A pyridine quaternary ammonium salt type perfluoroalkyl ether compound and its preparation method and application

Abstract

The present invention provides a quaternary pyridine ammonium salt type perfluoroalkyl ether compound and a preparation method and application thereof. The quaternary pyridine ammonium salt type perfluoroalkyl ether compound has a structural formula of: #imgabs0#. The quaternary pyridine ammonium salt type perfluoroalkyl ether compound of the present invention has multiple functional effects, taking into account the effects of corrosion inhibitor, bactericide and drainage agent for oil fields, and can be used as an oil field auxiliary agent and widely used in related fields, thereby solving the problems of single effect, poor compatibility and complicated liquid preparation of existing oil field auxiliary agents.

Description

Technical Field

[0001] The invention belongs to the field of new materials and relates to a pyridine quaternary ammonium salt type perfluoroalkyl ether compound and a preparation method thereof and application in the oil field. Background Art

[0002] Acidizing is an effective method to increase the injection of oil and gas wells or water injection wells. Acidizing is a process measure to increase the production of oil and gas wells or water injection wells by injecting one or more acidic liquids or acidic liquid mixtures into the formation through the wellbore, using the chemical reaction between the acid and some minerals in the formation to dissolve the connected pores or natural fracture wall rocks in the reservoir, increase the conductivity of the pores and fractures, and thus increase the production of oil and gas wells or increase the injection of water injection wells. During the acidizing operation, since the acid is in direct contact with the storage tank, fracturing equipment, downhole oil pipes, casing, etc., especially when high-concentration acid is used for construction in high-temperature deep wells or the acidizing construction time is long, it may cause serious corrosion to the equipment and pipelines. If corrosion inhibition measures are not taken during the acidizing treatment, it will not only damage the equipment, shorten the service life of the equipment, but also cause accidents. At the same time, the metal iron dissolved by the acid becomes ions and can cause damage to the formation under certain conditions. At present, there are many corrosion inhibition measures used in acidizing treatment, which are mainly reflected in three aspects: using corrosion-inhibiting acid, using corrosion inhibition technology or adding corrosion inhibitors. The so-called corrosion inhibitor refers to a substance that can significantly reduce the rate of metal corrosion when added to corrosive media. Corrosion inhibitors are currently the main means of oil well acidizing corrosion protection, and their costs account for a large proportion of the total acidizing cost.

[0003] Furthermore, the bacteria that are most harmful to oil fields are sulfate-reducing bacteria, iron bacteria and saprophytes, so it is necessary to select fungicides to treat these bacteria in a targeted manner. Sulfate-reducing bacteria are anaerobic bacteria that can oxidize carbon-containing organic matter or hydrogen and reduce sulfate to produce H2S. The pH range for the survival of sulfate-reducing bacteria is very wide, ranging from 5.5 to 9.0. The sulfate-reducing bacteria commonly found in oil fields are of the genus Desulfonated Vibrio, which mainly adhere to the pipe wall in groups or colonies. Its main harm is the depolarization effect on the metal surface; due to the action of its hydrogenase, sulfate is reduced to sulfide and primary ecological oxygen [O], and [O] and [H] depolarize to produce H2O. Its depolarization accelerates the corrosion of pipelines and equipment, and the corrosion product FeS can block pipelines and injection wells. Since sulfate-reducing bacteria are the most harmful and hinder oil production in almost every aspect, people have attached great importance to the research on sulfate-reducing bacteria in recent years, such as the discovery of new strains of sulfate-reducing bacteria and the range of their oxidation of carbon-containing organic matter. Saprophytes, also known as slime-forming bacteria, are aerobic heterotrophic bacteria that secrete a large amount of mucus that adheres to pipelines and equipment, causing bioscaling to clog injection wells and filters. At the same time, they also produce oxygen concentration cells, causing corrosion of equipment and pipelines and providing an environment for the survival and reproduction of sulfate-reducing bacteria. Among them, the most important saprophytes are iron bacteria, which are widely distributed multi-order and multi-family bacteria. They mainly oxidize ferrous iron into high-valent iron and use the energy released by iron oxidation to meet their survival needs. The harm of iron bacteria is greater than that of general saprophytes, and they are often the species selected when testing the effect of fungicides.

