CN105272916A - Novel rosin imidazoline corrosion inhibitor - Google Patents
Novel rosin imidazoline corrosion inhibitor Download PDFInfo
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- CN105272916A CN105272916A CN201510064954.3A CN201510064954A CN105272916A CN 105272916 A CN105272916 A CN 105272916A CN 201510064954 A CN201510064954 A CN 201510064954A CN 105272916 A CN105272916 A CN 105272916A
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- rosin
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Abstract
The invention relates to the synthesis and application technology field of compounds used for metal anticorrosion, and concretely discloses a novel rosin imidazoline corrosion inhibitor, a synthetic method and applications. The initial raw material of the provided compound is rosin acid, the raw material is single and the synthetic route operation is simple. The method for preparing a corrosion inhibitor from the synthesized compound is simple, the compound is dissolved in dimethyl formamide, then the obtained solution is dissolved in water, then 1-hydroxyethylidene-1,1-diphosphonic acid is added, and uniform stirring is carried out. The corrosion inhibitor is safe and environmentally friendly, and has excellent corrosion inhibition effects. The corrosion inhibitor can be used for oil and gas field ground gathering and storage and transportation pipes, prevents damage of corrosive gases to metal materials of steel and the like and reduces corrosion loss.
Description
Technical field
The present invention relates to the compou nd synthesis for anticorrosive metal and applied technical field, be specifically related to a kind of new rosin base imidazolines and synthetic method thereof and application, this compound can be used for oil, gas well liquid loading as inhibiter, the anti-corrosion of metal in pipeline transportation process.
Background technology
In recent decades, the oil-gas field of the multiple corrosive medium such as sulfide hydrogen, carbonic acid gas and highly mineralized formation brines occurs in succession.The heavy corrosion of oil-gas field equipment under sour environment, more and more causes the concern of people.The corrosion of oil-gas field is not only given the exploitation of oil-gas field, is produced and cause huge financial loss, also directly threatens the living environment of the mankind and healthy simultaneously.Visible, strengthen corrosion and protection technical study, implement monitoring and sfgd. increasing income and decreasing expenditure to manufacture effectively, increase production and improve productivity and be significant.
Add the anti-corrosion method that inhibiter is a kind of economical and effective and practicality in corrosive medium, in numerous inhibiter kind, imidazoline corrosion inhibitor is with high-efficiency low-toxicity, be quite popular without the advantage such as specific stimulation smell, environmental pollution be little.Imidazoline corrosion inhibitor is as the simple environmentally friendly inhibiter of a kind of preparation process, and range of application is very extensive.Organic acid kind for the synthesis of imidazoline corrosion inhibitor is a lot, but natural matter is fewer, China as rosin production and big export country, natural rosin aboundresources, cheap, with its synthesis inhibiter practice of putting into production will have very big Social benefit and economic benefit.The tricyclic diterpene molecular structure that rosinyl is unique, has better inhibition efficiency by the Rosin-based Imidazoline making to produce.Relevant report is there is not yet in prior art.
Summary of the invention
For the deficiencies in the prior art, first object of the present invention there are provided the Rosin-based Imidazoline compounds shown in a kind of formula (4):
Second object there are provided the synthetic method of Rosin-based Imidazoline compounds shown in a kind of above-mentioned formula (4), and this series of compounds contriver synthesizes first and confirms.
The object of the invention is achieved by the following technical programs.
