CN114014798A - Bipyridyl quaternary ammonium salt, and preparation method, detection method and application thereof - Google Patents
Bipyridyl quaternary ammonium salt, and preparation method, detection method and application thereof Download PDFInfo
- Publication number
- CN114014798A CN114014798A CN202111403033.7A CN202111403033A CN114014798A CN 114014798 A CN114014798 A CN 114014798A CN 202111403033 A CN202111403033 A CN 202111403033A CN 114014798 A CN114014798 A CN 114014798A
- Authority
- CN
- China
- Prior art keywords
- quaternary ammonium
- ammonium salt
- bipyridyl
- solvent
- bipyridyl quaternary
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- -1 Bipyridyl quaternary ammonium salt Chemical class 0.000 title claims abstract description 73
- 238000001514 detection method Methods 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000002904 solvent Substances 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 238000000870 ultraviolet spectroscopy Methods 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 230000035484 reaction time Effects 0.000 claims abstract description 7
- 238000001953 recrystallisation Methods 0.000 claims abstract description 6
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 5
- 125000005843 halogen group Chemical group 0.000 claims abstract description 5
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000012467 final product Substances 0.000 claims abstract description 3
- 125000004076 pyridyl group Chemical group 0.000 claims abstract description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 37
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 16
- 238000010521 absorption reaction Methods 0.000 claims description 16
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- 238000002835 absorbance Methods 0.000 claims description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- QWBPOZGPINSTMJ-UHFFFAOYSA-N BrCCC.N1(CC=CC=C1)C=1C=NC=CC1 Chemical group BrCCC.N1(CC=CC=C1)C=1C=NC=CC1 QWBPOZGPINSTMJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000011161 development Methods 0.000 claims description 2
- 238000005292 vacuum distillation Methods 0.000 claims 1
- 238000010992 reflux Methods 0.000 abstract description 9
- 238000006073 displacement reaction Methods 0.000 abstract description 6
- 239000000047 product Substances 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000012752 auxiliary agent Substances 0.000 abstract description 2
- 230000035945 sensitivity Effects 0.000 abstract description 2
- 239000003921 oil Substances 0.000 description 10
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 10
- 239000007787 solid Substances 0.000 description 9
- VEFLKXRACNJHOV-UHFFFAOYSA-N 1,3-dibromopropane Chemical compound BrCCCBr VEFLKXRACNJHOV-UHFFFAOYSA-N 0.000 description 7
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000010779 crude oil Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 238000002390 rotary evaporation Methods 0.000 description 4
- 239000012265 solid product Substances 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- DFWSKVHPPNBMGI-UHFFFAOYSA-N 3-pyridin-1-ium-1-ylpyridine Chemical compound C1=CC=CC=[N+]1C1=CC=CN=C1 DFWSKVHPPNBMGI-UHFFFAOYSA-N 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 230000009881 electrostatic interaction Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- IBODDUNKEPPBKW-UHFFFAOYSA-N 1,5-dibromopentane Chemical compound BrCCCCCBr IBODDUNKEPPBKW-UHFFFAOYSA-N 0.000 description 1
- SGRHVVLXEBNBDV-UHFFFAOYSA-N 1,6-dibromohexane Chemical compound BrCCCCCCBr SGRHVVLXEBNBDV-UHFFFAOYSA-N 0.000 description 1
- JGVIYCAYGMXJBC-UHFFFAOYSA-N 2-octylpyridine Chemical compound CCCCCCCCC1=CC=CC=N1 JGVIYCAYGMXJBC-UHFFFAOYSA-N 0.000 description 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000002579 anti-swelling effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- FJBFPHVGVWTDIP-UHFFFAOYSA-N dibromomethane Chemical compound BrCBr FJBFPHVGVWTDIP-UHFFFAOYSA-N 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000003129 oil well Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/16—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
- C07D213/20—Quaternary compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/84—Compositions based on water or polar solvents
- C09K8/86—Compositions based on water or polar solvents containing organic compounds
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/33—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using ultraviolet light
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Health & Medical Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Pyridine Compounds (AREA)
Abstract
The invention provides a bipyridyl quaternary ammonium salt, a preparation method, a detection method and application thereof. The general formula of the bipyridyl quaternary ammonium salt is Py+‑(CH2)n‑Py+2X‑Wherein Py is pyridyl, X is halogen atom, and n is an integer of 2-12; the preparation method comprises the following steps: dissolving dihaloalkane and pyridine in a solvent, reacting under the reflux condition, removing the solvent after the reaction is finished, filtering and drying after recrystallization to obtain the final product of the bipyridyl quaternary ammonium salt. The preparation method of the bipyridyl quaternary ammonium salt has the advantages of easily available raw materials, simple reaction operation, short reaction time, product yield of over 80 percent and capability of recovering reaction solventThe obtained product has wide application, and can be particularly used as an oil displacement agent, an oil field auxiliary agent and the like. The detection of the bipyridyl quaternary ammonium salt in the invention uses an ultraviolet-visible spectrophotometer method, and has the advantages of simple and rapid operation, high sensitivity and high result accuracy.