[0004] In addition, in oilfield fracturing and acidizing operations, the well fluid must be quickly and thoroughly discharged from the ground after the operation is completed to avoid secondary pollution to the formation and achieve the purpose of increasing production and injection. However, the residual fluid after the operation is often unable to be completely discharged due to the high surface tension. Adding drainage aids can effectively reduce the surface tension and increase the interfacial activity, which is conducive to the rapid and thorough return of the well fluid. In addition, adding drainage aids to the well fluid can effectively reduce the interfacial tension, thereby facilitating the smooth injection of the well fluid.

[0005] However, since the existing oilfield additives have a single function, corrosion inhibitors, antibacterial agents and drainage aids are usually required to be added separately to the acid solution used in acidizing operations for compounding. The liquid preparation is cumbersome and the compatibility is poor. At the same time, in order to take into account the compatibility, a variety of compatibility experiments must be carried out, which is a huge workload. Summary of the invention

[0006] The purpose of the present invention is to provide a pyridinium quaternary ammonium salt type perfluoroalkyl ether compound and a preparation method and application thereof, so as to solve the problems of single function, poor compatibility and complicated liquid preparation of oilfield additives in the prior art.

[0007] The present invention is achieved through the following technical solutions:

[0008] The present invention provides a pyridinium quaternary ammonium salt type perfluoroalkyl ether compound, the structural formula of which is as follows:

[0009] .

[0010] The method for preparing the quaternary pyridinium ammonium salt type perfluoroalkyl ether compound of the present invention comprises the following steps:

[0011] S1, reacting 1-chloromethylnaphthalene with 4-hydroxypyridine under heating conditions to obtain an intermediate product, a quaternary ammonium salt of pyridine;

[0012] S2, reacting the obtained quaternary pyridinium salt with hexafluoropropylene trimer under heating conditions to obtain a quaternary pyridinium salt type perfluoroalkyl ether compound.

[0013] Preferably, in S1, the heating temperature is 70-90°C.

[0014] Preferably, in S1, the reaction time is 3 to 5 hours.

[0015] Preferably, in S1, the molar ratio of 1-chloromethylnaphthalene to 4-hydroxypyridine is 1:(1-1.05).

[0016] Preferably, in S2, the heating temperature is 70-80°C.

[0017] Preferably, in S2, the reaction time is 1 to 3 hours.

[0018] Preferably, in S2, the molar ratio of the pyridinium quaternary ammonium salt to the hexafluoropropylene trimer is (1-1.05): (1-1.05).

[0019] The present invention provides the use of the pyridinium quaternary ammonium salt type perfluoroalkyl ether compound as an auxiliary agent in the field of oil fields.

[0020] The invention provides an acid solution for oil fields, comprising an acid and the above-mentioned pyridinium quaternary ammonium salt type perfluoroalkyl ether compound.

[0021] Compared with the prior art, the present invention has the following beneficial effects:

[0022] The pyridinium quaternary ammonium salt type perfluoroalkyl ether compound of the present invention has the triple effects of corrosion inhibitor, sterilization, and reducing the surface / interfacial tension between oil and water. First, the compound belongs to a cationic quaternary ammonium salt, and the N element in the structure contains a lone pair of electrons, which can form a coordination bond with the Fe hollow orbital, thereby playing a corrosion inhibition role. Secondly, the cation in the compound has a positive charge and can be adsorbed onto the negatively charged bacterial body through electrostatic attraction to form a chamber resistance effect; it can also change the permeability of the bacterial membrane through its hydrophobic alkyl group and the hydrophilic group of the bacteria, further induce lysis, destroy the cell structure, cause the dissolution and death of the cell, thereby playing a bactericidal role. Thirdly, the π electrons and non-bonding electrons in the naphthalene group are the key to the film formation of the corrosion inhibitor. Finally, the "three highs and two hates" characteristics of the fluorine-containing structure in the compound enable it to reduce the surface tension and interfacial tension between oil and water, so that it can be used as a drainage agent. Therefore, the pyridinium quaternary ammonium salt type perfluoroalkyl ether compound of the present invention has multiple functional effects, taking into account the effects of corrosion inhibitor, bactericide and drainage agent for oil fields, and can be used as an oil field additive and widely used in related fields, thereby solving the problems of existing oil field additives with single effect, poor compatibility and complicated liquid preparation.

[0023] The preparation method of the pyridinium quaternary ammonium salt type perfluoroalkyl ether compound of the present invention is achieved through a simple two-step reaction, and the reaction process is simple and easy to operate.

[0024] Furthermore, the preparation method of the present invention has mild reaction conditions and short reaction time, and is suitable for industrial production.

[0025] The quaternary pyridinium ammonium salt type perfluoroalkyl ether compound of the present invention is added as an auxiliary agent in the acid solution, so that the obtained acid solution has the characteristics of corrosion inhibition, sterilization and easy backflow, and multiple functions can be achieved without the need for compounding of multiple auxiliary agents, and the liquid preparation is simpler and easier. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0027] Figure 1 This is the infrared spectrum of the pyridinium quaternary ammonium salt type perfluoroalkyl ether prepared in Example 15. DETAILED DESCRIPTION

[0028] The following describes the embodiments of the present invention through specific examples, and those skilled in the art can easily understand other advantages and effects of the present invention from the contents disclosed in this specification. The present invention can also be implemented or applied through other different specific embodiments, and the details in this specification can also be modified or changed in various ways based on different viewpoints and applications without departing from the spirit of the present invention.

[0029] It should be noted that the process equipment or devices not specifically specified in the following embodiments are all conventional equipment or devices in the art.

[0030] It should be noted that the terms "include" and "have" and any variations thereof are intended to cover non-exclusive inclusions. For example, a process, method, system, product or device that includes a series of steps or units is not necessarily limited to those steps or units clearly listed, but may include other steps or units that are not clearly listed or inherent to these processes, methods, products or devices. Moreover, unless otherwise specified, the numbering of each method step is only a convenient tool for identifying each method step, and is not intended to limit the order of arrangement of each method step or to define the scope of the present invention. Changes or adjustments in their relative relationships should also be regarded as the scope of the present invention without substantially changing the technical content.

[0031] The pyridinium quaternary ammonium salt type perfluoroalkyl ether compound of the present invention has the structural formula shown below:

[0032] .

[0033] The pyridinium quaternary ammonium salt type perfluoroalkyl ether compound of the present invention has a unique structure and has multiple functions, taking into account the functions of corrosion inhibitor, bactericide and drainage aid for oil fields. The pyridinium quaternary ammonium salt type perfluoroalkyl ether compound contains a cationic quaternary ammonium salt structure, which has the functions of corrosion inhibition and bactericidal. The fluorine-containing structure has high chemical stability and can reduce the surface tension and interfacial tension between oil and water. It is a new material with multiple functions.

[0034] The method for preparing the quaternary pyridinium ammonium salt type perfluoroalkyl ether compound of the present invention comprises the following steps:

[0035] S1, reacting 1-chloromethylnaphthalene with 4-hydroxypyridine under heating conditions to obtain an intermediate product, a quaternary ammonium salt of pyridine;

[0036] S2, reacting the obtained quaternary pyridinium salt with hexafluoropropylene trimer under heating conditions to obtain a quaternary pyridinium salt type perfluoroalkyl ether compound.