The synthetic method of Rosin-based Imidazoline compounds shown in a kind of formula (4), its step is as follows:
Step a: by sylvic acid and K
2cO
3be dissolved in dimethyl formamide, add methyl iodide (MeI), stir 3 hours, TLC point plate reacts completely.Vacuum rotary steam removes MeI, extract by ethyl acetate (EA), concentrated, washing removing dimethyl formamide, organic layer saturated sodium-chloride washing, dry, concentrated, obtain formula (2) compound after ethyl acetate (EA)/sherwood oil (PE) mistake silicon gel column purifying of remaining ingredient 1:10, reaction formula is as follows:
Step b: under 0-10 DEG C of condition, adds quadrol and trimethyl aluminium (AlMe in toluene
3), mix, then add formula (2) compound that step a obtains, abundant stirring and refluxing 12 hours.Be cooled to 0 DEG C, filter, filtrate is extracted with ethyl acetate, and organic layers with sodium sulfate is dry, concentrated, and product is with purification by silica gel column chromatography (petrol ether/ethyl acetate=1/1), and obtain formula (3) compound, be white solid, reaction formula is as follows:
Step c: add MeI again add compound (3) and salt of wormwood in DMF after, fully stir 8 hours under normal temperature, then filter, filtrate carries out concentratedly obtaining crude product, again crude product HPLC purifying being obtained target product (4), is white solid.
3rd object of the present invention there are provided a kind of inhibiter containing formula (4) compound, and this inhibiter is mainly used in oil, gas well liquid loading, the anti-corrosion of metal in pipeline transportation process.New rosin base imidazoline inhibitor of the present invention is nontoxic, and inhibition efficiency is high, can reach more than 90%.The concrete formula of inhibiter of the present invention is:
The preparation method of above-mentioned formula inhibiter is: first by formula (4) compound dissolution in dimethyl formamide (DMF), obtain solution, then by gained solubilize in water, then add hydroxy ethylene diphosphonic acid, stir and get final product.
This inhibiter may be used for oil-gas field surface gathering and transferring and accumulating piping system, prevents etchant gas to the destruction of the metallic substance such as iron and steel, reduces corrosive wear.
Compared with prior art, advantage of the present invention and beneficial effect are:
1, Rosin-based Imidazoline compounds not only has good anti-H as inhibiter
2s/CO
2the corrosion inhibition of corrosion, have simultaneously Heat stability is good, toxicity low, without advantages such as specific stimulation smells.The tricyclic diterpene molecular structure that rosinyl is unique, new rosin base imidazoline inhibitor is nontoxic, and corrosion inhibition rate is high, can reach 90%.Rosin-based Imidazoline has better inhibition efficiency, is mainly used in oil, gas well liquid loading, the anti-corrosion of metal in pipeline transportation process.
2, the synthesis material of Rosin-based Imidazoline compounds of the present invention is single, and synthetic route is simple to operate.
3, prepare the method for inhibiter simply according to formula of the present invention, only by formula (4) compound dissolution in dimethyl formamide (DMF), need dissolve completely and be dissolved in the water again, finally add hydroxy ethylene diphosphonic acid and stir and get final product.This inhibiter safety and environmental protection simultaneously, has excellent corrosion mitigating effect.May be used for oil-gas field surface gathering and transferring and accumulating pipeline, prevent etchant gas to the destruction of the metallic substance such as iron and steel, reduce corrosive wear.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in further detail.
Except as otherwise noted, the per-cent occurred herein is all mass percentage.
Embodiment 1:
A kind of synthetic method of formula (4) compound, its step is as follows:
Step a: the synthesis of formula (2) compound:
By 100g sylvic acid (0.331mol) and 69gK
2cO
3(0.497mol) be dissolved in 800ml solvent dimethylformamide, add 56.4 grams of (0.397mol) MeI, stir 3 little time point plates and confirm to react completely.Vacuum rotary steam removes MeI, and with EA extraction, concentrated, DMF solvent is removed in washing, organic layer saturated sodium-chloride washing, dry, concentrated, obtains 100g formula (2) compound after the EA/PE of remaining ingredient 1:10 crosses silicon gel column purifying.
1HNMR(CDCl
3,400MHz):0.75(m,7H)；0.94(m,6H)；1.18(m,7H)；1.50(m,4H),1.73(m,6H)；2.01(m,4H)；2.14(m,1H)；3.55(s,3H)；5.29(d,1H)；5.70(s,1H).
