Compound, preparation method and application thereof

Abstract

The present invention relates to the technical field of oilfield development, and discloses a compound, a preparation method thereof, and an application thereof. The compound of the present invention has a structure shown in Formula I: #imgabs0# wherein A1, A2, A3, and A4 are each independently selected from a structure shown in Formula II: #imgabs1# wherein R1 is a C2-C4 alkyl group, R2 is a C2-C4 alkyl group, m is an integer of 1-8; n is an integer of 1-3, and P ‑ is a halogen ion; R3 is a C1-C4 alkyl group, R4 is a C3-C6 alkyl group, x+y+z is an integer of 6-30, and x, y, and z are all non-zero. The structure of the compound simultaneously contains multiple ammonium ions and multiple hydrophobic alkylene oxide segments, resulting in the compound having the advantages of strong adsorption, significant hydrophobic effect, and good temperature resistance. It can be directly used as a clay stabilizer under high temperature conditions, not only having excellent anti-swelling and anti-swelling effects, but also being a single substance, and not subject to chromatographic separation.

Description

Technical Field

[0001] The present invention relates to the technical field of oilfield development, in particular to a compound and a preparation method thereof, as well as application of the compound in a clay stabilizer. Background Art

[0002] Clay minerals are widely present in oil reservoirs, with 97% of oil reservoirs worldwide containing clay minerals to varying degrees. Reservoirs containing 5%-20% clay are generally considered to have a high clay content. Improper development practices can cause clay minerals to swell, disperse, and migrate, blocking the throats of the formation pore structure, reducing formation permeability and causing formation damage. During swelling, clay absorbs water into its crystal structure, increasing its volume and thus blocking formation pores. During migration, clay material can be dispersed by external fluids or carried by produced fluids, forming bridges or choke points in the capillary pore throats, which can easily lead to a decrease in formation permeability. Therefore, for reservoirs with high clay content and strong water sensitivity, any process measures such as drilling, cementing, water injection, fracturing, acidizing, well repair and well killing, as long as there is intrusion of water-based working fluid, it is possible to cause water-sensitive damage. The most common method to solve water-sensitive damage is to add clay stabilizers to the injected water. Therefore, the development and use of high-quality and efficient anti-swelling agents are important measures to ensure stable production of oil fields.

[0003] Currently, clay stabilizers are commonly used to protect formation permeability in shallow areas, with a temperature resistance generally below 200°C. Analysis of their insufficient temperature resistance suggests two main reasons: first, the agent's inherent thermal stability is insufficient, causing decomposition at high temperatures and failing to prevent swelling; second, the agent's adsorption to clay weakens at high temperatures, preventing effective absorption within the clay, resulting in poorer effectiveness. While combining several agents can improve temperature resistance, it also poses the risk of chromatographic separation within the reservoir pores, resulting in unsatisfactory field results and failure to achieve deep anti-swelling effectiveness. Summary of the Invention

[0004] The present invention aims to overcome the problem of poor anti-swelling and anti-shrinking effects of clay stabilizers in the prior art at high temperatures, and provides a compound, a preparation method, and an application thereof. The structure of the compound simultaneously contains multiple quaternary ammonium cations and multiple hydrophobic segments of alkylene oxide, so that the compound has the advantages of strong adsorption, obvious hydrophobic effect, and good temperature resistance. The compound can be directly used as a clay stabilizer under high temperature conditions, not only having better anti-swelling and anti-shrinking effects, but also being a single substance, and not subject to chromatographic separation.

[0005] In order to achieve the above object, the first aspect of the present invention provides a compound, characterized in that the compound has a structure shown in Formula I:

[0006]

[0007] Wherein, A1, A2, A3, and A4 are each independently selected from the structure shown in Formula II:

[0008]

[0009] Wherein, R1 is a C2-C4 alkyl group, R2 is a C2-C4 alkyl group, and m is an integer of 1-8;

[0010] n is an integer from 1 to 3, P - is a halide ion;

[0011] R3 is a C1-C4 alkyl group, R4 is a C3-C6 alkyl group, x+y+z is an integer of 6-30, and x, y, and z are not 0.

[0012] The second aspect of the present invention provides a method for preparing the compound according to the first aspect of the present invention, characterized in that it comprises the following steps:

[0013] The compound represented by formula III is contacted with the compound represented by formula V to undergo a first reaction to obtain the compound represented by formula I;

[0014]

[0015] Wherein, E1, E2, E3, and E4 are each independently selected from the structure shown in Formula IV:

[0016]

[0017] Wherein, R1 is a C2-C4 alkyl group, R2 is a C2-C4 alkyl group, and m is an integer of 1-8;

[0018] n is an integer of 1 to 3, and P is a halogen;

[0019] R3 is a C1-C4 alkyl group, R4 is a C3-C6 alkyl group, x+y+z is an integer of 6-30, and x, y, and z are not 0.

[0020] The third aspect of the present invention provides use of the compound described in the first aspect or the compound prepared by the method described in the second aspect in a clay stabilizer.