[0037] In the above S1 of the present invention, the heating temperature is preferably 70-90°C, more preferably 80°C; the reaction time is preferably 3-5h, more preferably 4h; the molar ratio of 1-chloromethylnaphthalene to 4-hydroxypyridine is preferably 1:(1-1.05), more preferably 1:1.02, that is, 4-hydroxypyridine is slightly excessive.

[0038] In the above S2 of the present invention, the heating temperature is preferably 70-80°C, more preferably 75°C; the reaction time is preferably 1-3h, more preferably 2h; the molar ratio of the pyridinium quaternary ammonium salt to the hexafluoropropylene trimer is preferably (1-1.05): (1-1.05), more preferably 1:1.

[0039] The present invention preferably uses high-content (content ≥ 99%) 1-chloromethylnaphthalene, which is an important organic synthesis intermediate and is widely used in the synthesis of fine chemicals such as pesticides, medicines, resins and dyes.

[0040] The 4-hydroxypyridine used in the present invention is a chemical and is a light brown to off-white powder.

[0041] The hexafluoropropylene trimer content used in the present invention is 99%. Hexafluoropropylene trimer has three structures, namely T-1, T-2, and T-3; T-1 includes two configurations (Z) T-1 and (E) T-1. Among them, T-1 has lower activity, T-2 has stronger reaction ability with nucleophilic reagents, and T-3 has no ability to react with nucleophilic reagents, but can be isomerized to T-2 in the presence of triethylamine. Therefore, it is required that the content of T-1 in the hexafluoropropylene trimer is less than or equal to 3% to ensure the product yield. The content of T1 in the hexafluoropropylene trimer used in the embodiment of the present invention is 2.6%.

[0042] Wherein, the structural formulas of (Z) T-1, (E) T-1, T-2 and T-3 are respectively as follows:

[0043]

[0044] Example 1

[0045] 1-Chloromethylnaphthalene and 4-hydroxypyridine were added to ethanol in a molar ratio of 1:1, stirred and mixed evenly, heated to 70° C., and reacted for 4 hours to obtain an ethanol solution of an intermediate product, pyridine quaternary ammonium salt.

[0046] Example 2

[0047] 1-Chloromethylnaphthalene and 4-hydroxypyridine were added to ethanol at a molar ratio of 1:1.02, stirred and mixed evenly, heated to 70° C., and reacted for 4 hours to obtain an ethanol solution of an intermediate product, pyridine quaternary ammonium salt.

[0048] Example 3

[0049] 1-Chloromethylnaphthalene and 4-hydroxypyridine were added to ethanol at a molar ratio of 1:1.05, stirred and mixed evenly, heated to 70° C., and reacted for 4 hours to obtain an ethanol solution of an intermediate product, pyridine quaternary ammonium salt.

[0050] Example 4

[0051] 1-Chloromethylnaphthalene and 4-hydroxypyridine were added to ethanol in a molar ratio of 1:1, stirred and mixed evenly, heated to 80° C., and reacted for 4 hours to obtain an ethanol solution of an intermediate product, pyridine quaternary ammonium salt.

[0052] Example 5

[0053] 1-Chloromethylnaphthalene and 4-hydroxypyridine were added to ethanol at a molar ratio of 1:1.02, stirred and mixed evenly, heated to 80° C., and reacted for 4 hours to obtain an ethanol solution of an intermediate product, pyridine quaternary ammonium salt.

[0054] Example 6

[0055] 1-Chloromethylnaphthalene and 4-hydroxypyridine were added to ethanol at a molar ratio of 1:1.05, stirred and mixed evenly, heated to 80° C., and reacted for 4 hours to obtain an ethanol solution of an intermediate product, pyridine quaternary ammonium salt.

[0056] Example 7

[0057] 1-Chloromethylnaphthalene and 4-hydroxypyridine were added to ethanol at a molar ratio of 1:1.02, stirred and mixed evenly, heated to 80°C, and reacted for 3h to obtain an ethanol solution of an intermediate product, pyridine quaternary ammonium salt.