Description
Technical Field
The invention relates to the field of preparation and application of quaternary ammonium salt, in particular to a bipyridyl quaternary ammonium salt and a preparation method, a detection method and application thereof.
Background
Quaternary ammonium salts play a very important role in the fields of industry, chemical industry, biomedicine and the like, particularly in the field of petrochemical industry. Simulation experiments and field experiments prove that the unimolecular single-quaternary ammonium salt and the unimolecular multi-quaternary ammonium salt can be used as Molecular Deposition (MD) films for oil displacement of oil fields and crude oil demulsification, and the method has the advantages of simple process, wide application range, no damage to stratums, high oil displacement efficiency and repeated utilization; the monomolecular quaternary ammonium salt can also improve the yield of light oil of the crude oil and the quality of colloid asphaltene by forming a nano molecular deposition film on the surface and inside the colloid and the asphaltene of the crude oil, and has the advantages of simple operation process, less material consumption, short period and high yield; in addition, the monomolecular quaternary ammonium salt can also generate strong electrostatic interaction with negative charges in clay minerals to improve the stratum permeability, and the monomolecular quaternary ammonium salt can be used as a clay stabilizing, anti-swelling and unblocking injection agent, has wide application range and can greatly improve the effects of water well injection and oil well unblocking.
The quaternary pyridinium salt is typically present in the aqueous solution as a single molecule quaternary ammonium salt. Compared with common monomolecular quaternary ammonium salt, the quaternary ammonium salt has a very unique structure, and cation electrons on a pyridine ring of the quaternary ammonium salt are easy to transfer and have good delocalization; secondly, the pyridine ring has alkalinity and aromaticity, and the nitrogen atom on the pyridine ring has electron-withdrawing effect, and the special structures determine that the quaternary ammonium salt of pyridine has very rich chemical properties. Researches show that the quaternary pyridinium salt has the common characteristics of gemini surfactants, such as hydrophilic and lipophilic characteristics, low critical micelle concentration, high surface activity, good compounding performance and the like, and also has the advantages of unique positive charge, bactericidal performance and the like. In addition, the pyridine salt structure contains nitrogen heterocycle, and pi-pi interaction exists between the pyridine salt structure and aromatic rings in pollutant molecule aromatic compounds, so that the adsorption performance of the organic clay is improved; and the Gemini cationic surfactant containing pyridine rings has excellent corrosion inhibition performance.
The molecular structure of the bipyridyl quaternary ammonium salt contains two N+Cationic active center is increased relative to single pyridine quaternary ammonium saltIn addition, the corresponding chemical activity is also enhanced. The bipyridyl quaternary ammonium salt serving as a novel MD membrane oil displacement agent has the advantages of more obvious advantages, low use concentration, less investment, simple construction process and simple operation of water injection equipment, can well improve the wettability of oil deposit minerals, obviously improves the crude oil recovery rate and has little damage to geology. The electrostatic interaction between the negative charges on the surface of the oil reservoir minerals and the cationic bipyridyl salt enables the bipyridyl salt to spontaneously form a single-layer film on the surface/interface of the oil reservoir minerals, so that the oil displacement efficiency and the recovery ratio are improved.