[0021] Through the above technical solution, the compound provided by the present invention, its preparation method, and the application of the compound in a clay stabilizer achieve the following beneficial effects:

[0022] The structure of the compound provided by the present invention simultaneously contains multiple ammonium ions and multiple hydrophobic alkylene oxide segments, which makes the compound have the advantages of strong adsorption, obvious hydrophobic effect, good temperature resistance, etc., and can be directly used as a clay stabilizer under high temperature conditions. It not only has excellent anti-swelling and anti-shrinking effects, but also is a single substance and does not undergo chromatographic separation. Specifically, the quaternary ammonium cations introduced into the compound structure have a much stronger adsorption force with the formation than the lone pair of electrons on the amine nitrogen, resulting in a strong adsorption force with the formation. The presence of multiple quaternary ammonium cations can form multiple adsorption interactions with the clay, which helps enhance its adsorption, allowing the compound to be adsorbed within the clay even under high temperature conditions, thereby preventing swelling. Secondly, the hydrophobic alkylene oxide chain segments introduced into the compound structure, when adsorbed within the clay, not only drive away water molecules that have already entered the clay lamellae, but also prevent external water molecules from re-entering the clay, thereby improving the anti-swelling performance. Thirdly, as a single compound with multiple properties, after injection into the reservoir, it does not undergo chromatographic separation, which helps maintain stable performance and achieve a long-lasting and deep anti-swelling effect. Fourthly, because the compound contains multiple quaternary ammonium cations, it can adsorb on the already hydrated and dispersed clay lamellae, pulling them closer and tightening them, thus achieving a shrinking and swelling effect. DETAILED DESCRIPTION

[0023] The endpoints of the ranges and any values ​​disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoints of each range, the endpoints of each range and individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered to be specifically disclosed herein.

[0024] The first aspect of the present invention provides a compound, characterized in that the compound has a structure shown in Formula I:

[0025]

[0026] Wherein, A1, A2, A3, and A4 are each independently selected from the structure shown in Formula II:

[0027]

[0028] Wherein, R1 is a C2-C4 alkyl group, R2 is a C2-C4 alkyl group, and m is an integer of 1-8;

[0029] n is an integer from 1 to 3, P - is a halide ion;

[0030] R3 is a C1-C4 alkyl group, R4 is a C3-C6 alkyl group, x+y+z is an integer of 6-30, and x, y, and z are not 0.

[0031] The structure of the compound provided by the present invention simultaneously contains multiple ammonium ions and multiple hydrophobic alkylene oxide segments, which makes the compound have the advantages of strong adsorption, obvious hydrophobic effect, good temperature resistance, etc., and can be directly used as a clay stabilizer under high temperature conditions. It not only has excellent anti-swelling and anti-shrinking effects, but also is a single substance and does not undergo chromatographic separation. Specifically, the quaternary ammonium cations introduced into the compound structure have a much stronger adsorption force with the formation than the lone pair of electrons on the amine nitrogen, resulting in a strong adsorption force with the formation. The presence of multiple quaternary ammonium cations can form multiple adsorption interactions with the clay, which helps enhance its adsorption, allowing the compound to be adsorbed within the clay even under high temperature conditions, thereby preventing swelling. Secondly, the hydrophobic alkylene oxide chain segments introduced into the compound structure, when adsorbed within the clay, not only drive away water molecules that have already entered the clay lamellae, but also prevent external water molecules from re-entering the clay, thereby improving the anti-swelling performance. Thirdly, as a single compound with multiple properties, after injection into the reservoir, it does not undergo chromatographic separation, which helps maintain stable performance and achieve a long-lasting and deep anti-swelling effect. Fourthly, because the compound contains multiple quaternary ammonium cations, it can adsorb on the already hydrated and dispersed clay lamellae, pulling them closer and tightening them, thus achieving a shrinking and swelling effect.

[0032] According to the present invention, x, y, and z are each independently selected from integers ranging from 5 to 8. When x, y, and z meet the above ranges, the hydrophobic properties of the compound are improved. When x, y, and z are below the above ranges, the hydrophobic properties of the compound are weakened, and it is not possible to completely prevent external water molecules from re-entering the clay. When x, y, and z are above the above ranges, the water solubility of the compound is weakened, which is not conducive to effective dissolution in water, making it inconvenient for on-site use and also affecting the use effect.

[0033] In the present invention, m is an integer of 1-5.

[0034] In the present invention, n is 1 or 2.

[0035] In the present invention, P - For chloride ion.

[0036] In the present invention, R3 is a methyl group or an ethyl group.

[0037] The second aspect of the present invention provides a method for preparing the compound according to the first aspect of the present invention, characterized in that it comprises the following steps:

[0038] The compound represented by formula III and the compound represented by formula V are contacted to cause a first reaction to obtain the compound represented by formula I;

[0039]

[0040] Wherein, E1, E2, E3, and E4 are each independently selected from the structure shown in Formula IV:

[0041]

[0042] Wherein, R1 is a C2-C4 alkyl group, R2 is a C2-C4 alkyl group, and m is an integer of 1-8;

[0043] n is an integer of 1 to 3, and P is a halogen atom;

[0044] R3 is a C1-C4 alkyl group, R4 is a C3-C6 alkyl group, x+y+z is an integer of 6-30, and x, y, and z are not 0.