[0058] Example 8

[0059] 1-Chloromethylnaphthalene and 4-hydroxypyridine were added to ethanol at a molar ratio of 1:1.02, stirred and mixed evenly, heated to 80°C, and reacted for 5 hours to obtain an ethanol solution of the intermediate product pyridine quaternary ammonium salt.

[0060] Example 9

[0061] 1-Chloromethylnaphthalene and 4-hydroxypyridine were added to ethanol in a molar ratio of 1:1, stirred and mixed evenly, heated to 90° C., and reacted for 4 hours to obtain an ethanol solution of an intermediate product, pyridine quaternary ammonium salt.

[0062] Example 10

[0063] 1-Chloromethylnaphthalene and 4-hydroxypyridine were added to ethanol at a molar ratio of 1:1.02, stirred and mixed evenly, heated to 90° C., and reacted for 4 hours to obtain an ethanol solution of an intermediate product, pyridine quaternary ammonium salt.

[0064] Embodiment 11

[0065] 1-Chloromethylnaphthalene and 4-hydroxypyridine were added to ethanol at a molar ratio of 1:1.05, stirred and mixed evenly, heated to 90° C., and reacted for 4 hours to obtain an ethanol solution of an intermediate product, pyridine quaternary ammonium salt.

[0066] The reaction conditions and yields of the intermediate product quaternary ammonium pyridine salt of Examples 1-11 of the present invention are shown in Table 1.

[0067] Table 1 Reaction conditions and yield of intermediate product pyridine quaternary ammonium salt of Examples 1-11

[0068]

[0069] As can be seen from Table 1, when the reaction temperature is 80°C and the molar ratio of 1-chloromethylnaphthalene to 4-hydroxypyridine is 1:1.02, the yield of the intermediate product pyridine quaternary ammonium salt is the highest. Therefore, this condition is the optimal condition for preparing the intermediate product pyridine quaternary ammonium salt.

[0070] Example 12

[0071] According to the molar ratio of pyridinium quaternary ammonium salt to hexafluoropropylene trimer of 1:1, hexafluoropropylene trimer was slowly added dropwise to the ethanol solution of the intermediate product pyridinium quaternary ammonium salt obtained in Example 5, stirred evenly, heated to 70° C., and reacted for 2 hours to obtain an ethanol solution of pyridinium quaternary ammonium salt type perfluoroalkyl ether.

[0072] Example 13

[0073] According to the molar ratio of pyridinium quaternary ammonium salt to hexafluoropropylene trimer of 1.01:1, hexafluoropropylene trimer was slowly added dropwise to the ethanol solution of the intermediate product pyridinium quaternary ammonium salt obtained in Example 5, stirred evenly, heated to 70° C., and reacted for 2 hours to obtain an ethanol solution of pyridinium quaternary ammonium salt type perfluoroalkyl ether.

[0074] Embodiment 14

[0075] According to the molar ratio of pyridinium quaternary ammonium salt to hexafluoropropylene trimer of 1:1.05, hexafluoropropylene trimer was slowly added dropwise to the ethanol solution of the intermediate product pyridinium quaternary ammonium salt obtained in Example 5, stirred evenly, heated to 70° C., and reacted for 2 hours to obtain an ethanol solution of pyridinium quaternary ammonium salt type perfluoroalkyl ether.

[0076] Embodiment 15

[0077] According to the molar ratio of pyridinium quaternary ammonium salt to hexafluoropropylene trimer of 1:1, hexafluoropropylene trimer was slowly added dropwise to the ethanol solution of the intermediate product pyridinium quaternary ammonium salt obtained in Example 5, stirred evenly, heated to 75° C., and reacted for 2 hours to obtain an ethanol solution of pyridinium quaternary ammonium salt type perfluoroalkyl ether.

