CN106083727A - A kind of mixing-in fat base double (benzimidazole hyamine) and preparation method and application - Google Patents
A kind of mixing-in fat base double (benzimidazole hyamine) and preparation method and application Download PDFInfo
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- CN106083727A CN106083727A CN201610398838.XA CN201610398838A CN106083727A CN 106083727 A CN106083727 A CN 106083727A CN 201610398838 A CN201610398838 A CN 201610398838A CN 106083727 A CN106083727 A CN 106083727A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
- C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
- C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
- C07D235/06—Benzimidazoles; Hydrogenated benzimidazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached in position 2
- C07D235/08—Radicals containing only hydrogen and carbon atoms
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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
- C23G1/24—Cleaning or pickling metallic material with solutions or molten salts with neutral solutions
- C23G1/26—Cleaning or pickling metallic material with solutions or molten salts with neutral solutions using inhibitors
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Abstract
The invention belongs to fine organic chemical industry field, particularly relate to a kind of mixing-in fat base double (benzimidazole hyamine) and preparation method and application.The invention provides the structure of a kind of mixing-in fat base double (benzimidazole hyamine), present invention also offers the preparation method and application of above-mentioned mixing-in fat base double (benzimidazole hyamine).After introducing mixing-in fat base and quaternary ammonium group in benzimidazoline molecule, both add the hydrophobicity of protecting film, reduced rate of metal corrosion, add again the water solublity of corrosion inhibiter.Can obtain through measuring, corrosion inhibiter involved in the technical scheme that the present invention provides, corrosion mitigating effect is substantially better than existing corrosion inhibiter.Solving in prior art, corrosion inhibiter also exists corrosion mitigating effect difference and the technological deficiency of poorly water-soluble.And, raw material used in the present invention is waste oil, while reducing production cost, and the advantage also with protection environment.
Description
Technical field
The invention belongs to fine organic chemical industry field, particularly relate to a kind of mixing-in fat base double (benzimidazole hyamine)
And preparation method and application.
Background technology
In oil gas well mining and industry heat power equipment acid cleaning process, in order to prevent acid solution to oil pipe, sleeve pipe and boiler
Deng the corrosion of equipment, adding corrosion inhibiter in acid solution is requisite anti-corrosion measure, and in recent years, imidazoline corrosion inhibitor is at oil
Field pipeline anticorrosion and pickling industry are applied the most extensive.
At present, the synthesis of benzimidazoline mainly with organic carboxyl acid and o-phenylenediamine or substituted o-phenylenediamine as raw material,
Use ladder-elevating temperature technology, be prepared by amidatioon and cyclodehydration.The concrete preparation method of prior art is: with C7～
The fatty acid of C20, o-phenylenediamine or substituted o-phenylenediamine are raw material, add azeotropic agent and catalyst carry out being acylated, cyclization
Synthesize a kind of fat-based benzimidazoline or fat-based substituted benzimidazole quinoline, but, the inhibition that this type of preparation method obtains
Agent, still also exists the technological deficiency of corrosion mitigating effect difference.
Therefore, develop and a kind of mixing-in fat base double (benzimidazole hyamine) and preparation method and application, use
In solving in prior art, corrosion inhibiter also exists corrosion mitigating effect difference technological deficiency, becomes those skilled in the art urgently to be resolved hurrily
Problem.
Summary of the invention
In view of this, the invention provides a kind of mixing-in fat base double (benzimidazole hyamine) and preparation method thereof with
Application, is used for solving in prior art, and corrosion inhibiter also exists corrosion mitigating effect difference technological deficiency.
The invention provides a kind of mixing-in fat base double (benzimidazole hyamine), described double (benzimidazoline quaternary ammoniums
Salt) chemical structural formula be:
Wherein, RnFor mixing-in fat base, R is CH3Or C6H5, Z be-CH=CH-or
Present invention also offers the preparation method of a kind of mixing-in fat base double (benzimidazole hyamine), its feature exists
In, described preparation method is: step one, by waste oil hydrolyze, obtain fatty acid mixed, gained fatty acid mixed is the first product；
Step 2, the first product react with N-substituted o-phenylenediamine generation amidatioon-cyclodehydration, generate the second product；Step 3, institute
After stating the second product cooling, add two bromo-hydrocarbons, quaterisation occurs, obtains product.
Preferably, described first product is 1:(0.61～0.70 with the mass ratio of N-substituted o-phenylenediamine).
Preferably, described amidatioon-cyclodehydration reaction is carried out under nitrogen protection.