[0045] The present invention produces a compound represented by Formula I by subjecting a compound represented by Formula III to a Menschutkin reaction with a compound represented by Formula V. The structure of the compound produced by the present invention simultaneously contains multiple ammonium ions and multiple hydrophobic alkylene oxide segments, resulting in the compound having the advantages of strong adsorption, significant hydrophobic effect, and good temperature resistance. The compound can be directly used as a clay stabilizer under high temperature conditions, not only having excellent anti-swelling and anti-swelling effects, but also being a single substance and not subject to chromatographic separation. Specifically, the quaternary ammonium cations introduced into the compound structure have a much stronger adsorption force with the formation than the lone pair of electrons on the amine nitrogen, resulting in a strong adsorption force with the formation. The presence of multiple quaternary ammonium cations can form multiple adsorption interactions with the clay, which helps enhance its adsorption, allowing the compound to be adsorbed within the clay even under high temperature conditions, thereby preventing swelling. Secondly, the hydrophobic alkylene oxide chain segments introduced into the compound structure, when adsorbed within the clay, not only drive away water molecules that have already entered the clay lamellae, but also prevent external water molecules from re-entering the clay, thereby improving the anti-swelling performance. Thirdly, as a single compound with multiple properties, after injection into the reservoir, it does not undergo chromatographic separation, which helps maintain stable performance and achieve a long-lasting and deep anti-swelling effect. Fourthly, because the compound contains multiple quaternary ammonium cations, it can adsorb on the already hydrated and dispersed clay lamellae, pulling them closer and tightening them, thus achieving a shrinking and swelling effect.

[0046] According to the present invention, x, y, and z are each independently selected from integers ranging from 5 to 8. When x, y, and z are each independently selected from integers ranging from 5 to 8, the hydrophobicity of the compound is improved. When the value is below the above range, the hydrophobicity of the compound is weakened, and it is not possible to completely prevent external water molecules from re-entering the clay. When the value is above the above range, the water solubility of the compound is weakened, which is not conducive to its effective dissolution in water, making it inconvenient for on-site use and also affecting the use effect.

[0047] In the present invention, m is an integer of 1-5.

[0048] In the present invention, n is 1 or 2.

[0049] In the present invention, P is a chlorine atom.

[0050] In the present invention, R3 is a methyl group or an ethyl group.

[0051] According to the present invention, the conditions of the first reaction include: a reaction temperature of 60-100°C and a reaction time of 1-8h; when the above ranges are met, it is conducive to the formation of the target product; further, in order to improve the conversion rate and selectivity of the reaction, preferably, the conditions of the first reaction include: a reaction temperature of 80-90°C and a reaction time of 2-6h.

[0052] According to the present invention, the molar ratio of the compound represented by Formula III to the compound represented by Formula V is 1:4-6. When the above range is met, the two can form the compound represented by Formula I. Preferably, when the molar ratio is 1:4-4.5, it is conducive to fully utilizing the raw materials.

[0053] The present invention illustratively provides a method for preparing a compound represented by formula III, comprising the following steps:

[0054] The compound represented by Formula VI is contacted with the compound represented by Formula VII to undergo a second reaction to obtain the compound represented by Formula III;

[0055]

[0056] Wherein, R1 is a C2-C4 alkyl group, R2 is a C2-C4 alkyl group, m is an integer of 1-8; n is an integer of 1-3, and P is a halogen atom.

[0057] In the present invention, m is an integer of 1-5.

[0058] In the present invention, n is 1 or 2.

[0059] In the present invention, P is a chlorine atom.

[0060] According to the present invention, the conditions for the second reaction include: a reaction temperature of 30-80°C and a reaction time of 2-8 hours. When the conditions for the second reaction are within the above ranges, it is conducive to the formation of the target product; further, in order to improve the conversion rate and selectivity of the reaction, preferably, the conditions for the second reaction include: a reaction temperature of 40-60°C and a reaction time of 3-6 hours.

[0061] According to the present invention, the molar ratio of the compound represented by Formula VI to the compound represented by Formula VII is 1:4-6. When the above range is met, the two can form the compound represented by Formula III. Preferably, when the molar ratio is 1:4-4.5, it is conducive to fully utilizing the raw materials.

[0062] The present invention illustratively provides a method for preparing a compound represented by Formula V, comprising the following steps: contacting a compound represented by Formula VIII with a compound represented by Formula IX in the presence of a catalyst to undergo a third reaction to obtain a compound represented by Formula V;

[0063]

[0064]

[0065] Wherein, R3 is a C1-C4 alkyl group, R5 is a C1-C4 alkyl group, and R6 is H or methyl group.