[0078] Example 16

[0079] According to the molar ratio of pyridinium quaternary ammonium salt to hexafluoropropylene trimer of 1.05:1, hexafluoropropylene trimer was slowly added dropwise to the ethanol solution of the intermediate product pyridinium quaternary ammonium salt obtained in Example 5, stirred evenly, heated to 75° C., and reacted for 2 hours to obtain an ethanol solution of pyridinium quaternary ammonium salt type perfluoroalkyl ether.

[0080] Embodiment 17

[0081] According to the molar ratio of pyridinium quaternary ammonium salt to hexafluoropropylene trimer of 1:1.05, hexafluoropropylene trimer was slowly added dropwise to the ethanol solution of the intermediate product pyridinium quaternary ammonium salt obtained in Example 5, stirred evenly, heated to 75° C., and reacted for 2 hours to obtain an ethanol solution of pyridinium quaternary ammonium salt type perfluoroalkyl ether.

[0082] Embodiment 18

[0083] According to the molar ratio of pyridinium quaternary ammonium salt to hexafluoropropylene trimer of 1:1, hexafluoropropylene trimer was slowly added dropwise to the ethanol solution of the intermediate product pyridinium quaternary ammonium salt obtained in Example 5, stirred evenly, heated to 75° C., and reacted for 1 hour to obtain an ethanol solution of pyridinium quaternary ammonium salt type perfluoroalkyl ether.

[0084] Embodiment 19

[0085] According to the molar ratio of pyridinium quaternary ammonium salt to hexafluoropropylene trimer of 1:1, hexafluoropropylene trimer was slowly added dropwise to the ethanol solution of the intermediate product pyridinium quaternary ammonium salt obtained in Example 5, stirred evenly, heated to 75° C., and reacted for 3 hours to obtain an ethanol solution of pyridinium quaternary ammonium salt type perfluoroalkyl ether.

[0086] Embodiment 20

[0087] According to the molar ratio of pyridinium quaternary ammonium salt to hexafluoropropylene trimer of 1:1, hexafluoropropylene trimer was slowly added dropwise to the ethanol solution of the intermediate product pyridinium quaternary ammonium salt obtained in Example 5, stirred evenly, heated to 80° C., and reacted for 2 hours to obtain an ethanol solution of pyridinium quaternary ammonium salt type perfluoroalkyl ether.

[0088] Embodiment 21

[0089] According to the molar ratio of pyridinium quaternary ammonium salt to hexafluoropropylene trimer of 1.05:1, hexafluoropropylene trimer was slowly added dropwise to the ethanol solution of the intermediate product pyridinium quaternary ammonium salt obtained in Example 5, stirred evenly, heated to 80° C., and reacted for 2 hours to obtain an ethanol solution of pyridinium quaternary ammonium salt type perfluoroalkyl ether.

[0090] Embodiment 22

[0091] According to the molar ratio of pyridinium quaternary ammonium salt to hexafluoropropylene trimer of 1:1.05, hexafluoropropylene trimer was slowly added dropwise to the ethanol solution of the intermediate product pyridinium quaternary ammonium salt obtained in Example 5, stirred evenly, heated to 80° C., and reacted for 2 hours to obtain an ethanol solution of pyridinium quaternary ammonium salt type perfluoroalkyl ether.

[0092] The reaction conditions and yields of quaternary pyridinium ammonium salt type perfluoroalkyl ethers of Examples 12-22 of the present invention are shown in Table 2.

[0093] Table 2 Reaction conditions and yields of quaternary pyridinium ammonium salt type perfluoroalkyl ethers of Examples 12-22

[0094]

[0095] As can be seen from Table 2, the yield of pyridinium quaternary ammonium salt type perfluoroalkyl ether obtained under the reaction conditions of Example 15 reached 96.2%. When the reaction time was extended to 3h on the basis of Example 15, the yield of pyridinium quaternary ammonium salt type perfluoroalkyl ether was 96.3%. Although the yield of Example 19 was improved relative to that of Example 15, the improvement was very small. Therefore, considering the reaction time and the yield of pyridinium quaternary ammonium salt type perfluoroalkyl ether, the optimal reaction conditions of pyridinium quaternary ammonium salt and hexafluoropropylene trimer were determined to be: reaction temperature of 75°C, molar ratio of pyridinium quaternary ammonium salt to hexafluoropropylene trimer of 1:1, and reaction time of 2h. Therefore, the optimal reaction conditions for preparing quaternary pyridine ammonium salt type perfluoroalkyl ether of the present invention are: the molar ratio of 1-chloromethylnaphthalene to 4-hydroxypyridine is 1:1.02, and the reaction is carried out at 80° C. for 4 hours to prepare the intermediate product quaternary pyridine ammonium salt; the molar ratio of the intermediate product quaternary pyridine ammonium salt to the hexafluoropropylene trimer is 1:1, and the reaction is carried out at 75° C. for 2 hours to prepare the quaternary pyridine ammonium salt type perfluoroalkyl ether.

[0096] The infrared spectrum of the pyridinium quaternary ammonium salt type perfluoroalkyl ether prepared in Example 15 is as follows: Figure 1 As shown. At 1472 cm -1 The characteristic peak at 1396 cm corresponds to the bending vibration absorption peak of -CH. -1 The characteristic peak at 3030cm is the -CH2 bending vibration absorption peak connected to the nitrogen cation. -1 The characteristic peak at ~1600cm -1 、~1500cm -1 The characteristic peaks near the pyridine ring increased from the original four absorption peaks to five absorption peaks (including 1472cm -1 ). At 1091cm -1 The characteristic peak at 798 cm is the stretching vibration absorption peak of -CCl on the benzene ring. -1 、732cm -1The characteristic peak at 1683 cm is the absorption peak of the para-substituted benzene ring. -1 The characteristic peak at is the single substitution absorption peak of pyridine. Fluorine-containing compounds usually show stretching vibration peaks of CH bonds and CF bonds, with a wave number range of 3000-2800cm -1 and 1200-1000cm -1 between.

[0097] The corrosion inhibition performance of the pyridinium quaternary ammonium salt type perfluoroalkyl ether prepared in Example 15 of the present invention was tested.

[0098] The test was carried out according to the indicators of 90℃ corrosion inhibitor and 120℃ corrosion inhibitor in SY / T 5405-2019 Performance test method and evaluation index of corrosion inhibitor for acidification, as shown in Table 3.

[0099] Table 3 Corrosion inhibition performance of quaternary ammonium pyridinium salt type perfluoroalkyl ether

[0100]

[0101] It can be seen from Table 3 that the acidification corrosion rate after adding the pyridinium quaternary ammonium salt type perfluoroalkyl ether of the present invention can meet the index requirements, indicating that the pyridinium quaternary ammonium salt type perfluoroalkyl ether prepared by the present invention has a good corrosion inhibition effect at both 90°C and 120°C and can be used as a corrosion inhibitor.

[0102] The surface tension and interfacial tension properties of the pyridinium quaternary ammonium salt type perfluoroalkyl ether prepared in Example 15 of the present invention and the intermediate product pyridinium quaternary ammonium salt obtained in Example 5 were tested.

[0103] According to the performance test method and evaluation index of SY / T 5755-2016 fracturing acidizing drainage agent, pyridinium quaternary ammonium salt type perfluoroalkyl ether and pyridinium quaternary ammonium salt were tested, and the results are shown in Table 4 and Table 5, respectively.

[0104] Table 4 Surface tension and interfacial tension properties of quaternary ammonium pyridinium perfluoroalkyl ethers

[0105]

[0106] Table 5 Surface tension and interfacial tension properties of intermediate product pyridinium quaternary ammonium salt

[0107]

[0108] It can be seen from Table 4 that the surface tension and interfacial tension of the fracturing acid solution to which the pyridinium quaternary ammonium salt type perfluoroalkyl ether of the present invention is added can meet the index requirements, indicating that the pyridinium quaternary ammonium salt type perfluoroalkyl ether of the present invention can be used as a drainage agent in the petroleum field.

[0109] As can be seen from Table 5, the surface tension and interfacial tension of the intermediate product pyridinium quaternary ammonium salt are significantly higher than those of the pyridinium quaternary ammonium salt type perfluoroalkyl ether, and cannot meet the index requirements, indicating that the fluorine-containing structure in the compound of the present invention enables it to reduce the surface tension and interfacial tension between oil and water.

[0110] The bactericidal properties of the pyridinium quaternary ammonium salt type perfluoroalkyl ether prepared in Example 15 of the present invention were tested.

[0111] The product was tested according to SY / T 5757-2010 Performance test method and evaluation index of fungicide for oil field water injection. The results are shown in Table 6.

[0112] Table 6 Bactericidal properties of quaternary ammonium pyridinium perfluoroalkyl ethers

[0113]

[0114] As can be seen from Table 6, the pyridinium quaternary ammonium salt type perfluoroalkyl ether of the present invention has a good bactericidal effect on sulfate-reducing bacteria, saprophytes and iron bacteria, all of which can meet the index requirements and can be used as a bactericide in the petroleum field.

[0115] From the above results, it can be seen that the pyridinium quaternary ammonium salt type perfluoroalkyl ether prepared by the present invention integrates the three functions of corrosion inhibition, drainage aid and bactericidal. Therefore, it is added to the acid solution or fracturing fluid as an auxiliary agent, which can play the role of corrosion inhibition, drainage aid and bactericidal at the same time, and can solve the problems of poor compatibility and cumbersome liquid preparation when adding corrosion inhibitors, drainage aids and bactericides separately.

Claims

1. A pyridinium quaternary ammonium salt type perfluoroalkyl ether compound, It is characterized in that Its structural formula is as follows: 。 2. The method for preparing the pyridinium quaternary ammonium salt type perfluoroalkyl ether compound according to claim 1, It is characterized in that The following steps are involved: S1, reacting 1-chloromethylnaphthalene with 4-hydroxypyridine under heating conditions to obtain a quaternary ammonium salt of pyridine; S2, reacting the obtained quaternary pyridinium salt with hexafluoropropylene trimer under heating conditions to obtain a quaternary pyridinium salt type perfluoroalkyl ether compound.

3. The method for preparing the pyridinium quaternary ammonium salt type perfluoroalkyl ether compound according to claim 2, It is characterized in that In S1, the heating temperature is 70~90℃.

4. The method for preparing the pyridinium quaternary ammonium salt type perfluoroalkyl ether compound according to claim 2, It is characterized in that In S1, the reaction time is 3~5h.

5. The method for preparing the pyridinium quaternary ammonium salt type perfluoroalkyl ether compound according to claim 2, It is characterized in that In S1, the molar ratio of 1-chloromethylnaphthalene to 4-hydroxypyridine is 1:(1~1.05).

6. The method for preparing the pyridinium quaternary ammonium salt type perfluoroalkyl ether compound according to claim 2, It is characterized in that In S2, the heating temperature is 70-80°C.

7. The method for preparing the pyridinium quaternary ammonium salt type perfluoroalkyl ether compound according to claim 2, It is characterized in that In S2, the reaction time is 1 to 3 hours.

8. The method for preparing the pyridinium quaternary ammonium salt type perfluoroalkyl ether compound according to claim 2, It is characterized in that In S2, the molar ratio of pyridinium quaternary ammonium salt and hexafluoropropylene trimer is (1~1.05):(1~1.05).

9. Use of the pyridinium quaternary ammonium salt type perfluoroalkyl ether compound according to claim 1 as an auxiliary agent in the field of oil fields.

10. An acid solution for oil fields, It is characterized in that The invention comprises an acid and the pyridinium quaternary ammonium salt type perfluoroalkyl ether compound according to claim 1.

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