Preferably, described amidatioon-cyclodehydration reaction is carried out in three stages: stage one, described first product take with N-
For o-phenylenediamine generation amidation process, with dimethylbenzene as solvent, course of reaction steams water that amidation process produces immediately；
After stage two, described stage one terminate, heat up and steam described solvent；After stage three, described stage two terminate, occur cyclisation anti-
Should, decompression distillation, to not having liquid to produce, obtains the second product.
Preferably, the time of described amidation process is 4～6h, and the temperature of described amidation process is 130～140 DEG C.
Preferably, the reaction temperature 170 in described stage two～180 DEG C, the response time in described stage two is 4～5h.
Preferably, the time of described cyclization is 3h, and the temperature of described cyclization is 210～220 DEG C；Stage three institute
The condition of the decompression distillation stated is 20～25mmHg.
The temperature of the most described cooling is 60 DEG C.Described first product is 1 with the mass ratio of described two bromo-hydrocarbons:
(0.39～0.46), the response time of described quaterisation is 1～1.5h, described quaternary ammonium words reaction reaction temperature be 60～
70℃。
Present invention also offers a kind of above-mentioned mixing-in fat base double (benzimidazole hyamine) or above-mentioned preparation method obtains
To product application in corrosion inhibiter.
In sum, the invention provides the structure of a kind of mixing-in fat base double (benzimidazole hyamine), the present invention
Additionally provide the preparation method and application of above-mentioned mixing-in fat base double (benzimidazole hyamine).Imidazoline molecule introduces
After mixing-in fat base and quaternary ammonium group, both added the hydrophobicity of protecting film, reduced rate of metal corrosion, added again slow
The water solublity of erosion agent.Can obtain through measuring, corrosion inhibiter involved in the technical scheme that the present invention provides, corrosion mitigating effect is obvious
It is better than existing corrosion inhibiter.Solving in prior art, corrosion inhibiter also exists corrosion mitigating effect difference and the technological deficiency of poorly water-soluble.
And, raw material used in the present invention is waste oil, while reducing production cost, and the advantage also with protection environment.
Detailed description of the invention
The invention provides a kind of mixing-in fat base double (benzimidazole hyamine) and preparation method and application, be used for
Solving in prior art, corrosion inhibiter also exists corrosion mitigating effect difference technological deficiency.
Technical scheme in the embodiment of the present invention will be clearly and completely described below, it is clear that described enforcement
Example is only a part of embodiment of the present invention rather than whole embodiments.Based on the embodiment in the present invention, this area is common
The every other embodiment that technical staff is obtained under not making creative work premise, broadly falls into the model of present invention protection
Enclose.
In order to the present invention is described in more detail, below in conjunction with embodiment, the present invention is provided, be specifically described.
Embodiment 1
The present embodiment is preparation 1,4-bis-(2-mixing-in fat base-1-benzimidazoline phenyl quaternary ammonium group)-2-butylene inhibition
The specific embodiment of agent.
The chemical equation of the reaction principle of the present embodiment is:
Waste oil is hydrolyzed to obtain fatty acid mixed, standby.
In the there-necked flask being furnished with water knockout drum, thermometer, condensing tube and agitating device, addition 27.2g fatty acid mixed,
16.6gN-phenyl o-phenylenediamine and 60ml dimethylbenzene, be passed through nitrogen protection, and in reaction, continuous water knockout drum is isolated from system
Water byproduct, is slowly heated to 140 DEG C, reacts 3.5～4.0h.When collecting the water yield close to theoretical aquifer yield, then it is warming up to 170
～180 DEG C steam solvent, it is heated to reflux 4～5 hours.Continue after 210～220 DEG C of cyclization 3h, subtract 20～25mmHg
Pressure distillation, until not having liquid to flow out.
Reaction system being cooled to 60 DEG C, adds the bromo-2-butylene of 9.7g1,4-bis-in mixture, mixture is warming up to 60
～70 DEG C, after stirring reaction 1.5h, decompression distillation, obtain water solublity Isosorbide-5-Nitrae-two (2-mixing-in fat base-1-benzimidazoline quaternary ammonium
Base)-2-butylene corrosion inhibiter, it is product 1.Receive to obtain product 1 36.6g altogether.
Embodiment 2
The present embodiment is preparation 1,4-bis-(2-mixing-in fat base-1-benzimidazoline methylmethylene quaternary ammonium group) benzene inhibition
The specific embodiment of agent.
The chemical equation of the reaction principle of the present embodiment is:
Waste oil is hydrolyzed to obtain fatty acid mixed, standby.