Step b: the synthesis of formula (3) compound:
Under 0-10 DEG C of condition, in 1L toluene, add 57.0g (0.949mol) quadrol and 0.949molAlMe
3, mix, then add 100g (0.123mol) formula (2) compound that step a obtains, abundant stirring and refluxing 12 hours.Be cooled to 0 DEG C, filter, filtrate is extracted with ethyl acetate, and organic layers with sodium sulfate is dry, concentrated, and product purification by silica gel column chromatography (petrol ether/ethyl acetate=1/1) obtains white solid 17g, is formula (3) compound:
1HNMR:(CDCl
3,400MHz):0.88(m,9H)；1.00(m,6H)；1.28(m,10H)；1.66(m,4H),1.80(m,5H)；2.08(m,4H)；2.20(m,1H)；5.38(d,1H)；5.77(s,1H).
Step c: the synthesis of formula (4) compound:
122.7mmol (17.42g) MeI is added again add 61.36mmol (20g) compound (3) and salt of wormwood 61.36mmol (8.46g) in the DMF of 200mL after, fully stir 8 hours under normal temperature, then filter, filtrate carries out concentrated obtaining crude product, again crude product HPLC purifying is obtained target product (4), 6.5g white solid.
1HNMR:(DMSO,400MHz):0.85(m,3H)；1.04(m,6H)；1.23(m,2H)；1.30(m,3H),1.58(m,3H)；1.92(m,6H)；1.95(m,3H)；2.10(m,1H)；2.98(s,3H)；3.26(m,2H)；3.44(m,2H)；5.39(s,1H)；5.77(s,1H).
Embodiment 2:
First, formula (4) compound obtained for embodiment 1 is prepared into inhibiter, and described inhibiter is made up of formula (4) compound, dimethyl formamide, hydroxy ethylene diphosphonic acid and water, and concrete content range is as follows:
More specifically, each corrosion inhibitor formula is as shown in table 1 below:
Table 1 corrosion inhibitor formula is tested
| Numbering | Formula (4) compound (mg/L) | DMF(g/L) | Hydroxy ethylene diphosphonic acid (g/L) | Water |
| Formula 1 | 15 | 5.0 | 0.5 | Surplus |
| Formula 2 | 30 | 7.5 | 0.75 | Surplus |
| Formula 3 | 45 | 10.0 | 1.0 | Surplus |
| Formula 4 | 60 | 5.0 | 0.5 | Surplus |
| Formula 5 | 75 | 7.5 | 0.75 | Surplus |
| Formula 6 | 90 | 10.0 | 1.0 | Surplus |
The preparation method of the inhibiter of each formula is all as follows above: first by formula (4) compound dissolution in dimethyl formamide (DMF), again by gained solubilize in water, then stir after adding hydroxy ethylene diphosphonic acid and obtain inhibiter.
Under acid condition, inhibition efficiency is measured:
According to SY/T5405-1996 " acidifying inhibiter method for testing performance and evaluation index ", illustrate formula (4) compound prepared by the present invention corrosion mitigating effect as inhibiter, in table 2 by test simulation.
Table 2
In table 2, the density of corrosion inhibitor metering of each formula to be filled a prescription the inhibiter prepared in table 1.
The tricyclic diterpene molecular structure that rosinyl is unique, new rosin base imidazoline inhibitor is nontoxic, and corrosion inhibition rate is high, can reach more than 98%.Rosin-based Imidazoline has better inhibition efficiency, is mainly used in oil, gas well liquid loading, the anti-corrosion of metal in pipeline transportation process.
Specific embodiment described in this specification sheets is only to the explanation for example of the present invention's spirit.Those skilled in the art can make various amendment or supplement or adopt similar mode to substitute to described specific embodiment, but can't depart from spirit of the present invention or surmount the scope that appended claims defines.
Claims (5)
1. the Rosin-based Imidazoline compounds shown in a formula (4):
2. a synthetic method for Rosin-based Imidazoline compounds according to claim 1, its step is as follows:
Step a: by sylvic acid and K
2cO
3be dissolved in dimethyl formamide, add methyl iodide, after reacting completely, vacuum rotary steam removes methyl iodide, be extracted with ethyl acetate, concentrated, washing removing dimethyl formamide, organic layer saturated sodium-chloride washing, dry, concentrated, obtain formula (2) compound after the ethyl acetate/petroleum ether of remaining ingredient 1:10 crosses silicon gel column purifying, reaction formula is as follows:
Step b: under 0-10 DEG C of condition, in toluene, add quadrol and trimethyl aluminium, mix, then add formula (2) compound that step a obtains, abundant stirring and refluxing reaction, be cooled to 0 DEG C, filter, filtrate is extracted with ethyl acetate, organic layers with sodium sulfate is dry, concentrated, product purification by silica gel column chromatography, obtain formula (3) compound, reaction formula is as follows:
Step c: add methyl iodide again add compound (3) and salt of wormwood in dimethyl formamide after, fully stir 8 hours under normal temperature, then filter, filtrate carries out concentratedly obtaining crude product, again crude product HPLC purifying is obtained target product (4), reaction formula is as follows:
3. the inhibiter containing Rosin-based Imidazoline compounds according to claim 1.
4. the inhibiter of the Rosin-based Imidazoline compounds containing synthetic method synthesis according to claim 2.
5. the inhibiter according to claim 3 or 4, is characterized in that, the formula of described inhibiter is as follows:
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108727268A (en) * | 2017-04-20 | 2018-11-02 | 中国石油天然气股份有限公司 | A kind of rosin imidazoline quaternary ammonium salt compound, corrosion inhibiter and preparation method |
| CN112048722A (en) * | 2020-09-01 | 2020-12-08 | 武汉思越化学技术有限公司 | Preparation method and preparation system of special corrosion inhibitor for metal equipment |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101687812A (en) * | 2007-07-02 | 2010-03-31 | 弗·哈夫曼-拉罗切有限公司 | The 2-imidazolinium compounds that trace amine associated receptors (TAAR) is had good affinity |
-
2015
- 2015-02-08 CN CN201510064954.3A patent/CN105272916B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101687812A (en) * | 2007-07-02 | 2010-03-31 | 弗·哈夫曼-拉罗切有限公司 | The 2-imidazolinium compounds that trace amine associated receptors (TAAR) is had good affinity |
Non-Patent Citations (5)
| Title |
|---|
| A. EDWARDS, ET AL: "Mechanistic Studies of the Corrosion Inhibitor Oleic Imidazoline", 《CORROSION SCIENCE》 * |
| GIANFABIO GIORGIONI, ET AL: "Novel imidazoline compounds as partial or full agonists of D2-like dopamine receptors inspired by I2-imidazoline binding sites ligand 2-BFI", 《BIOORGANIC & MEDICINAL CHEMISTRY》 * |
| P. C. OKAFOR，等: "Corrosion and Corrosion Inhibition Behavior of N80 and P110 Carbon Steels in CO2-Saturated Simulated Formation Water by Rosin Amide Imidazoline", 《IND. ENG. CHEM. RES.》 * |
| XIAOQING LIU, ET AL: "Rosin-based acid anhydrides as alternatives to petrochemical curing agents", 《GREEN CHEM.》 * |
| 周永红，等: "水溶性松香基咪唑啉的合成及缓蚀性能", 《林产化学与工业》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108727268A (en) * | 2017-04-20 | 2018-11-02 | 中国石油天然气股份有限公司 | A kind of rosin imidazoline quaternary ammonium salt compound, corrosion inhibiter and preparation method |
| CN108727268B (en) * | 2017-04-20 | 2020-08-07 | 中国石油天然气股份有限公司 | Rosin imidazoline quaternary ammonium salt compound, corrosion inhibitor and preparation method |
| CN112048722A (en) * | 2020-09-01 | 2020-12-08 | 武汉思越化学技术有限公司 | Preparation method and preparation system of special corrosion inhibitor for metal equipment |
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