[0066] The preparation method provided by the present invention can form a compound represented by formula V through a ring-opening polymerization reaction. The compound is a tertiary amine structure containing multiple alkylene oxide hydrophobic chains. The tertiary amine can be converted into a quaternary ammonium cation by reacting with a halogen-containing compound represented by formula III, while introducing multiple alkylene oxide hydrophobic chains into the synthesized compound.

[0067] In the present invention, R3 is a methyl group or an ethyl group.

[0068] According to the present invention, the conditions of the third reaction include: a reaction temperature of 70-120°C and a reaction time of 4-10h. When the above ranges are met, it is conducive to the formation of the target product; further, in order to improve the conversion rate and selectivity of the reaction, preferably, the conditions of the third reaction include: a reaction temperature of 80-110°C and a reaction time of 5-8h.

[0069] According to the present invention, the molar ratio of the compound represented by Formula VIII to the compound represented by Formula IX is 1:6-30; when preferably 1:15-24, it is beneficial to improve the solubility of the final product in water, facilitating on-site use. At the same time, hydrophobic chains with excellent hydrophobic effect are introduced into the product to prevent external water molecules from entering the interior of the clay, thereby achieving an excellent anti-swelling effect.

[0070] According to the present invention, the catalyst is selected from alkali metal hydroxides. The specific type of the alkali metal hydroxide of the present invention is not particularly limited. For example, the catalyst is potassium hydroxide.

[0071] The third aspect of the present invention provides use of the compound described in the first aspect of the present invention or the compound prepared by the method described in the second aspect in a clay stabilizer.

[0072] The compound of the invention is a single compound with multiple functional groups and can be directly used as a clay stabilizer for water injection well water injection prevention or oil well expansion control and prevention treatment.

[0073] The clay stabilizer of the present invention can be directly dissolved in deionized water or clean water to obtain a clay stabilizer aqueous solution. The concentration of the clay stabilizer aqueous solution is adjusted according to actual needs. For example, the concentration of the clay stabilizer aqueous solution is 0.001-0.05 g / mL.

[0074] The present invention will be described in detail below through examples.

[0075] In the following examples and comparative examples, the testing methods for each parameter are as follows:

[0076] 1. Anti-swelling rate at room temperature: According to the "SY / T5971-2016 Performance Evaluation Method of Clay Stabilizer for Water Injection", the anti-swelling rate test is carried out as follows:

[0077] Weigh 0.5g of sodium bentonite into a 10mL centrifuge tube. Add deionized water to the 10mL mark, shake thoroughly, and let stand at room temperature for 2 hours. Place the tube in a centrifuge and centrifuge at 1500 rpm for 15 minutes. Read the volume (V2) of the sodium bentonite in water. Use the same procedure but replace deionized water with a 4% aqueous solution of clay stabilizer to determine the volume (V1) of the sodium bentonite after centrifugation. Use the same procedure but replace deionized water with kerosene to determine the volume (V0) of the sodium bentonite.

[0078] The anti-swelling rate calculation formula is as follows:

[0079]

[0080] Where: η is the anti-swelling rate, %; V0 is the volume of sodium bentonite in kerosene, mL; V1 is the volume of sodium bentonite in clay stabilizer solution, mL; V2 is the volume of sodium bentonite in deionized water, mL.

[0081] 2. Anti-swelling rate after aging at 300℃, the steps are as follows:

[0082] (1) Weigh 3 g of sodium bentonite and place it into a high-temperature and high-pressure closed reactor;

[0083] (2) Add 60 mL of a 4% clay stabilizer aqueous solution to the reactor, shake well, place in an oven at 300±2°C for 24 hours, and then cool to room temperature;

[0084] (3) Transfer all the clay mixture in the high-temperature and high-pressure closed reactor into a 100 mL beaker, shake it thoroughly, quickly take out 10 mL and add it to a glass centrifuge tube, put it into a centrifuge with an automatic balancing function, centrifuge it at 1500 r / min for 15 min, and read the expansion volume V1 of the sodium bentonite.

[0085] The clay stabilizer aqueous solution in step (2) was replaced by kerosene and deionized water, respectively, to obtain V0 and V2.

[0086] The calculation formula for the anti-swelling rate after aging at 300°C is as follows:

[0087]

[0088] Where: V0 is the expansion volume of sodium bentonite in kerosene, mL; V1 is the expansion volume of sodium bentonite in clay stabilizer aqueous solution, mL; V2 is the expansion volume of sodium bentonite in deionized water, mL.

[0089] 3. Washability: the test steps are as follows:

[0090] After aging at 300°C, the supernatant in the centrifuge tube after centrifugation in step (3) of the anti-swelling rate test was poured out, deionized water was added to 10 mL, the mixture was thoroughly stirred and allowed to stand for 2 h, and then centrifuged at 1500 r / min for 15 min in a centrifuge. Finally, the final volume V1' of the sodium bentonite in the centrifuge tube was read.

[0091] Calculation formula for wash resistance:

[0092]

[0093] Where: V1 and V2 are the same as V1 and V2 in formula 2; V1' is the expansion volume of sodium bentonite after washing, mL.