In the there-necked flask being furnished with water knockout drum, thermometer, condensing tube and agitating device, addition 27.2g fatty acid mixed,
17.5gN-methyl-o-phenylenediamine and 80ml dimethylbenzene, be passed through nitrogen protection, and in reaction, continuous water knockout drum is isolated from system
Water byproduct, is slowly heated to 140 DEG C, reacts 3.5～4.0h.When collecting the water yield close to theoretical aquifer yield, then it is warming up to 170
～180 DEG C steam solvent, it is heated to reflux 4～5 hours.Continue after 210～220 DEG C of cyclization 3h, subtract 20～25mmHg
Pressure distillation, until not having liquid to flow out.
Reaction system being cooled to 60 DEG C, adds 11.9g1,4-bis-(bromomethyl) benzene in mixture, mixture is warming up to
60～70 DEG C, after stirring reaction 1h, decompression distillation, obtain water solublity Isosorbide-5-Nitrae-two (2-mixing-in fat base-1-benzimidazoline methyl
Quaternary ammonium group methylene) benzene corrosion inhibiter, it is product 2.Receive to obtain product 2 36.6g altogether.
Embodiment 3
The present embodiment delays for preparation 1,4-bis-(2-mixing-in fat base-1-benzimidazoline ylmethyl quaternary ammonium group)-2-butylene
The specific embodiment of erosion agent.
The chemical equation of the reaction principle of the present embodiment is:
Waste oil is hydrolyzed to obtain fatty acid mixed, standby.
In the there-necked flask being furnished with water knockout drum, thermometer, condensing tube and agitating device, addition 27.2g fatty acid mixed,
18.5gN-methyl-o-phenylenediamine and 40ml dimethylbenzene, be passed through nitrogen protection, and in reaction, continuous water knockout drum is isolated from system
Water byproduct, is slowly heated to 140 DEG C, reacts 3.5～4.0h.When collecting the water yield close to theoretical aquifer yield, then it is warming up to 170
～180 DEG C steam solvent, it is heated to reflux 4～5 hours.Continue after 210～220 DEG C of cyclization 3h, subtract 20～25mmHg
Pressure distillation, until not having liquid to flow out.
Reaction system being cooled to 60 DEG C, adds the bromo-2-butylene of 9.7g1,4-bis-in mixture, mixture is warming up to 60
～70 DEG C, after stirring reaction 1h, decompression distillation, obtain water solublity Isosorbide-5-Nitrae-two (2 '-mixing-in fat base-1 '-benzimidazoline methyl
Quaternary ammonium group)-2-butylene corrosion inhibiter, it is product 3.Receive to obtain product 3 36.3g altogether.
Embodiment 4
The present embodiment is preparation 1,4-bis-(2-mixing-in fat base-1-benzimidazoline phenylmethylene quaternary ammonium group) benzene inhibition
The specific embodiment of agent.
The chemical equation of the reaction principle of the present embodiment is:
By implement 2 examples test method, with N-phenyl o-phenylenediamine substitute N-methyl-o-phenylenediamine, obtain water solublity Isosorbide-5-Nitrae-
Two (2-mixing-in fat base-1-benzimidazoline phenyl quaternary ammonium group methylene) benzene corrosion inhibiter, is product 4.Receive product 4 amounts to
32.2g。
Embodiment 5
The present embodiment is the specific experiment of the corrosion mitigating effect measuring product 1～4.
The present embodiment illustrates the corrosion mitigating effect of product 1～6 by measuring simulation oil field pipeline corrosion protection inhibition experiment.Due to
Oil field pipe is mainly Q235 steel, therefore the present embodiment uses Q235 metal material to come simulation experiment, the performance of inspection corrosion inhibiter.
In the present embodiment, the reference substance used is water solublity oleic imidazolinone.
In the 5%HCl solution of 1000ml, add product 1, Q235 steel disc hung in the solution, water bath with thermostatic control 60 DEG C,
After placing 6h, weight-loss method is used to measure the etching extent of steel disc.In the present embodiment, the mass percentage concentration of product 1 is 0.25%.
The corrosion mitigating effect determination experiment of product 2～product 4 and reference substance ibid, does not repeats them here.After measuring
The corrosion inhibition rate result calculating gained refers to table 1.
Table 1: corrosion inhibition rate experimental result
| Product | Product 1 | Product 2 | Product 3 | Product 4 | Reference substance |
| Corrosion inhibition rate | 98.2 | 96.5 | 95.9 | 98.4 | 92.5 |
Can obtain from table 1, the corrosion inhibition rate of product 1～4 to illustrate apparently higher than comparison, the technical scheme that the present invention provides
Corresponding product, has the advantage that corrosion mitigating effect is good.
In sum, the invention provides the structure of a kind of mixing-in fat base double (benzimidazole hyamine), the present invention
Additionally provide the preparation method and application of above-mentioned mixing-in fat base double (benzimidazole hyamine).Imidazoline molecule introduces
After mixing-in fat base and quaternary ammonium group, both added the hydrophobicity of protecting film, reduced rate of metal corrosion, added again slow
The water solublity of erosion agent.Can obtain through measuring, corrosion inhibiter involved in the technical scheme that the present invention provides, corrosion mitigating effect is obvious
It is better than existing corrosion inhibiter.Solving in prior art, corrosion inhibiter also exists corrosion mitigating effect difference and the technological deficiency of poorly water-soluble.
And, raw material used in the present invention is waste oil, while reducing production cost, and the advantage also with protection environment.
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For Yuan, under the premise without departing from the principles of the invention, it is also possible to make some improvements and modifications, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (10)
1. a mixing-in fat base is double (benzimidazole hyamine), it is characterised in that the change of described double (imidazoline quaternary ammonium salt)
Structural formula is:
Wherein, RnFor mixing-in fat base, R is CH3Or C6H5, Z be-CH=CH-or
2. the preparation method of a mixing-in fat base double (benzimidazole hyamine), it is characterised in that described preparation method is:
Step one, by waste oil hydrolyze, obtain fatty acid mixed, gained fatty acid mixed is the first product；
Step 2, the first product react with N-substituted o-phenylenediamine generation amidatioon-cyclodehydration, generate the second product；
After step 3, described second product cooling, add two bromo-hydrocarbons, quaterisation occurs, obtains product.
Preparation method the most according to claim 2, it is characterised in that described first product and the matter of N-substituted o-phenylenediamine
Amount ratio is 1:(0.61～0.70).
Preparation method the most according to claim 2, it is characterised in that described amidatioon-cyclodehydration reaction is protected at nitrogen
Protect down carry out.
Preparation method the most according to claim 2, it is characterised in that described amidatioon-cyclodehydration is reacted in three stages
Carry out:
Stage one, described first product and N-substituted o-phenylenediamine generation amidation process, with dimethylbenzene as solvent, course of reaction
In immediately steam amidation process produce water；
After stage two, described stage one terminate, heat up and steam described solvent；
After stage three, described stage two terminate, cyclization, decompression distillation is occurred to not having liquid to produce, to obtain the second product.
Preparation method the most according to claim 5, it is characterised in that the time of described amidation process is 4～6h, described
The temperature of amidation process is 130～140 DEG C.
Preparation method the most according to claim 5, it is characterised in that the reaction temperature 170 in described stage two～180 DEG C,
The response time in described stage two is 4～5h.
Preparation method the most according to claim 5, it is characterised in that the time of described cyclization is 3h, described cyclisation
The temperature of reaction is 210～220 DEG C；The condition of the decompression distillation described in the stage three is 20～25mmHg.
Preparation method the most according to claim 2, it is characterised in that the temperature of described cooling is 60 DEG C.Described first produces
Thing is 1:(0.39～0.46 with the mass ratio of described two bromo-hydrocarbons), the response time of described quaterisation is 1～1.5h, institute
The reaction temperature stating quaterisation is 60～70 DEG C.
10. the mixing-in fat base that a kind includes described in claim 1 double (benzimidazole hyamine) or claim 2 to 9 times
The product that a described preparation method of anticipating obtains application in corrosion inhibiter.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112876483A (en) * | 2021-01-18 | 2021-06-01 | 邓颖菁 | Dicationic benzimidazole corrosion inhibitor and preparation method thereof |
| CN114106788A (en) * | 2021-12-15 | 2022-03-01 | 湖南省希润弗高分子新材料有限公司 | Industrial circulating cooling liquid |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US7057050B2 (en) * | 2003-04-11 | 2006-06-06 | Nalco Energy Services L.P. | Imidazoline corrosion inhibitors |
| CN101565608A (en) * | 2009-05-25 | 2009-10-28 | 新疆大学 | Preparation method of novel acidified corrosion inhibitor and use thereof |
| CN101613622B (en) * | 2009-07-29 | 2012-08-22 | 中国石油化工集团公司 | Composite inhibiter and preparation method and application thereof |
| CN103289671B (en) * | 2013-05-28 | 2016-10-05 | 四川安东油气工程技术服务有限公司 | Corrosion inhibiter and preparation method thereof |
| CN105088252B (en) * | 2015-08-19 | 2018-03-09 | 广东工业大学 | A kind of benzimidazoline corrosion inhibiter being prepared with refined gutter oil |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112876483A (en) * | 2021-01-18 | 2021-06-01 | 邓颖菁 | Dicationic benzimidazole corrosion inhibitor and preparation method thereof |
| CN114106788A (en) * | 2021-12-15 | 2022-03-01 | 湖南省希润弗高分子新材料有限公司 | Industrial circulating cooling liquid |
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