dichloromethane and ethyl acetate volume ratio 1:10, obtains white solid and is bromotetradecane base (O, O '-diethylpropyl phosphonate ester) N, N-Dimethyl Ammonium (NP-14).
NP-14 inhibitor structure formula is:
NP-14. Yield: 78%.1H
NMR (400 MHz, CDCl3)
δ
: 4.07 (tt,J = 55.2, 27.4 Hz,
4H), 3.75 (dd,J = 36.8, 5.8 Hz, 2H), 3.55 – 3.24 (m, 8H), 1.89 (ddd,J
= 60.7, 59.9, 28.1 Hz, 7H), 1.44 – 1.16 (m, 29H), 0.91 – 0.78 (m, 3H). 13C
NMR (101 MHz, CDCl3) δ: 62.18, 62.12, 62.09, 51.22, 31.91,
29.66, 29.57, 29.45, 29.39, 29.22, 26.29, 22.75, 22.57, 21.16, 16.74, 16.52,
16.46, 14.12.
Embodiment 3
The preparation of bromohexadecane base (O, O '-diethylpropyl phosphonate ester) N, N-Dimethyl Ammonium (NP-16) corrosion inhibiter
Preparation process:
250 milliliters of round-bottomed flasks add 0.05 mole of N, N-dimethyl hexadecyl amine, 0.05 mole of O, O '-diethyl bromopropyl phosphonate ester, adds the acetonitrile of 100 milliliters as solvent, the lower 80 degrees Celsius of reactions of inert gas shielding 8 hours.After reaction terminates, decompression steams solvent, obtains oily residue and repeatedly washs with normal hexane in refrigerating process.Afterwards, the residual solid obtained is dissolved in and carries out recrystallization by dichloromethane and ethyl acetate volume ratio 1:10, obtains white solid and is bromohexadecane base (O, O '-diethylpropyl phosphonate ester) N, N-Dimethyl Ammonium (NP-16).
NP-16 inhibitor structure formula is:
NP-16. Yield: 84%. 1H
NMR (400 MHz, CDCl3)
δ
: 4.19 – 4.03 (m, 4H), 3.91 – 3.65 (m, 2H), 3.51 – 3.21 (m, 9H), 2.14 – 1.99 (m, 2H), 1.95 – 1.80 (m, 2H), 1.73 (s,
2H), 1.46 – 1.10 (m, 32H), 0.87 (t,J
= 6.8 Hz, 3H). 13C NMR (101 MHz, CDCl3) δ:64.57, 62.25, 62.18, 51.21,
31.39, 29.70, 29.68, 29.66, 29.64, 29.58, 29.45, 29.38, 29.214, 26.28, 22.76,
22.70, 22.55, 21.22, 16.76, 16.72, 16.52, 16.46, 14.13.
Embodiment 4
Corrosion inhibiter of the present invention mainly in industrial acid-washed, acid dip, show, accordingly, it is capable to no, one of the key index that high inhibition efficiency is the application of this series corrosion inhibiter.We use the static steel corrosion testing of classics to have rated interpolation variable concentrations NP-12, corrosion inhibition to mild steel in NP-14, NP-16 1 mol/L hydrochloric acid solution at different temperatures.Concrete corrosion inhibition rate data are as shown in the table 1-23 in embodiment 4.
First we have rated the NP-12 of variable concentrations corrosion inhibition in 1 mol/L hydrochloric acid solution of different temperatures.Experimental data is as shown in following table 1-7:
We have observed that from the data of table 1-7, compare and for blank hydrochloric acid, NP-12 add high degree inhibit mild steel corrosion rate in 1 mol/L hydrochloric acid solution, in all temperature ranges, add in 300 micromole NP-12 to 1 mol/L hydrochloric acid solutions, corrosion rate is substantially all reduction an order of magnitude, and corrosion inhibition rate is up to more than 90% simultaneously.Meanwhile, the data from table 1-7 also are able to significantly find, in all temperature ranges, the inhibition speed of corrosion inhibiter is all as the increase of concentration and increases, and reduces along with the rising of temperature.