However, the preparation of the bipyridyl quaternary ammonium salt is difficult. In the prior art, the following technical scheme is adopted:
the first technical scheme is as follows: pyridine and dibromomethane are used for synthesizing bipyridyl quaternary ammonium salt according to the feeding ratio of 2:1, acetonitrile is used as a solvent, and the reflux is carried out for 72 hours at the temperature of 70 ℃ to obtain bipyridyl quaternary ammonium salt; the technology has complex reaction conditions and long reaction time, and is not suitable for industrial batch production.
The second technical scheme is as follows: a flask equipped with a stirrer, reflux condenser was charged with the reactant α -octyl pyridine: dibromo halohydrocarbon is 2.4:1 (mol ratio), the mass fraction of the absolute ethyl alcohol solvent in the reaction mixture is 40%, the reflux reaction is carried out for 72 hours, the absolute ethyl alcohol is distilled off by a rotary evaporator and then recrystallized by acetone and the absolute ethyl alcohol for three times, and the obtained white solid is dissolved in P2O5Drying at room temperature under reduced pressure for 24h in the presence of the (C) to obtain the product, wherein the yield is only 25-30%; the technology has long reaction time, low yield and complex drying conditions, and is not suitable for industrial production.
The third technical scheme is as follows: the preparation of bis-tribromo 1, 3-bipyridinium base propane is carried out by synthesizing 1, 3-bipyridinium bromide propane by three methods, and further preparing bis-tribromo 1, 3-bipyridinium base propane. The first method is to mix pyridine and 1, 3-dibromopropane and then carry out reflux reaction until solid is generated, and the solid is washed by ether to obtain 1, 3-dipyridyl bromopropane, wherein the molar ratio of the pyridine to the 1, 3-dibromopropane is (2-2.5): 1; the second method is that 1, 3-dibromopropane, pyridine and methanol are mixed and react at normal temperature to reflux temperature until solid is precipitated, then the mixture is filtered, and the solid is obtained by washing and filtering with ether, and 1, 3-dipyridyl bromopropane is obtained, wherein the molar ratio of the pyridine to the 1, 3-dibromopropane is (2-2.5): 1; the third method is that 1, 3-dibromopropane, pyridine and ethanol are mixed, stirred at normal temperature until solid is precipitated, then filtered and washed by ether to obtain 1, 3-dipyridyl bromopropane, wherein the molar ratio of the pyridine to the 1, 3-dibromopropane is (2-2.5): 1; although the reaction can synthesize the 1, 3-dipyridyl bromopropane, the method is not suitable for other dibromo alkanes, and whether the reaction is complete or not can not be determined after solids are separated out.
Disclosure of Invention
In order to solve the problems, the invention provides a bipyridyl quaternary ammonium salt, and a preparation method, a detection method and application thereof. The preparation method of the invention takes the dihalogenated alkane and the pyridine as raw materials, adopts a one-step method to synthesize the bipyridyl quaternary ammonium salt, and has the advantages of simple and convenient operation, shorter reaction time and high yield.
To achieve the above object, the present invention provides a bipyridyl quaternary ammonium salt having the general formula Py+-(CH2)n-Py+2X-Wherein Py is pyridyl, X is halogen atom, and n is an integer of 2-12.
The invention also provides a preparation method of the bipyridyl quaternary ammonium salt, which comprises the following steps: dissolving dihaloalkane and pyridine in a certain proportion in a solvent, reacting at 60-90 ℃, removing the solvent by rotary evaporation (such as distillation or reduced pressure distillation in industry) after the reaction is finished, recrystallizing, filtering and drying to obtain the bipyridyl quaternary ammonium salt final product;
the dihaloalkane has the general formula X- (CH)2)n-X, wherein X is a halogen atom and n is an integer between 2 and 12.
According to an embodiment of the present invention, in the above preparation method, preferably, when X is Br atom, the synthesis equation of the bipyridyl quaternary ammonium salt is as follows:
wherein n is an integer between 2 and 12.
According to a specific embodiment of the present invention, in the above production method, preferably, the reaction temperature is 60 to 90 ℃, preferably 80 ℃; the reaction time is 6-10 h.
According to a specific embodiment of the present invention, in the above production method, it is preferable that the molar ratio of the dihaloalkane and the pyridine is 1 (2.0 to 2.3), preferably 1: 2.1.