[0094] 4. Shrinkage and expansion rate. The test steps are as follows:

[0095] Weigh 0.5g of sodium bentonite into a 10mL centrifuge tube. Add deionized water to the 10mL mark, shake thoroughly, let stand at room temperature for 2 hours, place in a centrifuge, and centrifuge at 1500 r / min for 15 minutes. Read the volume (V2) of the sodium bentonite in deionized water. Pour out the water, add a 4% aqueous solution of clay stabilizer to the 10mL mark, shake thoroughly, let stand at room temperature for 2 hours, place in a centrifuge, and centrifuge at 1500 r / min for 15 minutes. Measure the volume (V1) of the sodium bentonite after centrifugation.

[0096] The calculation formula of shrinkage and expansion rate is as follows:

[0097]

[0098] Wherein: η' is the shrinkage / swelling ratio, %; V0 is the same as V0 in formula 1, mL; V1 is the volume of the expanded sodium bentonite in the clay stabilizer aqueous solution, mL; V2 is the volume of the sodium bentonite in deionized water, mL.

[0099] 5. The test method of core permeability retention value is based on the research and practice of water injection for anti-swelling development of sensitive heavy oil reservoirs, Song Dougui et al., Oilfield Chemistry, 2004, 21(4): 320-323.

[0100] The core flooding test was used to test the original core permeability K0, and then the core was flooded with simulated formation water (total salinity 25×10 4 ppm, divalent calcium ion concentration 5000 ppm) was used to saturate the core tube with water. A 4% clay stabilizer aqueous solution (PV represents pore volume, which is the volume required to fill the pores) was then injected into the core tube at 300°C. High-temperature steam at 300°C was then injected. The permeability, K1, of the core tube was measured after the experiment. K1 / K0 is the core permeability retention value. The blank test in Table 11 was performed by saturating the core tube with simulated formation water and then directly injecting high-temperature steam.

[0101] In the following examples and comparative examples, the specific structures of the raw materials are as follows:

[0102] The structure of the compound represented by formula VI is shown in Table 1:

[0103] Table 1

[0104] Test number Formula VI label <![CDATA[R1]]> <![CDATA[R2]]> m Preparation Example 1-1 VI-T1 n-propyl Isopropyl 2 Preparation Example 1-2 VI-T2 Ethyl Isopropyl 3 Preparation Examples 1-3 VI-T3 Isobutyl Isopropyl 4 Preparation Examples 1-4 VI-T4 Ethyl Isopropyl 1 Preparation Examples 1-5 VI-T5 n-propyl Isopropyl 5 Preparation Examples 1-6 VI-T6 Ethyl Isopropyl 2 Preparation Examples 1-7 VI-T7 Ethyl Isopropyl 4 Preparation Examples 1-8 VI-T8 n-propyl Isopropyl 3 Preparation Examples 1-9 VI-T9 Isobutyl Ethyl 1 Preparation Example 1-10 VI-T10 n-propyl Isopropyl 4 Preparation Example 1-11 VI-T11 Ethyl Isobutyl 8 Comparative Preparation Example 1-1 VI-W1 n-propyl Isopropyl 2

[0105] The structure of the compound represented by formula VII is shown in Table 2:

[0106] Table 2

[0107] Test number Formula VII n P Preparation Example 1-1 VII-T1 1 Cl Preparation Example 1-2 VII-T2 1 Cl Preparation Examples 1-3 VII-T3 1 Cl Preparation Examples 1-4 VII-T4 1 Cl Preparation Examples 1-5 VII-T5 1 Cl Preparation Examples 1-6 VII-T6 1 Cl Preparation Examples 1-7 VII-T7 1 Cl Preparation Examples 1-8 VII-T8 1 Cl Preparation Examples 1-9 VII-T9 3 I Preparation Example 1-10 VII-T10 1 F Preparation Example 1-11 VII-T11 2 Br Comparative Preparation Example 1-1 VII-W1 1 Cl

[0108] The structure of the compound represented by formula VIII is shown in Table 3:

[0109] Table 3

[0110] Test number Formula VIII <![CDATA[R3 <!-- 8 -->]]> Preparation Example 2-1 VIII-T1 Ethyl Preparation Example 2-2 VIII-T2 Ethyl Preparation Example 2-3 VIII-T3 Ethyl Preparation Example 2-4 VIII-T4 Ethyl Preparation Example 2-5 VIII-T5 Ethyl Preparation Example 2-6 VIII-T6 Ethyl Preparation Example 2-7 VIII-T7 Ethyl Preparation Example 2-8 VIII-T8 Ethyl Preparation Example 2-9 VIII-T9 n-propyl Preparation Example 2-10 VIII-T10 Ethyl Preparation Example 2-11 VIII-T11 methyl Preparation Example 2-12 VIII-T12 n-Butyl Preparation Example 2-13 VIII-T13 methyl Preparation Example 2-14 VIII-T14 methyl Comparative Preparation Example 2-1 VIII-W1 Ethyl Comparative Preparation Example 2-2 VIII-W2 Ethyl

[0111] The structure of the compound represented by Formula IX is shown in Table 4:

[0112] Table 4

[0113] Test number Formula IX number <![CDATA[R5]]> <![CDATA[R6]]> Preparation Example 2-1 IX-T1 methyl H Preparation Example 2-2 IX-T2 methyl H Preparation Example 2-3 IX-T3 methyl H Preparation Example 2-4 IX-T4 methyl H Preparation Example 2-5 IX-T5 methyl H Preparation Example 2-6 IX-T6 methyl H Preparation Example 2-7 IX-T7 methyl H Preparation Example 2-8 IX-T8 methyl H Preparation Example 2-9 IX-T9 methyl H Preparation Example 2-10 IX-T10 Ethyl H Preparation Example 2-11 IX-T11 Ethyl H Preparation Example 2-12 IX-T12 methyl methyl Preparation Example 2-13 IX-T13 n-propyl H Preparation Example 2-14 IX-T14 Butyl H Comparative Preparation Example 2-1 IX-W1 H H Comparative Preparation Example 2-2 IX-W2 methyl H

[0114] Sodium bentonite meets the requirements of SY / T 5490.

[0115] Unless otherwise specified, the raw materials used in the present invention are all commercially available conventional products.

[0116] 1. Preparation of the compound represented by formula III

[0117] Preparation Example 1-1

[0118] Compound VI-T1 and compound VII-T1 were added to a reactor, and the molar ratio of compound VI-T1 to compound VII-T1 was controlled to be 1:5. The reaction was carried out at 50°C for 4 hours. After the reaction was completed, the generated salt was filtered out to obtain the purified chlorine-containing intermediate III-T1. The specific structure is shown in Table 5.

[0119] Preparation Examples 1-2 to 1-11

[0120] Chlorine-containing intermediates III-T2 to III-T11 were prepared according to the method of Preparation Example 1-1, except that the type of raw materials and / or reaction conditions were different from those in Preparation Example 1-1, as shown in Table 5. The structures of the prepared chlorine-containing intermediates III-T2 to III-T11 are shown in Table 6.

[0121] Comparative Preparation Example 1-1

[0122] Chlorine-containing intermediate III-W1 was prepared according to the method of Preparation Example 1-1, except that the molar ratio of compound VI-T1 to compound VII-T1 was 1:3, as shown in Table 5. The structure of the obtained chlorine-containing intermediate III-W1 is shown in Table 6.

[0123] Table 5

[0124]

[0125] Table 6

[0126]

[0127]

[0128] 2. Preparation of the compound represented by Formula V

[0129] Preparation Example 2-1

[0130] Compound VIII-T1 was added to a reactor, potassium hydroxide was added as a catalyst, the temperature of the reactor was controlled at 80°C, and then compound IX-T1 was continuously introduced. The molar ratio of compound VIII-T1 to compound IX-T1 was 1:24, and the reaction time was 8 hours. After the reaction, the obtained crude product was neutralized with acid, adsorbed on an adsorbent, and then dehydrated by reduced pressure distillation to obtain purified tertiary amine V-T1. The specific structure is shown in Table 8.

[0131] Preparation Examples 2-2 to 2-14

[0132] Tertiary amines V-T2 to V-T14 were prepared according to the method of Preparation Example 2-1, except that the type of raw materials and / or reaction conditions were different from those in Preparation Example 2-1, as shown in Table 7. The structures of the obtained tertiary amines V-T2 to V-T14 are shown in Table 8.

[0133] Comparative Preparation Example 2-1

[0134] The tertiary amine V-W1 was prepared according to the method of Preparation Example 2-1, except that R5 and R6 in Formula IX-W1 were both H, as shown in Table 7. The structure of the obtained tertiary amine V-W1 is shown in Table 8.

[0135] Comparative Preparation Example 2-2

[0136] The tertiary amine V-W2 was prepared according to the method of Preparation Example 2-1, except that the reaction conditions were different from those of Preparation Example 2-1, as shown in Table 7. The structure of the obtained tertiary amine V-W2 was shown in Table 8.

[0137] Table 7

[0138]

[0139] Table 8

[0140]

[0141]

[0142] III. Preparation of the compound represented by Formula I

[0143] Example 1

[0144] Compound III-T1 and compound V-T1 were added to a reactor and reacted at 90°C for 4 hours. The molar ratio of compound III-T1 to compound V-T1 was 1:4.2. After the reaction, the crude product was washed with anhydrous ethanol, and the insoluble matter was filtered out. The filtrate was then distilled under reduced pressure to remove ethanol to obtain purified compound I-T1, the specific structure of which is shown in Table 10.

[0145] Example 2-17

[0146] Compounds I-T2 to I-T17 were prepared according to the method of Example 1, except that the type of raw materials and / or reaction conditions were different from those in Example 1, as shown in Table 9. The structures of the prepared compounds I-T2 to I-T17 are shown in Table 10.

[0147] Comparative Examples 1-3

[0148] Compounds I-W1 to I-W3 were prepared according to the method of Example 1, except that the type of raw materials and / or reaction conditions were different from those in Example 1, as shown in Table 9. The structures of the prepared compounds I-W1 to I-W3 are shown in Table 10.

[0149] Comparative Example 4

[0150] The tertiary amine V-T1 containing a propylene oxide hydrophobic chain was directly used as a clay stabilizer, denoted as I-W4, and the specific structure is shown in Table 10.

[0151] Comparative Example 5

[0152] The chlorine-containing intermediate III-T4 was reacted with trimethylamine. The reaction conditions are detailed in Table 9. The structure of the reaction product is shown in the following formula. It is used as a clay stabilizer and is denoted as I-W5. The structure of I-W5 differs from that of I-T4 in that three methyl groups are connected to each quaternary ammonium cation.

[0153] Table 9

[0154]

[0155] Table 10

[0156] Label <![CDATA[R1]]> <![CDATA[R2]]> m n <![CDATA[P - ]]> <![CDATA[R3]]> <![CDATA[R4]]> x y z I-T1 n-propyl Isopropyl 2 1 <![CDATA[Cl - ]]> Ethyl Isopropyl 8 8 8 I-T2 Ethyl Isopropyl 3 1 <![CDATA[Cl - ]]> Ethyl Isopropyl 5 5 5 I-T3 Isobutyl Isopropyl 4 1 <![CDATA[Cl - ]]> Ethyl Isopropyl 6 6 6 I-T4 Ethyl Isopropyl 1 1 <![CDATA[Cl - ]]> Ethyl Isopropyl 5 5 5 I-T5 n-propyl Isopropyl 5 1 <![CDATA[Cl - ]]> Ethyl Isopropyl 8 8 8 I-T6 Ethyl Isopropyl 2 1 <![CDATA[Cl - ]]> Ethyl Isopropyl 7 7 7 I-T7 Ethyl Isopropyl 4 1 <![CDATA[Cl - ]]> Ethyl Isopropyl 7 7 7 I-T8 n-propyl Isopropyl 3 1 <![CDATA[Cl - ]]> Ethyl Isopropyl 7 7 7 I-T9 Isobutyl Ethyl 1 3 <![CDATA[I - ]]> Ethyl Isopropyl 8 8 8 I-T10 n-propyl Isopropyl 4 1 <![CDATA[F - ]]> Ethyl Isopropyl 8 8 8 I-T11 Ethyl Isobutyl 8 2 <![CDATA[Br - ]]> Ethyl Isopropyl 8 8 8 I-T12 n-propyl Isopropyl 2 1 <![CDATA[Cl - ]]> n-propyl Isopropyl 10 10 10 I-T13 n-propyl Isopropyl 2 1 <![CDATA[Cl - ]]> Ethyl Isobutyl 9 9 9 I-T14 n-propyl Isopropyl 2 1 <![CDATA[Cl - ]]> methyl Isobutyl 3 3 3 I-T15 n-propyl Isopropyl 2 1 <![CDATA[Cl - ]]> n-Butyl tert-butyl 8 8 8 I-T16 n-propyl Isopropyl 2 1 <![CDATA[Cl - ]]> methyl Isoamyl 3 3 3 I-T17 n-propyl Isopropyl 2 1 <![CDATA[Cl - ]]> methyl Isohexyl 2 2 2 *I-W1 n-propyl Isopropyl 2 1 <![CDATA[Cl - ]]> Ethyl Isopropyl 8 8 8 I-W2 n-propyl Isopropyl 2 1 <![CDATA[Cl - ]]> Ethyl Ethyl 8 8 8 I-W3 n-propyl Isopropyl 2 1 <![CDATA[Cl - ]]> Ethyl Isopropyl 12 12 12 I-W4 -- -- -- -- -- Ethyl Isopropyl 8 8 8

[0157] Note: *The number of hydrophobic segments in I-W1 is different from that in I-T1. See Comparative Preparation Example 1-1 for details.

[0158] Test Case

[0159] The compounds prepared in each example and comparative example were dissolved in deionized water to obtain an aqueous solution of the compound. The mass concentration of the aqueous solution of the compound was 4%. Under different conditions, the compounds were evaluated for the room temperature anti-swelling rate of clay, the anti-swelling rate after aging at 300°C, the water washing resistance, the shrinkage and expansion rate, and the core permeability retention value of the clay as clay stabilizers. The results are shown in Table 11.

[0160] Table 11

[0161]

[0162]

[0163] Among them, insoluble matter existed in sample I-W3.

[0164] The results in Table 11 show that the clay stabilizers of Examples 1-8, 9-11, and 15 of the present invention have an anti-swelling rate of over 90% at room temperature, and the anti-swelling rate after aging at 300°C is still over 90%, showing excellent high temperature resistance. The shrinkage and expansion rates are over 50%, the water washability is 100%, and the core permeability retention value is over 90%. These stabilizers can be used for anti-swelling of water injection wells as well as for expansion control and preventive treatment of oil wells.