Table
1. NP-12 corrosion inhibiter corrosion inhibition in the 1 mol/L hydrochloric acid of 30 degrees Celsius
Table
2. NP-12 corrosion inhibiter corrosion inhibition in the 1 mol/L hydrochloric acid of 40 degrees Celsius
Table
3. NP-12 corrosion inhibiter corrosion inhibition in the 1 mol/L hydrochloric acid of 50 degrees Celsius
Table
4. NP-12 corrosion inhibiter corrosion inhibition in the 1 mol/L hydrochloric acid of 60 degrees Celsius
Table
5. NP-12 corrosion inhibiter corrosion inhibition in the 1 mol/L hydrochloric acid of 70 degrees Celsius
Table
6. NP-12 corrosion inhibiter corrosion inhibition in the 1 mol/L hydrochloric acid of 80 degrees Celsius
Table
7. NP-12 corrosion inhibiter corrosion inhibition in the 1 mol/L hydrochloric acid of 90 degrees Celsius
Embodiment 5
In fact, commonly used commercially quaternary ammonium salt inhibitor molecular comprises long alkyl chain more, in order to be better understood from the impact for corrosion inhibition of the alkyl chain length in this series inhibitor molecular, we examine NP-14 at variable concentrations, corrosion inhibition in 1 molar hydrochloric acid solution of different temperatures, result is as shown in following table 8-14.Find out from table 8 below-14, compared with the NP-12 of same concentrations, NP-14 shows more preferable corrosion inhibition at low concentrations, give an example, in the 1 mol/L hydrochloric acid solution of 30 degrees Celsius, 20 micromolar NP-14 corrosion inhibition rates i.e. can reach 89%, and under comparable sodium, the corrosion inhibition rate of NP-12 is only 64%.And in the range of temperature 30-60 degree Celsius, corrosion inhibition rate still can be maintained in the stability range of 80-90%.When concentration increases, corrosion inhibition rate there is no significantly increase, indicates absorption and has reached balance.When temperature is higher than 70 DEG C, an obvious corrosion inhibition rate reduces and occurs, and indicates the increase along with temperature, and inhibitor molecular metal surface there occurs desorption.But within the scope of whole temperature, NP-14 all shows more stable than NP-12, more preferable inhibition efficiency.These results prove along with the increase of alkyl chain length, and inhibitor molecular significantly more efficient absorption can form stable protecting film at steel surface, and alkyl chain length has very important impact to the stability of adsorbed film.
Table
8. NP-14 corrosion inhibiter corrosion inhibition in the 1 mol/L hydrochloric acid of 30 degrees Celsius
Table
9. NP-14 corrosion inhibiter corrosion inhibition in the 1 mol/L hydrochloric acid of 40 degrees Celsius
Table
10. NP-14 corrosion inhibiter corrosion inhibition in the 1 mol/L hydrochloric acid of 50 degrees Celsius
Table
11. NP-14 corrosion inhibiter corrosion inhibition in the 1 mol/L hydrochloric acid of 60 degrees Celsius
Table
12. NP-14 corrosion inhibiter corrosion inhibition in the 1 mol/L hydrochloric acid of 70 degrees Celsius
Table
13. NP-14 corrosion inhibiter corrosion inhibition in the 1 mol/L hydrochloric acid of 80 degrees Celsius
Table
14. NP-14 corrosion inhibiter corrosion inhibition in the 1 mol/L hydrochloric acid of 90 degrees Celsius
Embodiment 6
In order to further investigate the alkyl chain length impact for inhibitor molecular corrosion inhibition rate, we have rated NP-16 inhibition efficiency in the hydrochloric acid solution of 1 mole, and experimental result is as described in following table 15-21.From table 15 it can be seen that, when 30 degrees Celsius, NP-16 is when the lowest concentration such as 3 micromole, just can effectively suppress mild steel corrosion in 1 mol/L hydrochloric acid solution, inhibition efficiency is up to 83%, and when temperature is higher than 70 degrees Celsius, corrosion inhibition rate seems to have and a little reduces, when but density of corrosion inhibitor is higher than 15 micromoles, it is the least that corrosion inhibition rate reduces amplitude with the rising of temperature, and when 60 degrees Celsius, corrosion inhibition rate is still more than 90%.NP-16 shows high corrosion inhibition when low concentration, and main cause is that its long hydrophobic chain can reversely extend in water, forms stable screen layer, suppresses corrosive ion attack metal substrate.In addition the N in inhibitor molecular+Site is also adsorbed on the metallic substrate easily by electrostatic interaction.Additionally, due to the phosphate functional group in inhibitor molecular is easy and metallic substrates forms firm coordinate bond, causing the protecting film formed in metal surface more stable, protective effect is more lasting.