According to a specific embodiment of the present invention, in the above production method, preferably, the solvent accounts for 30 to 60%, preferably 40%, of the total mass of the reaction system.
According to a specific embodiment of the present invention, in the above preparation method, preferably, the solvent is selected from one or a combination of two or more of C2-C4 alcohol, acetonitrile, acetone, ethyl acetate, dichloromethane, chloroform and toluene, preferably, anhydrous ethanol.
According to a specific embodiment of the present invention, in the above preparation method, preferably, the solvent used for recrystallization is one or a combination of two or more selected from the group consisting of diethyl ether, C1-C4 alcohol, acetonitrile, acetone and ethyl acetate, preferably ethanol or diethyl ether.
The invention also provides a detection method of the bipyridyl quaternary ammonium salt, which comprises the following steps:
(1) measuring the maximum ultraviolet absorption wavelength of the sample to be measured by using an ultraviolet-visible spectrophotometer;
(2) preparing bipyridine quaternary ammonium salt standard samples with different concentrations, measuring the absorbance of the standard samples at the ultraviolet maximum absorption wavelength, and drawing a standard curve between the concentration and the absorbance;
(3) and measuring the absorbance of the sample to be measured by using an ultraviolet-visible spectrophotometer, and calculating the concentration of the bipyridyl quaternary ammonium salt according to the standard curve.
According to a specific embodiment of the present invention, in the above detection method, preferably, when the bipyridyl quaternary ammonium salt is 1, 3-bipyridyl bromopropane, the maximum ultraviolet absorption wavelength is 258 ± 1 nm.
According to an embodiment of the present invention, in the above detection method, preferably, when the bipyridyl quaternary ammonium salt is 1, 5-bipyridyl bromopentane, the maximum ultraviolet absorption wavelength is 242 ± 1 nm.
According to an embodiment of the present invention, in the above detection method, preferably, when the bipyridyl quaternary ammonium salt is 1, 6-bipyridyl bromohexane, the maximum ultraviolet absorption wavelength is 259 ± 1 nm.
The invention also provides application of the bipyridyl quaternary ammonium salt in oilfield development, wherein the bipyridyl quaternary ammonium salt is used as an oil displacement agent and an oilfield auxiliary agent.
The bipyridyl quaternary ammonium salt, the preparation method, the detection method and the application thereof have the following beneficial effects:
the preparation method of the bipyridyl quaternary ammonium salt has the advantages of easily available raw materials, simple reaction operation, short reaction time, product yield of over 80 percent, recyclable reaction solvent and wide application of the obtained product; the detection method of the bipyridyl quaternary ammonium salt is simple and rapid to operate, high in sensitivity and high in result accuracy.
Drawings
FIG. 1 is a standard curve for 1, 3-dipyridyl bromopropane of example 1 of the present invention;
FIG. 2 is a standard curve of 1, 5-dipyridyl bromopentane of example 2 of the present invention;
FIG. 3 is a standard curve of 1, 6-dipyridyl bromohexane of example 3 of the present invention.
Detailed Description
The technical solutions of the present invention will be described in detail below in order to clearly understand the technical features, objects, and advantages of the present invention, but the present invention is not limited to the practical scope of the present invention.
Example 1
The embodiment provides a bipyridyl quaternary ammonium salt, and a preparation method thereof comprises the following steps:
adding 0.05mol of 1, 3-dibromopropane and 0.105mol of pyridine into a round-bottom flask, adding 12ml of absolute ethyl alcohol as a solvent, stirring and refluxing for 8h at 80 ℃, then removing the absolute ethyl alcohol by rotary evaporation, filtering after recrystallization, and drying for 24h in a vacuum drying oven to obtain a white solid product.
The white solid obtained was tested to be 1, 3-dipyridyl bromopropane.