[0165] In addition, the data comparison of Example 1 and Comparative Example 1 shows that the compound of the specific structure of the present invention has a better anti-swelling and shrinking effect as a clay stabilizer. When some hydrophobic segments and quaternary ammonium cations are missing, the anti-swelling and shrinking properties after high-temperature aging are significantly reduced; the data comparison of Example 1 and Comparative Example 2 shows that after the introduction of a specific hydrophobic chain into the molecular structure, the anti-swelling and shrinking properties are greatly improved; the data comparison of Example 1 and Comparative Example 3 shows that when the chain length of the hydrophobic chain exceeds a certain range, the solubility of the clay stabilizer in water will be reduced, and insoluble matter will be produced. These insoluble matter will block the pores of the core and damage the permeability of the core; the data comparison of Example 1 and Comparative Example 4 shows that the introduction of a certain number of quaternary ammonium cations is beneficial to improving the adsorption of the clay stabilizer on the clay, which is beneficial to improving its temperature resistance and scour resistance; the data comparison of Example 4 and Comparative Example 5 shows that the introduction of a hydrophobic chain with a specific structure can improve the anti-swelling and shrinking properties of the clay stabilizer, which is beneficial to protecting the permeability of the core.

[0166] The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, various simple variations of the technical solution of the present invention may be made, including combining the various technical features in any other appropriate manner. These simple variations and combinations should also be regarded as disclosed in the present invention and fall within the scope of protection of the present invention.

Claims

1. A compound, characterized in that The compound has the structure shown in Formula I: Formula I; Wherein, A1, A2, A3, and A4 are each independently selected from the structure shown in Formula II: Formula II; Wherein, R1 is a C2-C4 alkyl group, R2 is a C2-C4 alkyl group, and m is an integer of 1-8; n is an integer from 1 to 3, P - is a halide ion; R3 is a C1-C4 alkyl group, R4 is a C3-C6 alkyl group, x, y, and z are each independently selected from an integer of 5 to 8, and x, y, and z are not 0; The preparation method of the compound comprises the following steps: The compound represented by formula III and the compound represented by formula V are contacted to cause a first reaction to obtain the compound represented by formula I; Formula III; Wherein, E1, E2, E3, and E4 are each independently selected from the structure shown in Formula IV: Formula IV; Formula V; Wherein, R1 is a C2-C4 alkyl group, R2 is a C2-C4 alkyl group, and m is an integer of 1-8; n is an integer of 1 to 3, and P is a halogen atom; R3 is a C1-C4 alkyl group, R4 is a C3-C6 alkyl group, x, y, and z are each independently selected from an integer of 5 to 8, and x, y, and z are not 0; The preparation of the compound represented by formula V comprises the following steps: In the presence of a catalyst, the compound represented by Formula VIII is contacted with the compound represented by Formula IX to undergo a third reaction to obtain a compound represented by Formula V; Formula VIII; Formula IX; Wherein, R3 is a C1-C4 alkyl group, R5 is a C1-C4 alkyl group, and R6 is H or methyl group.

2. The compound according to claim 1, characterized in that The conditions for the first reaction in the preparation method of the compound include: reaction temperature of 60-100° C.; reaction time of 1-8 h; And / or, the molar ratio of the compound represented by formula III to the compound represented by formula V is 1:4-6.

3. The compound according to claim 2, characterized in that The conditions of the first reaction in the preparation method of the compound include: reaction temperature of 80-90° C.; reaction time of 2-6 h; And / or, the molar ratio of the compound represented by formula III to the compound represented by formula V is 1:4-4.

5.

4. The compound according to claim 3, characterized in that The preparation of the compound represented by formula III comprises the following steps: The compound represented by Formula VI is contacted with the compound represented by Formula VII to undergo a second reaction to obtain the compound represented by Formula III; Formula VI; Formula VII; Wherein, R1 is a C2-C4 alkyl group, R2 is a C2-C4 alkyl group, and m is an integer of 1-8; n is an integer of 1 to 3, and P is a halogen atom.

5. The compound according to claim 4, characterized in that The conditions for the second reaction in the preparation method of the compound include: reaction temperature of 30-80° C.; reaction time of 2-8 h; And / or, the molar ratio of the compound represented by Formula VI to the compound represented by Formula VII is 1:4-6.

6. The compound according to claim 5, characterized in that The conditions for the second reaction in the preparation method of the compound include: reaction temperature of 40-60° C.; reaction time of 3-6 h; And / or, the molar ratio of the compound represented by Formula VI to the compound represented by Formula VII is 1:4-4.

5.

7. The compound according to claim 1, characterized in that The conditions of the third reaction in the preparation method of the compound include: reaction temperature of 70-120° C.; reaction time of 4-10 h; And / or, the molar ratio of the compound represented by formula VIII to the compound represented by formula IX is 1:6-30; And / or, the catalyst is selected from alkali metal hydroxides.

8. The compound according to claim 7, characterized in that The conditions of the third reaction in the preparation method of the compound include: reaction temperature of 80-110° C.; reaction time of 5-8 h; And / or, the molar ratio of the compound represented by formula VIII to the compound represented by formula IX is 1:15-24.

9. Use of the compound according to claims 1 to 8 in a clay stabilizer.

Images