Table
15. NP-16 corrosion inhibiter corrosion inhibition in the 1 mol/L hydrochloric acid of 30 degrees Celsius
Table
16. NP-16 corrosion inhibiter corrosion inhibition in the 1 mol/L hydrochloric acid of 40 degrees Celsius
Table
17. NP-16 corrosion inhibiter corrosion inhibition in the 1 mol/L hydrochloric acid of 50 degrees Celsius
Table
18. NP-16 corrosion inhibiter corrosion inhibition in the 1 mol/L hydrochloric acid of 60 degrees Celsius
Table
19. NP-16 corrosion inhibiter corrosion inhibition in the 1 mol/L hydrochloric acid of 70 degrees Celsius
Table
20. NP-16 corrosion inhibiter corrosion inhibition in the 1 mol/L hydrochloric acid of 80 degrees Celsius
Table
21. NP-16 corrosion inhibiter corrosion inhibition in the 1 mol/L hydrochloric acid of 90 degrees Celsius
Embodiment 7
Metal corrosion in sour environment is an electrochemical process, corrosion inhibiter add the electric charge transmission that membership significantly has influence in corrosion system, suppression corrosion.In order to the generation of the most effective monitoring corrosion, electrochemical means is used to have become as widely used method, electrochemical impedance spectroscopy (EIS), it is also called ac impedance technology as most commonly seen electro-chemical test means, the interface capacitance obtaining being formed between metal and medium can be measured accurately, the dielectric resistance of system, charge transfer resistance, corrosion rate.
For the slow-releasing agent system of at present research, the results are shown in Table 22 in the concrete analysis of Based on AC Impedance Measurements, as seen from Table 22, for NP-12, NP-14, NP-16 when concentration increases to 300 micromole from 0 respectively, charge transfer resistance value (R ct) progressively increase to 178.1 Ω cm from 3.006 respectively2And electric double layer holds (Cdl) it is reduced to 23.59 from 35.89 respectively, 16.5 uF/cm2.For NP-16, the concentration of addition is when 3 micromoles increase to 30 micromoles, and corresponding charge transfer resistance increases to 110.5 Ω cm from 3.0062And corresponding electric double layer capacitance is gradually lowered to 20.05 uF/cm from 35.892.These results all demonstrate along with corrosion inhibiter adds, and what increasing inhibitor molecular can be spontaneous is adsorbed onto on carbon steel substrates, causes corrosive ion (Cl-) it is difficult to attack substrate, along with the concentration of inhibitor molecular increases, inhibitor molecular adsorbed film is all the more stable and fine and close, and electric double layer distance is the least, and electric capacity is the biggest.Ultimately result in charge transfer resistance to be gradually increased.It should be noted that and compare and NP-12 and NP-16, NP-16 but has and NP-12 in the concentration range of order of magnitude lower, the close inhibition efficiency of NP-14.These results the most further demonstrate hydrophobic chain length in inhibitor molecular and play very important effect for the raising of inhibition efficiency, alkyl chain is the longest, the easiest formed in metal surface stable hydrophobic once, improve integrity and the stability of inhibitor molecular adsorption layer further.
Table
22 different chain length inhibitor moleculars AC impedance spectral measurement of corrosion inhibition when 30 degrees Celsius in 1 mol/L hydrochloric acid solution
Embodiment 8
In order to be further understood from the inhibition mechanism of inhibitor molecular, we have carried out polarization curve test to corrosion system, some experiment parameters such as metal balance corrosion potential in corrosive medium (E corr), corrosion electric current density (I corr), cathode reaction Tafel slope (β c) and anode reaction Tafel slope (β a) and calculated corrosion inhibition rate percent (η) it is listed in the table below 23.
Can be seen that from the data of table 23, for current research system, corrosion electric current density all reduces with the increase of density of corrosion inhibitor, such as: when 30 degrees Celsius, density of corrosion inhibitor is respectively 0,30,50,100,200 and during 300 micromole, and mild steel is in NP-12 solution I corr It is followed successively by 1182,584,559,252,201.1 and 128.1,174.1 μ Acm-2, in NP-14 solutionI corrIt is followed successively by 1182.0,66.9,58.76,42.26,32.83,42.76 μ Acm-2, and in NP-16 solution 0,3,5,10,20,30 micromole timeI corrIt is respectively 1182,143.9,115.4,90.59,44.81,39.44,53.22 μ Acm-2.ObviouslyI corr Reducing along with the increase adding density of corrosion inhibitor, the addition of this explanation corrosion inhibiter significantly inhibits the corrosion of metallic substrates.Additionally, also there is significant change along with the concentration of corrosion inhibiter increases the corresponding corrosion potential of mild steel.Under normal circumstances, after corrosion inhibiter adds, the Δ of corrosion systemE corr (ΔE corr=E′corr –E corr . E′corrAdd the corrosion potential after corrosion inhibiter,E corrNot adding the corrosion potential of corrosion inhibiter) can indirectly to illustrate that corrosion inhibiter plays the mechanism of corrosion inhibition be negative electrode suppressive or anode suppressive on earth in change.If document report △E corrChanging value less than 85 millivolts, this compound is just considered hybrid corrosion inhibitor.For current research system, when adding the inhibitor molecular of variable concentrations, mild steelE corrAll there occurs significantly shuffle (anode polarization region), ΔE corrMaximum is 29 millivolts, illustrates that the compound of these three series is the corrosion inhibiter of mixed type, but mainly based on anode suppression.All these data are with consistent by weight-loss method and the proper experimental result of electrochemical method before, all prove the increase along with density of corrosion inhibitor, have a lot of inhibitor moleculars to be adsorbed onto the surface of carbon steel and play the effect of suppression substrate corrosion, simultaneously, the increase of alkyl chain causes the inhibitor molecular of absorption to have more preferable hydrophobic performance, shows more stable and efficient antiseptic property.
Table
The potentiodynamic polarization of 23 different chain length inhibitor moleculars corrosion inhibition when 30 degrees Celsius in 1 mol/L hydrochloric acid solution is measured
。
Claims (5)
1. the quaternary ammonium salt corrosion inhibitor of phosphate ester functionalization, it is characterised in that the general structure of this corrosion inhibiter is as follows:
Wherein, R represents the alkyl that carbon number is 8 to 18；N represents 2 or 3.
2. the preparation method of the quaternary ammonium salt corrosion inhibitor of phosphate ester functionalization as claimed in claim 1, it is characterised in that concretely comprising the following steps of this preparation method:
By in O, O '-diethyl phosphonic acid ethyl bromide ester or O, O '-diethyl bromopropyl phosphonate ester and N, N-dimethyl alkylamine addition acetonitrile, being stirred at reflux 8 ~ 12 hours under inert gas shielding, then decompression steams solvent, residue from dichloromethane and normal hexane recrystallization.
3. preparation method as claimed in claim 2, it is characterised in that the mol ratio of described O, O '-diethyl phosphonic acid ethyl bromide ester or O, O '-diethyl bromopropyl phosphonate ester and N, N-dimethyl alkylamine is 1:1.0 ~ 1.5.
4. preparation method as claimed in claim 2 or claim 3, it is characterised in that described N, N-dimethyl alkylamine is N, N-dimethyl octylame, N, N-dimethyl lauryl amine, N, N-dimethyl tetradecy lamine, N, N-dimethyl cetylamine or N, Dymanthine.
5. preparation method as claimed in claim 2, it is characterised in that the volume ratio of described dichloromethane and normal hexane is 1:10-15.
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| CN108840804A (en) * | 2018-06-21 | 2018-11-20 | 中国科学院兰州化学物理研究所 | Functionalization propargyl alcohol quaternary ammonium salt and its preparation method and application |
| WO2019081907A1 (en) * | 2017-10-26 | 2019-05-02 | Johnson Matthey Public Limited Company | Ionic liquid |
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| WO2014127451A1 (en) * | 2013-02-19 | 2014-08-28 | Nano Safe Coatings Incorporated (A Florida Corporation 3 P 14000024914) | Phosphorus functional antimicrobial coatings for metal surfaces |
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| CN108840804A (en) * | 2018-06-21 | 2018-11-20 | 中国科学院兰州化学物理研究所 | Functionalization propargyl alcohol quaternary ammonium salt and its preparation method and application |
| CN108840804B (en) * | 2018-06-21 | 2021-02-12 | 中国科学院兰州化学物理研究所 | Functionalized propargyl alcohol quaternary ammonium salt and preparation method and application thereof |
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