The characterization result is as follows: 82.87 percent of Yield;1H-NMR(600MHz,D2O):δ8.92(4H,d,PyH),8.56(2H,t,PyH),8.10(4H,t,PyH),4.82(4H,t,CH2),2.82(2H,m,CH2)；Elemental ananlysis,calcd(％):C,43.32；H,4.44；N,7.78.found(％)C,41.52；H,4.09；N,7.43。
the embodiment also provides a detection method of the bipyridyl quaternary ammonium salt, which comprises the following steps:
(1) detecting the ultraviolet maximum absorption wavelength of the 1, 3-dipyridyl propyl bromide by using an ultraviolet visible spectrophotometer to obtain the maximum ultraviolet absorption wavelength of 258 nm;
(2) preparing low-concentration 1, 3-dipyridyl bromopropane with concentration of 0.02mmol/L, 0.04mmol/L, 0.06mmol/L, 0.08mmol/L, 0.1mmol/L, measuring absorbance at 258nm with ultraviolet-visible spectrophotometer, and drawing to obtain standard curve with correlation coefficient R as shown in FIG. 12>0.999, the linear relation is good;
(3) and measuring the absorbance of the sample to be measured by using an ultraviolet-visible spectrophotometer, and calculating the concentration of the 1, 3-dipyridyl bromopropane according to a standard curve.
Example 2
The embodiment provides a bipyridyl quaternary ammonium salt, and a preparation method thereof comprises the following steps:
adding 0.05mol of 1, 5-dibromopentane and 0.105mol of pyridine into a round-bottom flask, adding 13ml of absolute ethyl alcohol as a solvent, stirring and refluxing for 8h at 80 ℃, then removing the absolute ethyl alcohol by rotary evaporation, filtering after recrystallization, and drying for 24h in a vacuum drying oven to obtain a white solid product.
The white solid obtained was tested to be 1, 5-dipyridyl bromopentane.
The characterization result is as follows: 90.64 percent of Yield;1H-NMR(600MHz,D2O):δ8.77(4H,d,PyH),8.47(2H,t,PyH),7.99(4H,t,PyH),4.55(4H,t,CH2),2.02(4H,m,CH2),1.37(2H,m,CH2)；Elemental ananlysis,calcd(％):C,46.37；H,5.15；N,7.34.found(％)C,44.74；H,4.898；N,6.93。
the embodiment also provides a detection method of the bipyridyl quaternary ammonium salt, which comprises the following steps:
(1) detecting the maximum ultraviolet absorption wavelength of the 1, 5-dipyridyl bromopentane by using an ultraviolet visible spectrophotometer to obtain the maximum ultraviolet absorption wavelength of 242 nm;
(2) preparing low-concentration 1, 5-dipyridyl bromopentane of 0.1mmol/L, 0.2mmol/L, 0.3mmol/L, 0.4mmol/L and 0.5mmol/L, measuring the absorbance at 242nm with an ultraviolet-visible spectrophotometer, respectively, and drawing a standard curve with a correlation coefficient R as shown in FIG. 22>0.999, the linear relation is good;
(3) and measuring the absorbance of the sample to be measured by using an ultraviolet-visible spectrophotometer, and calculating the concentration of the 1, 5-dipyridyl bromopentane according to a standard curve.
Example 3
The embodiment provides a bipyridyl quaternary ammonium salt, and a preparation method thereof comprises the following steps:
adding 0.05mol of 1, 6-dibromohexane and 0.105mol of pyridine into a round-bottom flask, adding 15ml of absolute ethyl alcohol as a solvent, stirring and refluxing for 8h at 80 ℃, then removing the absolute ethyl alcohol by rotary evaporation, filtering after recrystallization, and drying for 24h in a vacuum drying oven to obtain a white solid product.
The white solid product obtained by the test is 1, 6-dipyridyl bromohexane.
The characterization result is as follows: 81.26 percent of Yield;1H-NMR(600MHz,D2O):δ8.71(4H,d,PyH),8.42(2H,t,PyH),7.93(4H,t,PyH),4.46(4H,t,CH2),1.27(4H,m,CH2)1.89(2H,t,CH2)；Elemental ananlysis,calcd(％):C,47.74；H,5.47；N,6.96.found(％)C,47.23；H,5.126；N,6.82。
the embodiment also provides a detection method of the bipyridyl quaternary ammonium salt, which comprises the following steps:
(1) detecting the ultraviolet maximum absorption wavelength of the 1, 6-dipyridyl bromohexane by using an ultraviolet visible spectrophotometer to obtain the maximum ultraviolet absorption wavelength of 259 nm;
(2) preparing 0.02mmol/L, 0.04mmol/L, 0.06mmol/L, 0.08mmol/L, 0.1mmol/L low concentration 1, 6-dipyridyl bromohexane, measuring absorbance at 259nm with UV-visible spectrophotometer, and plotting into standard curve with correlation coefficient R as shown in FIG. 32>0.999, the linear relation is good;
(3) and measuring the absorbance of the sample to be measured by using an ultraviolet-visible spectrophotometer, and calculating the concentration of the 1, 6-dipyridyl bromohexane according to a standard curve.
It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations or modifications may be made on the basis of the above description, and all embodiments may not be exhaustive, and all obvious variations or modifications may be included within the scope of the present invention.
Claims (10)
1. A bipyridyl quaternary ammonium salt is characterized in that the general formula is Py+-(CH2)n-Py+2X-Wherein Py is pyridyl, X is halogen atom, and n is an integer of 2-12.
2. A method for preparing the bipyridyl quaternary ammonium salt according to claim 1, comprising: dissolving dihaloalkane and pyridine in a solvent according to a certain proportion, reacting at 60-90 ℃, removing the solvent after the reaction is finished, recrystallizing, filtering and drying to obtain the final product of the bipyridyl quaternary ammonium salt;
the dihaloalkane has the general formula X- (CH)2)n-X, wherein X is a halogen atom and n is an integer between 2 and 12;
preferably, the solvent removal method is distillation, and more preferably rotary distillation or vacuum distillation.
3. The method of claim 2, wherein the reaction temperature is 60-90 ℃, preferably 80 ℃; the reaction time is 6-10 h.
4. The production method according to claim 2, wherein the molar ratio of the dihaloalkane to the pyridine is 1 (2.0 to 2.3), preferably 1: 2.1.
5. The process according to claim 2, wherein the solvent is 30 to 60%, preferably 40% by mass based on the total mass of the reaction system.
6. The method according to claim 5, wherein the solvent is selected from the group consisting of C2-C4 alcohol, acetonitrile, acetone, ethyl acetate, dichloromethane, chloroform and toluene, and preferably is anhydrous ethanol.
7. The method of claim 2, wherein the solvent used for recrystallization is selected from one or a combination of two or more of ethyl ether, C1-C4 alcohol, acetonitrile, acetone and ethyl acetate, preferably ethanol or ethyl ether.
8. The method for detecting the bipyridyl quaternary ammonium salt according to claim 1, comprising the steps of:
(1) measuring the maximum ultraviolet absorption wavelength of the sample to be measured by using an ultraviolet-visible spectrophotometer;
(2) preparing bipyridine quaternary ammonium salt standard samples with different concentrations, measuring the absorbance of the standard samples at the ultraviolet maximum absorption wavelength, and drawing a standard curve between the concentration and the absorbance;
(3) and measuring the absorbance of the sample to be measured by using an ultraviolet-visible spectrophotometer, and calculating the concentration of the bipyridyl quaternary ammonium salt according to the standard curve.
9. The detection method according to claim 8, wherein when the bipyridyl quaternary ammonium salt is 1, 3-bipyridyl bromopropane, the maximum ultraviolet absorption wavelength is 258 ± 1 nm;
preferably, when the bipyridyl quaternary ammonium salt is 1, 5-dipyridyl bromopentane, the maximum ultraviolet absorption wavelength is 242 +/-1 nm;
preferably, the maximum ultraviolet absorption wavelength of the bipyridyl quaternary ammonium salt is 259 +/-1 nm when the bipyridyl quaternary ammonium salt is 1, 6-dipyridyl bromohexane.
10. The use of the quaternary bis-pyridinium salt of claim 1 in oil field development as an oil displacing agent and an oil field aid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111403033.7A CN114014798A (en) | 2021-11-24 | 2021-11-24 | Bipyridyl quaternary ammonium salt, and preparation method, detection method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111403033.7A CN114014798A (en) | 2021-11-24 | 2021-11-24 | Bipyridyl quaternary ammonium salt, and preparation method, detection method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114014798A true CN114014798A (en) | 2022-02-08 |
Family
ID=80066099
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111403033.7A Pending CN114014798A (en) | 2021-11-24 | 2021-11-24 | Bipyridyl quaternary ammonium salt, and preparation method, detection method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114014798A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1556169A (en) * | 2004-01-12 | 2004-12-22 | 高芒来 | Use of single moleule quarternary ammonium salt compound as clay stabilizing, antiexpanding and deblocking extender |
| CN1557535A (en) * | 2004-01-13 | 2004-12-29 | ����ʦ����ѧ | Gemini quaternary surfactant containing pyridine rings and preparing method thereof |
-
2021
- 2021-11-24 CN CN202111403033.7A patent/CN114014798A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1556169A (en) * | 2004-01-12 | 2004-12-22 | 高芒来 | Use of single moleule quarternary ammonium salt compound as clay stabilizing, antiexpanding and deblocking extender |
| CN1557535A (en) * | 2004-01-13 | 2004-12-29 | ����ʦ����ѧ | Gemini quaternary surfactant containing pyridine rings and preparing method thereof |
Non-Patent Citations (13)
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109679599B (en) | Shale intercalation inhibitor prepared from hyperbranched quaternary ammonium salt | |
| EP1406905B1 (en) | Water- and organic-soluble cucurbituril derivatives, their preparation methods, their separation methods and uses | |
| CN108546267B (en) | Organic conjugated micromolecule material with terminal group containing cycloalkyl chain, preparation method thereof and application thereof in solar cell | |
| CN111995761B (en) | Tripyridyl transition metal organic polymer, preparation method thereof and application thereof in carbon dioxide photocatalytic reduction | |
| JP5792275B2 (en) | Polymer material | |
| CN112062756B (en) | Stenhouse donor-acceptor adducts of mevalonate activated furan and 3-pyridylethylamine and methods of synthesizing the same | |
| CN116333759B (en) | Preparation method of temperature-resistant surfactant | |
| CN114014798A (en) | Bipyridyl quaternary ammonium salt, and preparation method, detection method and application thereof | |
| CN104262127B (en) | Brush-type two fluorine monomer and synthetic method thereof | |
| CN114133385B (en) | Hole transport material with carbazole as core and thiophene or phenoxazine as end group, and synthesis method and application thereof | |
| CN113087702B (en) | Multifunctional perchloroethylene derivative and preparation method and application thereof | |
| CN103626405A (en) | Single-layer fluorescent conjugated polymer membrane and preparation method thereof | |
| JP5214096B2 (en) | Novel bipyridine derivatives | |
| CN111217842B (en) | Spiro-dipyrromethene boron complex/dipyrromethene boron complex and preparation method and application thereof | |
| CN113754868A (en) | Conjugated polymer based on thiophene and benzothiadiazole and preparation method thereof | |
| KR101092332B1 (en) | Fluorescent Anion Receptor of Tweezer-type : Using Pyrene Amide Unit with Cationic Pyridinium Skeleton | |
| Kammer et al. | 2, 11‐Dialkylated 1, 12‐Diazaperylene Copper (I) Complexes: First Supramolecular Column Assemblies by π‐π Stacking between Homoleptic Tetrahedral Metal Complexes, Exhibiting Low‐Energy MLCT Transitions | |
| KR100931860B1 (en) | Phosphonium Aromatic Derivatives for Anion Molecule Detection | |
| CN112851716B (en) | Terpyridyl ruthenium acetylene triphenylamine compound and preparation method and application thereof | |
| CN115417999B (en) | One-dimensional polyrotaxane constructed based on coordination boron-nitrogen bond, and preparation method and application thereof | |
| CN116535320A (en) | Preparation method for green synthesis of polyquaternium by one-step method | |
| KR101024503B1 (en) | Preparation of Catenane with Anion Template | |
| CN114057622A (en) | Short-chain bisimidazole quaternary ammonium salt and preparation and detection method thereof | |
| TW201642515A (en) | Dye-sensitized solar cell and electrolysis solution for dye-sensitized solar cell | |
| Patra et al. | A Stimuli-Responsive Dual-Emitting Covalent Organic Framework Shows Selective Sensing of Highly Corrosive Acidic Media via Fluorescence Turn-On Signal with White Light Emission |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |