Compound and formulation having emulsifying function, and preparation and application thereof

Abstract

The present invention relates to the field of drilling fluids. Disclosed are a compound and a formulation having an emulsifying function, and a preparation and application thereof. The compound has a chemical structure as shown in formula 1. The compound exhibits high-temperature resistance, allowing a maximum service temperature of a drilling fluid to reach 240°C, with good long-term aging stability, and can significantly improve stability of water-in-oil emulsion under high temperature conditions; moreover, the compound can be used alone without the need for an auxiliary emulsifier, is synthesized by a straightforward method under mild conditions, and effectively solves the problem of inadequate temperature resistance of existing emulsifiers.

Description

Compounds and preparations with emulsifying function, their preparation and application

[0001] Cross-references to related applications

[0002] This application claims the benefit of Chinese Patent Application No. 202411873245.5, filed on December 18, 2024, the contents of which are incorporated herein by reference. Technical Field

[0003] This invention relates to the field of drilling fluids, and more specifically to a compound and preparation with emulsifying function, as well as its preparation and application. Background Technology

[0004] In drilling complex formations such as shale gas horizontal wells and easily fractured zones, the dispersive effect of water on clay makes conventional water-based drilling fluid systems prone to clay hydration and dispersion, leading to wellbore instability, especially in formations with high shale and mud content, which can severely impact downhole safety. In contrast, oil-based drilling fluids, with diesel (or white oil) as the continuous phase, do not cause clay hydration and dispersion, thus promoting wellbore stability. Furthermore, compared to water-based drilling fluids, oil-based fluids offer better lubrication, lower friction, and are beneficial for reservoir protection, and are now widely used in drilling various complex formations. Currently, the oil-water ratio of oil-based drilling fluids used in the field is generally between 8:2 and 95:5. To ensure the stability of oil-based drilling fluid performance, oil-based emulsifiers must be used to reduce the interfacial tension between oil and water and maintain emulsion stability.

[0005] With the development of drilling technology, the number of deep and ultra-deep wells is increasing. Influenced by geothermal gradients, bottom-hole temperatures are rising, with some exceeding 200°C. Therefore, ensuring emulsion stability at high temperatures is a primary concern for oil-based drilling fluids during drilling, and oil-based emulsifiers are crucial. For example, CN109097005B discloses an oil-based emulsifier synthesized from cashew phenol, epichlorohydrin, dimethylamine, and 1,3-propanesulfonic acid lactone, exhibiting temperature resistance up to 180°C. CN106367041B discloses an emulsifier synthesized from oxidized tall oil fatty acids, diethylenetriamine, tetraethylenepentamine, p-methylpropanesulfonic acid, and chlorosulfonic acid, demonstrating good emulsion stability and temperature resistance up to 200°C. The oil-based emulsifiers synthesized in these two schemes are mainly oil-soluble molecules with linear or comb-like structures, lacking sufficient temperature resistance to meet the drilling requirements of high-temperature formations exceeding 230°C.

[0006] Therefore, there is a need to develop an oil-based emulsifier compound that can withstand higher temperatures, as well as its preparation method and composition. Summary of the Invention

[0007] The purpose of this invention is to overcome the problem of insufficient high-temperature resistance in the prior art, and to provide a compound and preparation with emulsifying function, as well as its preparation and application.

[0008] To achieve the above objectives, a first aspect of the present invention provides a compound with emulsifying function, characterized in that the compound has the chemical structure shown in Formula 1:

[0009] In Formula 1, at least one R1 is selected from the chemical structure shown in Formula 2;

[0010] In Formula 1, the six R1s are the same or different and are each independently selected from H, C1-C4 alkyl groups or the chemical structure shown in Formula 2;

[0011] In Formula 2, R2 may be the same or different and each is independently selected from C1-C4 alkylene groups;

[0012] In Formula 2, R is the same or different and is independently selected from substituted or unsubstituted C8-C22 alkyl or C6-C30 aryl groups;

[0013] In Formula 2, Z may be the same or different and each is independently selected from carbonyl, sulfoxide or sulfone groups;

[0014] In Formula 2, the five R3s are the same or different and are each independently selected from H, C1-C4 alkyl or amino-substituted formyl groups;

[0015] In Equation 2, a and b are either the same or different and are each independently selected from natural numbers between 0 and 4.

[0016] A second aspect of the present invention provides a method for preparing an emulsifying agent, characterized in that the method comprises: sequentially reacting a compound of formula B with a compound of formula A and a compound of formula C, or sequentially reacting a compound of formula B with a compound of formula C and a compound of formula A;

[0017] Wherein, R1' is selected from H, C1-C4 alkyl, carboxyl, acyl halide or forms an anhydride with an adjacent R1', and at least one R1' in formula A is selected from carboxyl, acyl halide or forms an anhydride with an adjacent R1';

[0018] c is 1 or 2;

[0019] L is selected from hydroxyl, oxygen, or halogen;

[0020] The definitions of R2, R3, R, Z, a, and b are the same as those described in the first aspect of this invention.

[0021] The third aspect of the present invention provides a formulation prepared by the method described in the second aspect of the present invention.

[0022] The fourth aspect of the present invention provides the application of the formulations described in the first aspect of the present invention and / or the formulations described in the third aspect of the present invention in drilling fluids.

[0023] A fifth aspect of the present invention provides a composition, characterized in that the composition comprises a liquid hydrocarbon, a compound having emulsifying function, and a treatment agent;

[0024] The definition of the compound is the same as that described in the first and / or third aspects of this invention.

[0025] The sixth aspect of the present invention provides the use of the composition described in the fifth aspect of the present invention in drilling fluids.

[0026] Through the above technical solution, the present invention has the following beneficial effects:

[0027] 1. The compounds provided by this invention have high temperature resistance, especially those prepared by using pyromellitic tricarbonyl or tetracarbonyl compounds, as well as triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine or hexaethyleneheptamine as raw materials as emulsifiers, which can enable drilling fluids to withstand high temperatures up to 240°C.

[0028] 2. The high-temperature resistant oil-based drilling fluid emulsifier prepared by the technical solution of the present invention can significantly improve the stability of water-in-oil emulsions under high temperature conditions, has good long-term aging stability, and can be used alone without the need for auxiliary emulsifiers. The synthesis method is simple and the conditions are mild, which can effectively solve the problem of insufficient temperature resistance of existing emulsifiers. Attached Figure Description

[0029] Figure 1 is the infrared spectrum of the target compound described in Example 3;

[0030] Figure 2 is the carbon NMR spectrum of the target compound described in Example 3;

[0031] Figure 3 is the 1H NMR spectrum of the target compound described in Example 3. Detailed Implementation

[0032] The endpoints and any values ​​of the ranges 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 endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0033] To achieve the above objectives, a first aspect of the present invention provides a compound with emulsifying function, characterized in that the compound has the chemical structure shown in Formula 1:

[0034] In Formula 1, at least one R1 is selected from the chemical structure shown in Formula 2;

[0035] In Formula 1, the six R1s are the same or different and are each independently selected from H, C1-C4 alkyl groups or the chemical structure shown in Formula 2;

[0036] In Formula 2, each R2 may be the same or different and is independently selected from C1-C4 alkylene groups;

[0037] In Formula 2, each R is the same or different and is independently selected from substituted or unsubstituted C8-C22 alkyl or C6-C30 aryl groups;

[0038] In Formula 2, each Z is the same or different and is independently selected from carbonyl, sulfoxide or sulfone groups;

[0039] In Formula 2, the five R3s are the same or different and are each independently selected from H, C1-C4 alkyl or amino-substituted formyl groups;

[0040] In Equation 2, a and b are either the same or different and are each independently selected from natural numbers between 0 and 4.

[0041] In some embodiments of the present invention, preferably, the amino-substituted formyl group has the structure shown in Formula 3:

[0042] In Formula 3, the two R4s are the same or different and are each independently selected from H, C1-C4 alkyl groups or the chemical structure shown in Formula 4.

[0043] In some embodiments of the present invention, preferably, at least one of R3 in Formula 2 is selected from the chemical structure shown in Formula 3.

[0044] In some embodiments of the present invention, preferably, R2 in Formula 4 is the same or different and each is independently selected from C1-C4 alkylene groups.

[0045] In some embodiments of the present invention, preferably, each R in Formula 4 is the same or different and is independently selected from substituted or unsubstituted C8-C22 alkyl or C6-C30 aryl.

[0046] In some embodiments of the present invention, preferably, each Z in Formula 4 is the same or different and is independently selected from carbonyl or sulfone groups.

[0047] In some embodiments of the present invention, preferably, a and b in Formula 4 are the same or different and are each independently selected from natural numbers from 0 to 4.

[0048] In some embodiments of the present invention, preferably, R1 is selected from H, C1-C2 alkyl groups or the chemical structure shown in Formula 2.

[0049] In some embodiments of the present invention, preferably, R2 is selected from C1-C2 alkylene groups.

[0050] In some embodiments of the present invention, preferably, R3 is selected from H, C1-C2 alkyl groups or the chemical structure shown in Formula 3.

[0051] In some embodiments of the present invention, preferably, R4 is selected from H, C1-C2 alkyl groups or the chemical structure shown in Formula 4.

[0052] In some embodiments of the present invention, preferably, R is selected from substituted or unsubstituted C10-C20 alkyl or C6-C28 aryl.

[0053] In some embodiments of the present invention, preferably, Z is a carbonyl group or a sulfone group.

[0054] In some embodiments of the present invention, preferably, a and b are each independently selected from natural numbers from 0 to 3.

[0055] In some embodiments of the present invention, preferably, at least two R1s in Formula 1 are selected from the chemical structures shown in Formula 2.

[0056] In some embodiments of the present invention, preferably, at least two R3s in Formula 2 are selected from the chemical structures shown in Formula 3.

[0057] In some embodiments of the present invention, preferably, R1 is selected from H or the chemical structure shown in Formula 2.

[0058] In some embodiments of the present invention, R2 is preferably ethylene.

[0059] In some embodiments of the present invention, preferably, R3 is selected from H or the chemical structure shown in Formula 3.

[0060] In some embodiments of the present invention, preferably, R4 is selected from H or the chemical structure shown in Formula 4.

[0061] In some embodiments of the present invention, preferably, R is selected from substituted or unsubstituted C11-C18 alkyl or C6-C26 aryl.

[0062] In some embodiments of the present invention, preferably, a and b are each independently selected from natural numbers between 0 and 2.

[0063] In some embodiments of the present invention, preferably, at least three R1s in Formula 1 are selected from the chemical structures shown in Formula 2.

[0064] In some embodiments of the present invention, preferably, at least three R3s in Formula 2 are selected from the chemical structures shown in Formula 3.

[0065] In some embodiments of the present invention, preferably, R is selected from substituted or unsubstituted C14-C18 alkyl or C6-C24 aryl.

[0066] In some embodiments of the present invention, preferably, three or four R1s in Formula 1 are selected from the chemical structures shown in Formula 2.

[0067] In some embodiments of the present invention, preferably, three or four R3s in Formula 2 are selected from the chemical structures shown in Formula 3.

[0068] In some embodiments of the present invention, preferably, the chemical structure of the compound is shown in Formula 1-1 or 1-2:

[0069] In Formula 1-1, R1 represents the chemical structure shown in Formula 2-1; in Formula 1-2, R1 represents the chemical structure shown in Formula 2-2; R2 represents 1,2-ethylidene; and R3 represents the chemical structure shown in Formula 3.

[0070] In Formula 3, R4 represents the chemical structure shown in Formula 4; in Formula 2 and Formula 4, a is the same and is selected from natural numbers between 0 and 2; in Formula 2 and Formula 4, b is the same and is selected from natural numbers between 0 and 2.

[0071] In this invention, there are no particular requirements for the specific preparation method of the compound described in the first aspect. Those skilled in the art can determine a suitable synthesis method based on the structural formula provided by this invention and known knowledge in the field of organic synthesis, or they can prepare the aforementioned compound using the specific examples (replacement raw materials) provided later in this invention. However, preferably, the second aspect of this invention provides a method for preparing the emulsifying agent comprising:

[0072] The compound shown in Formula B is subjected to a condensation reaction in sequence with the compound shown in Formula A and the compound shown in Formula C, or the compound shown in Formula B is subjected to a condensation reaction in sequence with the compound shown in Formula C and the compound shown in Formula A.

[0073] Wherein, R1' is selected from H, C1-C4 alkyl, carboxyl, acyl halide or forms an anhydride with an adjacent R1', and at least one R1' in formula A is selected from carboxyl, acyl halide or forms an anhydride with an adjacent R1';

[0074] c is 1 or 2;

[0075] L is selected from hydroxyl, oxygen, or halogen;

[0076] The definitions of R2, R3, R, Z, a, and b are the same as those described in the first aspect of this invention.

[0077] In some embodiments of the present invention, preferably, R1' is selected from H, C1-C2 alkyl, carboxyl, acyl halide or forms an anhydride with an adjacent R1', and at least two R1' in Formula A are selected from carboxyl, acyl halide or form an anhydride with an adjacent R1'.

[0078] In some embodiments of the present invention, preferably, R1' is selected from H, carboxyl, acyl halide or forms an anhydride with adjacent R1', and at least three R1' in formula A are selected from carboxyl, acyl halide or form an anhydride with adjacent R1'.

[0079] In some embodiments of the present invention, preferably, three or four R1' in Formula A are selected from carboxyl groups, acyl halides, or form an anhydride with adjacent R1'.

[0080] In some embodiments of the present invention, preferably, the compound represented by Formula A is pyromellitic acid, pyromellitic anhydride, pyromellitic tetracarboxylic acid, or pyromellitic tetracarboxylic anhydride.

[0081] In some embodiments of the present invention, preferably, the compound represented by formula C is decanoic acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, octadecanoic acid, benzenesulfonic acid, dodecylbenzenesulfonic acid, tetradecylbenzenesulfonic acid, hexadecylbenzenesulfonic acid, or octadecylbenzenesulfonic acid.

[0082] In some embodiments of the present invention, preferably, the condensation reaction is carried out in the presence of a solvent and a protective gas.

[0083] In some embodiments of the present invention, the protective gas does not react with other components in the reaction system and is an inactive gas. Preferably, the protective gas is selected from nitrogen and / or argon.

[0084] In some embodiments of the present invention, preferably, the solvent is selected from dimethylformamide, dimethyl sulfoxide and N-methylpyrrolidone, and more preferably dimethyl sulfoxide.

[0085] In this invention, there is no particular limitation on the amount of solvent used, but preferably, the molar ratio of the compound represented by Formula A to the solvent is 1:0.5-10.

[0086] In some embodiments of the present invention, preferably, the molar ratio of the compound represented by formula A (used in the condensation reaction, as in step (3) described later), the compound represented by formula B, and the compound represented by formula C (used in the condensation reaction, as in step (4) described later) is 1:1-15:5-100, more preferably 1:1-12:6-90, and more preferably 1:1-10:7-80.

[0087] In this invention, the amount of compound B can be measured by the amount of compound A in the following amidation reaction.

[0088] In some embodiments of the present invention, preferably, the temperature of the condensation reaction is 120-300°C, more preferably 150-250°C.

[0089] In some embodiments of the present invention, preferably, the condensation reaction time is 0.5-16 h, more preferably 2-12 h.

[0090] In some embodiments of the present invention, preferably, the method for preparing the compound represented by formula B includes:

[0091] The compounds shown in Formula A, Formula C, and Formula D are contacted and subjected to an amidation reaction to obtain a product containing the compound with the structure shown in Formula B, which is then used for a further reaction with the compounds shown in Formula A and Formula C.

[0092] Wherein, the definitions of R2, a, and b correspond to the definitions described in the first aspect of the present invention. Preferably, the compound represented by formula D is selected from triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, or heptaethyleneoctamine.

[0093] The definitions of the compounds shown in Formula A and Formula C are the same as those defined above.

[0094] In some embodiments of the present invention, preferably, the amidation reaction is carried out in the presence of a solvent and a protective gas.

[0095] In some embodiments of the present invention, the protective gas does not react with other components in the reaction system and is an inactive gas. Preferably, the protective gas is selected from nitrogen and / or argon.

[0096] In some embodiments of the present invention, preferably, the solvent is selected from at least one of dimethyl sulfoxide, dimethylformamide and N-methylpyrrolidone, and more preferably dimethyl sulfoxide.

[0097] In some embodiments of the present invention, preferably, the molar ratio of the compound represented by formula A (used in the amidation reaction, as in step (1) described later), the compound represented by formula C (used in the amidation reaction, as in step (2) described later) and the compound represented by formula D is 1:3-30:1-4.2, more preferably 1:3-25:2-4.2, and more preferably 1:4-22:3-4.1.

[0098] In some embodiments of the present invention, preferably, the temperature of the amidation reaction is 150-300°C, more preferably 170-250°C.

[0099] In some embodiments of the present invention, preferably, the amidation reaction takes 0.5-16 hours, more preferably 2-12 hours.

[0100] According to a particularly preferred embodiment of the present invention, the method for preparing the emulsifying agent includes:

[0101] (1) Contact the compound shown in formula A and the compound shown in formula D and carry out the first amidation reaction;

[0102] (2) The product of the first amidation reaction is mixed with the compound shown in formula C to carry out a second amidation reaction;

[0103] (3) The product of the second amidation reaction is mixed with the compound shown in Formula A to carry out the first condensation reaction;

[0104] (4) The product of the first condensation reaction is mixed with the compound shown in formula C to carry out a second condensation reaction.

[0105] In this preferred embodiment, the preferred raw materials and their proportions are as described above.

[0106] Preferably, the conditions for the first amidation reaction are: a temperature of 150-300°C, more preferably 170-250°C (e.g., any value or a range between any two of 170°C, 180°C, 190°C, 200°C, 210°C, 220°C, 230°C, 240°C, and 250°C); and a time of 0.3-8 h, more preferably 0.5-6 h (e.g., any value or a range between any two of 0.5 h, 0.7 h, 0.9 h, 1 h, 2 h, 3 h, 4 h, 5 h, and 6 h).

[0107] Preferably, the conditions for the second amidation reaction are: a temperature of 150-300°C, more preferably 170-250°C (e.g., any value or a range between any two of 170°C, 180°C, 190°C, 200°C, 210°C, 220°C, 230°C, 240°C, and 250°C); and a time of 0.3-8 h, more preferably 0.5-6 h (e.g., any value or a range between any two of 0.5 h, 0.7 h, 0.9 h, 1 h, 2 h, 3 h, 4 h, 5 h, and 6 h).

[0108] Preferably, the conditions for the first condensation reaction are: a temperature of 120-300°C, more preferably 150-250°C (e.g., any value or a range between any two of 150°C, 160°C, 170°C, 180°C, 190°C, 200°C, 210°C, 220°C, 230°C, 240°C, and 250°C); and a time of 0.5-8 h, more preferably 1-6 h (e.g., any value or a range between any two of 1 h, 2 h, 3 h, 4 h, 5 h, and 6 h).

[0109] Preferably, the conditions for the second condensation reaction are: a temperature of 120-300°C, more preferably 150-250°C (e.g., any value or a range between any two of 150°C, 160°C, 170°C, 180°C, 190°C, 200°C, 210°C, 220°C, 230°C, 240°C, and 250°C); and a time of 0.3-8 h, more preferably 0.5-6 h (e.g., any value or a range between any two of 0.5 h, 0.7 h, 0.9 h, 1 h, 2 h, 3 h, 4 h, 5 h, and 6 h).

[0110] The third aspect of the present invention provides a formulation prepared by the method described in the second aspect of the present invention.

[0111] The fourth aspect of the present invention provides the use of the compounds described in the first aspect of the present invention and / or the formulations described in the third aspect of the present invention in drilling fluids.

[0112] A fifth aspect of the present invention provides a composition, characterized in that the composition comprises a liquid hydrocarbon, a compound having emulsifying function, and a treatment agent;

[0113] The definition of the compound is the same as that described in the first aspect of the present invention.

[0114] In some embodiments of the present invention, preferably, the liquid hydrocarbon is selected from at least one of diesel oil, white oil, kerosene and liquid paraffin, and more preferably diesel oil and / or white oil.

[0115] In some embodiments of the present invention, preferably, the content of the liquid hydrocarbon is 22-52 wt%, more preferably 27-39 wt%, based on the total weight of the composition.

[0116] In some embodiments of the present invention, preferably, the content of the compound is 0.6-2.6 wt%, more preferably 1.1-2.1 wt%, based on the total weight of the composition.

[0117] In some embodiments of the present invention, preferably, the treatment agent is selected from at least one of organic soil, organic diatomaceous earth, organic sepiolite soil and organic attapulgite soil, and preferably organic soil.

[0118] In some embodiments of the present invention, preferably, the content of the treatment agent is 0.4-2.4 wt%, more preferably 1-2 wt%, based on the total weight of the composition.

[0119] In some embodiments of the present invention, preferably, the composition further includes at least one of a filtration loss reducer, a water activity control agent, and an alkalinity regulator.

[0120] In some embodiments of the present invention, preferably, the filtration loss reducing agent is selected from at least one of oxidized asphalt, humic acid amide and ammonium humate, and preferably oxidized asphalt and humic acid amide.

[0121] In some embodiments of the present invention, preferably, the water activity control agent is selected from soluble hydrochloride, nitrate and sulfate, and more preferably at least one of calcium chloride, magnesium chloride, sodium chloride and potassium chloride.

[0122] In some embodiments of the present invention, preferably, the alkalinity regulator is selected from metal oxides, and more preferably calcium oxide and / or magnesium oxide.

[0123] In some embodiments of the present invention, the content of the filtration loss reducing agent is 1.3-5.3 wt%, preferably 2.3-4.3 wt%, based on the total weight of the composition.

[0124] In some embodiments of the present invention, preferably, the content of the water activity control agent is 0.1-1.1 wt%, more preferably 0.3-0.9 wt%, based on the total weight of the composition.

[0125] In some embodiments of the present invention, preferably, the content of the alkalinity regulator is 0.6-2.6 wt%, more preferably 1.1-2.1 wt%, based on the total weight of the composition.

[0126] In some embodiments of the present invention, preferably, the composition further includes water.

[0127] In some embodiments of the present invention, preferably, the water content is 0.8-2.8 wt%, more preferably 1.3-2.3 wt%, based on the total weight of the composition.

[0128] The sixth aspect of the present invention provides the use of the composition described in the fifth aspect of the present invention in drilling fluids.

[0129] The compounds / compositions provided by this invention have high temperature resistance (withstanding temperatures up to 240°C), can significantly improve the stability of water-in-oil emulsions under high temperature conditions, have high emulsification rates, and can be used alone without the need for commonly used auxiliary emulsifiers such as polysorbate, sodium dodecylbenzenesulfonate, and polyether emulsifiers. This simplifies the formulation, reduces compatibility requirements, and lowers material and labor costs.

[0130] The present invention will be described in detail below through embodiments. In the following embodiments, the diesel feedstock is a commercially available product of grade 0 from Qilu Petrochemical Company; the white oil feedstock is a commercially available product of grade 3 from Qilu Petrochemical Company.

[0131] Example 1

[0132] 1 mol of pyromellitic acid was dissolved in 1 mol of dimethyl sulfoxide and then added to a reaction vessel. Nitrogen gas was purged for 30 min to remove oxygen. 3 mol of tetraethylenepentamine was added under stirring. The mixture was heated to 180°C and reacted for 1 h. 10 mol of dodecanoic acid was added to the reaction vessel and reacted for 0.5 h. Then, 0.1 mol of pyromellitic acid was added to the reaction vessel and the reaction continued for 3 h. The temperature was lowered to 150°C. 4.5 mol of dodecylbenzenesulfonic acid was added to the reaction vessel and the reaction continued for 0.5 h. The temperature was lowered to 100°C. White oil, accounting for 25% of the total mass of the above raw materials, was added to the reaction vessel and cooled to room temperature to obtain a high-temperature resistant oil-based drilling fluid emulsifier, denoted as S1.

[0133] Example 2

[0134] 1 mol of pyromellitic acid was dissolved in 5 mol of N,N-dimethylformamide and then added to a reaction vessel. Nitrogen gas was purged for 10 min to remove oxygen. Under stirring, 4.1 mol of triethylenetetramine was added, and the mixture was heated to 220°C and reacted for 0.5 h. 11 mol of oleic acid was added to the reaction vessel, and the mixture was reacted for 1.5 h. Then, 0.05 mol of pyromellitic acid was added to the reaction vessel, and the reaction was continued for 2 h. The temperature was lowered to 170°C, and then 4 mol of dodecylbenzenesulfonic acid was added to the reaction vessel, and the reaction was continued for 0.6 h. The temperature was lowered to 80°C, and then 20% of the total mass of the above raw materials (white oil) was added to the reaction vessel. The mixture was cooled to room temperature to obtain a high-temperature resistant oil-based drilling fluid emulsifier, denoted as S2.

[0135] Example 3

[0136] 1 mol of pyromellitic anhydride was dissolved in 0.5 mol of dimethyl sulfoxide and then added to a reaction vessel. Nitrogen gas was purged for 15 min to remove oxygen. Under stirring, 4 mol of hexaethylene heptaamine was added, and the mixture was heated to 170°C and reacted for 2 h. 6 mol of oleic acid was added to the reaction vessel and the mixture was reacted for 2 h. Then, 0.3 mol of pyromellitic anhydride was added to the reaction vessel and the reaction was continued for 1 h. The temperature was lowered to 140°C, and then 22 mol of dodecylbenzenesulfonic acid was added to the reaction vessel and the reaction was continued for 1 h. The temperature was lowered to 90°C, and then 30% of the total mass of the above raw materials (white oil) was added to the reaction vessel. The mixture was then cooled to room temperature to obtain a high-temperature resistant oil-based drilling fluid emulsifier, denoted as S3.

[0137] Before adding the white oil, 1g of the reaction system in the reaction vessel was taken and washed five times with deionized water while stirring, then washed twice with ethanol to purify the target product of the reaction. After removing the ethanol, the obtained product was characterized by infrared spectroscopy, carbon NMR spectroscopy, and hydrogen NMR spectroscopy, and the results are shown in Figures 1-3, respectively. As shown in Figure 1, 3440cm -1 The absorption peak at 2925 cm⁻¹ is due to the stretching vibration of the amide group (-CONH-), indicating that the reaction formed an amide bond. -1 Yes, it is the absorption peak of the CH3 stretching vibration, 1722 cm⁻¹. -1 It is the absorption peak of the -C=O stretching vibration, at 1179 cm⁻¹. -1 and 1036cm -1 The absorption peak for the -SO3 stretching vibration indicates that the S3 contains the aforementioned functional groups.

[0138] As shown in Figure 2, 178 ppm is the carbon signal in C=O. 125-153 ppm is the carbon signal in the benzene ring, and below 50 ppm is the saturated C signal, indicating that the S3 contains these chemical groups.

[0139] As shown in Figure 3, the 7-8 ppm peaks represent hydrogen atoms on the benzene ring, and the multiplet at 5.2 ppm represents -HC=CH- hydrogen atoms, indicating that the S3 contains these types of hydrogen nuclei.

[0140] By comprehensively analyzing Figures 1-3, it can be determined that the target structure of the compound was synthesized in this embodiment, and the structure is shown below. Since the preparation methods of other embodiments and comparative examples are basically the same as those of Example 3, the only difference is that the raw materials and solvents used and their proportions are different, and some comparative examples have omitted some steps of Example 3. Therefore, the same separation, purification, characterization and analysis methods can be used to conclude that each embodiment and comparative example has prepared its own compound structure.

[0141] Where RZ is CH3(CH2)7CH=CH(CH2)7CO or CH3(CH2) 11C6H6SO2, a, b = 0, 1, 2, 3 or 4, and a + b = 4.

[0142] Example 4

[0143] 1 mol of pyromellitic acid was dissolved in 1 mol of dimethyl sulfoxide and then added to a reaction vessel. Nitrogen gas was purged for 30 min to remove oxygen. 3.1 mol of triethylenetetramine was added under stirring. The mixture was heated to 180°C and reacted for 1 h. 4 mol of tetradecanoic acid was added to the reaction vessel and reacted for 0.5 h. Then, 0.1 mol of pyromellitic acid was added to the reaction vessel and the reaction continued for 3 h. The temperature was lowered to 150°C. 7 mol of dodecylbenzenesulfonic acid was added to the reaction vessel and the reaction continued for 0.5 h. The temperature was lowered to 100°C. White oil, accounting for 25% of the total mass of the above raw materials, was added to the reaction vessel and cooled to room temperature to obtain a high-temperature resistant oil-based drilling fluid emulsifier, denoted as S4.

[0144] Example 5

[0145] 1 mol of pyromellitic anhydride was dissolved in 1 mol of dimethyl sulfoxide and then added to a reaction vessel. Nitrogen gas was purged for 30 min to remove oxygen. Under stirring, 4.1 mol of pentaethylenehexamine was added, and the mixture was heated to 180°C and reacted for 1 h. 10 mol of stearic acid was added to the reaction vessel and the mixture was reacted for 0.5 h. Then, 0.2 mol of pyromellitic anhydride was added to the reaction vessel and the reaction was continued for 3 h. The mixture was cooled to 150°C, and 14 mol of dodecylbenzenesulfonic acid was added to the reaction vessel and the reaction was continued for 0.5 h. The mixture was cooled to 100°C, and white oil, which accounted for 25% of the total mass of the above raw materials, was added to the reaction vessel. The mixture was then cooled to room temperature to obtain a high-temperature resistant oil-based drilling fluid emulsifier, denoted as S5.

[0146] Example 6

[0147] 1 mol of pyromellitic acid was dissolved in 1 mol of dimethyl sulfoxide and then added to a reaction vessel. Nitrogen gas was purged for 30 min to remove oxygen. Under stirring, 4 mol of tetraethylenepentamine was added, and the mixture was heated to 180°C and reacted for 1 h. 15.5 mol of hexadecanoic acid was added to the reaction vessel and the mixture was reacted for 0.5 h. Then, 0.25 mol of pyromellitic acid was added to the reaction vessel and the reaction was continued for 3 h. The temperature was lowered to 150°C, and 3 mol of dodecylbenzenesulfonic acid was added to the reaction vessel and the reaction was continued for 0.5 h. The temperature was lowered to 100°C, and white oil of 25% of the total mass of the above raw materials was added to the reaction vessel. The mixture was cooled to room temperature to obtain a high-temperature resistant oil-based drilling fluid emulsifier, denoted as S6.

[0148] Example 7

[0149] 1 mol of pyromellitic anhydride was dissolved in 1 mol of dimethyl sulfoxide and then added to a reaction vessel. Nitrogen gas was purged for 30 min to remove oxygen. Under stirring, 4 mol of hexaethyleneheptaamine was added, and the mixture was heated to 180°C and reacted for 1 h. 22 mol of oleic acid was added to the reaction vessel and the mixture was reacted for 0.5 h. Then, 0.15 mol of pyromellitic acid was added to the reaction vessel and the reaction was continued for 3 h. The temperature was lowered to 150°C, and 6 mol of dodecylbenzenesulfonic acid was added to the reaction vessel and the reaction was continued for 0.5 h. The temperature was lowered to 100°C, and white oil, which accounted for 25% of the total mass of the above raw materials, was added to the reaction vessel. The mixture was then cooled to room temperature to obtain a high-temperature resistant oil-based drilling fluid emulsifier, denoted as S7.

[0150] Example 8

[0151] The method of Example 1 was followed, except that 1.5 mol of terephthalic acid was used to replace 1 mol of trimesic acid to obtain an emulsifier for high-temperature oil-based drilling fluid, denoted as S8.

[0152] Example 9

[0153] The method was carried out according to Example 1, except that 2.1 mol of heptaethyleneoctamine was used to replace 3 mol of tetraethylenepentamine to obtain an emulsifier for high-temperature oil-based drilling fluid, denoted as S9.

[0154] Example 10

[0155] The method of Example 1 was followed, except that 10 mol of octanoic acid was used to replace 10 mol of dodecanoic acid to obtain an emulsifier for high-temperature oil-based drilling fluid, denoted as S10.

[0156] Example 11

[0157] The method was carried out according to Example 1, except that 0.1 mol of pyromellitic acid was replaced with 0.1 mol of 1,2,4-phenyltricarboxylic acid to obtain an emulsifier for high-temperature oil-based drilling fluid, denoted as S11.

[0158] Example 12

[0159] The method of Example 1 was followed, except that 4.5 mol of n-octanoic acid was used to replace 4.5 mol of dodecylbenzenesulfonic acid to obtain an emulsifier for high-temperature oil-based drilling fluid, denoted as S12.

[0160] Example 13

[0161] The method of Example 2 was followed, except that 2 mol of terephthalic acid was used to replace 1 mol of pyromellitic acid to obtain an emulsifier for high-temperature oil-based drilling fluid, denoted as S13.

[0162] Example 14

[0163] The method of Example 2 was followed, except that 2.3 mol of heptaethyleneoctamine was used to replace 4.1 mol of triethylenetetramine to obtain an emulsifier for high-temperature oil-based drilling fluid, denoted as S14.

[0164] Example 15

[0165] The method of Example 2 was followed, except that 11 mol of octanoic acid was used to replace 11 mol of oleic acid to obtain an emulsifier for high-temperature oil-based drilling fluid, denoted as S15.

[0166] Example 16

[0167] The method of Example 2 was followed, except that 0.05 mol of pyromellitic acid was replaced with 0.07 mol of 1,2,4-benzenetricarboxylic acid to obtain an emulsifier for high-temperature oil-based drilling fluid, denoted as S16.

[0168] Example 17

[0169] The method of Example 2 was followed, except that 4 mol of n-octanoic acid was used to replace 4 mol of dodecylbenzenesulfonic acid to obtain an emulsifier for high-temperature oil-based drilling fluid, denoted as S17.

[0170] Example 18

[0171] The process was carried out according to Example 2, except that 4.1 mol of triethylenetetramine was added, the temperature was raised to 140°C, 0.05 mol of pyromellitic acid was added, the reaction was continued for 2 hours, and the temperature was lowered to 130°C to obtain an emulsifier for high-temperature oil-based drilling fluid, denoted as S18.

[0172] Comparative Example 1

[0173] The method of Example 1 was followed, except that 1 mol trimellitic acid was used to replace 1 mol pyromellitic acid, and 0.1 mol pyromellitic acid and 4.5 mol dodecylbenzenesulfonic acid were not added, resulting in an emulsifier for high-temperature oil-based drilling fluid, denoted as D1.

[0174] Comparative Example 2

[0175] The method of Example 2 was followed, except that 11 mol of hexanoic acid was used to replace 11 mol of oleic acid to obtain an emulsifier for high-temperature oil-based drilling fluid, denoted as D2.

[0176] Comparative Example 3

[0177] The method of Example 3 was followed, except that 4 mol of hexanoic acid was used to replace 4 mol of dodecylbenzenesulfonic acid to obtain an emulsifier for high-temperature oil-based drilling fluid, denoted as D3.

[0178] Test case

[0179] (1) Emulsification rate

[0180] Measure 240 mL of 0# diesel oil and 12 g of emulsifier from each example and comparative example, and add them to a high-speed stirring cup. Stir at 10000 rpm for 20 min, then add 60 mL of distilled water and continue stirring for 30 min. Pour the prepared emulsion into a high-temperature aging tank, place it in a high-temperature roller furnace, and roll it at 240°C for 16 h. After cooling, stir at 10000 rpm for 20 min, pour it into a 500 mL graduated cylinder, and let it stand at room temperature for 24 h. Observe the volume V of the clear oil separated in the upper layer. Calculate the emulsification rate using the following formula:

[0181] W—Emulsification rate, %; V—Volume of oil layer separated in 24 hours, in milliliters (mL). The emulsification rates of the emulsifiers in each example and comparative example are shown in Table 1.

[0182] Table 1

[0183] (2) Temperature resistance

[0184] Measure 285 mL (239.4 g) of 0# diesel oil and add it to a high-speed stirring cup. Then, under high-speed stirring (stirring speed 11000 r / min, the same below), add 15 g of the high-temperature resistant oil-based drilling fluid emulsifier samples prepared in each example and comparative example, and stir at 11000 r / min for 10 min. Then, add 15 mL of calcium chloride aqueous solution (mass concentration 25%, density 1.2 g / cm³). 3 Add 4.5g of calcium chloride and 13.5g of water, and stir at 11000r / min for 20min; then add 10.5g of organic clay for oil-based drilling fluid and stir at high speed for 5min; then add 24.0g of oxidized asphalt filtration reducer and stir at high speed for 5min; then add 3.0g of oil-based cutting agent LVSP (produced by Sinopec Zhongyuan Petroleum Engineering Company) and stir at high speed for 5min; then add 12.0g of calcium oxide and stir at 11000r / min for 5min; then add 405g of barite and stir at 11000r / min for 20min. Pour into an aging tank and roll-age at 240℃ for 16h. The comprehensive performance of the oil-based drilling fluid after high-temperature aging is investigated according to the performance evaluation method of oil-based drilling fluid in GB / T 16783.2-2012, Field Testing of Drilling Fluids in the Petroleum and Natural Gas Industry. The comprehensive performance of the emulsifiers in each embodiment and comparative example is shown in Table 2 (where AV is the apparent viscosity, PV is the plastic viscosity, YP is the dynamic shear force, Gel is the initial and final shear, and ES is the demulsification voltage (instrument range ≤2048V)).

[0185] Table 2

[0186] (3) Long-term aging stability

[0187] Measure 285 mL (239.4 g) of 0# diesel oil and add it to a high-speed stirring cup. Then, under high-speed stirring (stirring speed 11000 r / min, the same below), add 15 g of the high-temperature resistant oil-based drilling fluid emulsifier samples prepared in each example and comparative example, and stir at 11000 r / min for 10 min. Then, add 15 mL of calcium chloride aqueous solution (mass concentration 25%, density 1.2 g / cm³). 3 Add 4.5g of calcium chloride and 13.5g of water, and stir at 11000r / min for 20min; then add 10.5g of organic soil for oil-based drilling fluid, and stir at 11000r / min for 5min; then add 24.0g of oxidized asphalt filtration reducer, and stir at 11000r / min for 5min; then add 12.0g of calcium oxide, and stir at 11000r / min for 5min; then add 3.0g of oil-based cutting agent LVSP (produced by Sinopec Zhongyuan Petroleum Engineering Company), and stir at high speed for 5min; then add 405g of barite, and stir at 11000r / min for 20min. Pour into an aging tank and roll age at 240℃ for 88h. The comprehensive performance of the oil-based drilling fluid after high-temperature aging is investigated according to the performance evaluation method of oil-based drilling fluid in GB / T 16783.2-2012, Field Testing of Drilling Fluids in the Petroleum and Natural Gas Industry.

[0188] Table 3

[0189] As shown in Table 3, the embodiment using the technical solution of the present invention can still maintain certain comprehensive performance after rolling aging at 240℃ for 88 hours. Compared with the comparative example that barite precipitation occurred after aging at the same temperature for 16 hours, the embodiment has obvious advantages in long-term aging stability.

[0190] As can be seen from the results in Tables 1-3, the embodiments using the technical solution of the present invention have significantly better effects compared with the comparative examples, including high temperature resistance (the highest temperature that can be withstood is up to 240℃), good long-term aging stability, significant improvement in the stability of water-in-oil emulsions under high temperature conditions, high emulsification rate, and the ability to be used alone without the need for auxiliary emulsifiers.

[0191] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

A compound having an emulsifying function, characterized by The compound has a chemical structure shown in Formula 1: In Formula 1, at least one R1 is selected from the chemical structure shown in Formula 2; In Formula 1, the six R1s are the same or different and are each independently selected from H, C1-C4 alkyl groups or the chemical structure shown in Formula 2; In Formula 2, R2 may be the same or different and each is independently selected from C1-C4 alkylene groups; In Formula 2, R is the same or different and is independently selected from substituted or unsubstituted C8-C22 alkyl or C6-C30 aryl groups; In Formula 2, Z may be the same or different and each is independently selected from carbonyl, sulfoxide or sulfone groups; In Formula 2, the five R3s are the same or different and are each independently selected from H, amino-substituted formyl or C1-C4 alkyl; In Equation 2, a and b are either the same or different and are each independently selected from natural numbers between 0 and 4. The compound according to claim 1, wherein, The amine group-substituted formyl group has a structure shown in Formula 3: In Formula 3, the two R4s are the same or different and are each independently selected from H, C1-C4 alkyl groups or the chemical structure shown in Formula 4; Preferably, at least one of R3 in Formula 2 is selected from the chemical structure shown in Formula 3; Preferably, R2 in Formula 4 is the same or different and each is independently selected from C1-C4 alkylene groups; Preferably, the R in Formula 4 are the same or different and are each independently selected from substituted or unsubstituted C8-C22 alkyl or C6-C30 aryl groups; Preferably, the Z in Formula 4 are the same or different and are each independently selected from carbonyl or sulfone groups; Preferably, in Equation 4, a and b are the same or different and are each independently selected from natural numbers between 0 and 4. The compound according to claim 1 or 2, wherein, R1 is selected from H, C1-C2 alkyl groups, or the chemical structure shown in Formula 2; And / or, R2 is selected from C1-C2 alkylene groups; And / or, R3 is selected from H, C1-C2 alkyl groups or the chemical structure shown in Formula 3; And / or, R4 is selected from H, C1-C2 alkyl groups or the chemical structure shown in Formula 4; And / or, R is selected from substituted or unsubstituted C10-C20 alkyl, C6-C28 aryl; And / or, Z is a carbonyl or sulfone group; And / or, a and b are each independently selected from natural numbers between 0 and 3; And / or, at least two R1s in Formula 1 are selected from the chemical structures shown in Formula 2; And / or, at least two of the R3s in Formula 2 are selected from the chemical structures shown in Formula 3. The compound according to claim 3, wherein, R1 is selected from H or the chemical structure shown in Formula 2; And / or, R2 is ethylene; And / or, R3 is selected from H or the chemical structure shown in Formula 3; And / or, R4 is selected from H or the chemical structure shown in Formula 4; And / or, R is selected from substituted or unsubstituted C11-C18 alkyl, C6-C26 aryl; And / or, a and b are each independently selected from natural numbers between 0 and 2; And / or, at least three R1s in Formula 1 are selected from the chemical structures shown in Formula 2; And / or, at least three R3s in Formula 2 are selected from the chemical structures shown in Formula 3. The compound according to claim 4, wherein, R is selected from substituted or unsubstituted C14-C18 alkyl, C6-C24 aryl; And / or, in Formula 1, three or four R1s are selected from the chemical structures shown in Formula 2; And / or, in Formula 2, three or four R3s are selected from the chemical structures shown in Formula 3. The compound according to claim 5, wherein, The chemical structure of the compound is shown as Formula 1-1 or 1-2: In Formula 1-1, R1 represents the chemical structure shown in Formula 2-1; in Formula 1-2, R1 represents the chemical structure shown in Formula 2-2; R2 represents 1,2-ethylidene; R3 represents the chemical structure shown in Formula 3; and R4 represents the chemical structure shown in Formula 4. In Formula 2 and Formula 4, a is the same and is selected from natural numbers from 0 to 2. In Equations 2 and 4, b is the same and is selected from natural numbers between 0 and 2. A method for preparing a formulation having an emulsifying function, characterized by, The method comprises: sequentially subjecting a compound shown in formula B to condensation reaction with a compound shown in formula A and a compound shown in formula C, or sequentially subjecting a compound shown in formula B to condensation reaction with a compound shown in formula C and a compound shown in formula A; Wherein, R1' is selected from H, C1-C4 alkyl, carboxyl, acyl halide or forms an anhydride with an adjacent R1', and at least one R1' in formula A is selected from carboxyl, acyl halide or forms an anhydride with an adjacent R1'; c is 1 or 2; L is selected from hydroxyl, oxygen, or halogen; The definitions of R2, R3, R, Z, a, and b are identical to those of any one of claims 1-6. The method of claim 7, wherein, R1' is selected from H, C1-C2 alkyl, carboxyl, acyl halide or forms an anhydride with an adjacent R1', and at least two R1' in Formula A are selected from carboxyl, acyl halide or form an anhydride with an adjacent R1'; Preferably, R1' is selected from H, carboxyl, acyl halide or forms an anhydride with an adjacent R1', and at least three R1' in Formula A are selected from carboxyl, acyl halide or form an anhydride with an adjacent R1'; Preferably, in formula A, three or four R1' are selected from carboxyl groups, acyl halides, or form an anhydride with adjacent R1'; Preferably, the compound represented by Formula A is pyromellitic acid, pyromellitic anhydride, pyromellitic tetracarboxylic acid, or pyromellitic tetracarboxylic anhydride; Preferably, the compound represented by Formula C is decanoic acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, octadecanoic acid, benzenesulfonic acid, dodecylbenzenesulfonic acid, tetradecylbenzenesulfonic acid, hexadecylbenzenesulfonic acid, or octadecylbenzenesulfonic acid. The method according to claim 7 or 8, wherein The condensation reaction is carried out in the presence of a solvent and a protective gas. Preferably, the protective gas is selected from nitrogen and / or argon; Preferably, the solvent is selected from dimethylformamide, dimethyl sulfoxide, and N-methylpyrrolidone, and more preferably dimethyl sulfoxide. The method according to any one of claims 7-9, wherein, The molar ratio of the compound represented by Formula A to the solvent is 1:0.5-10; Preferably, the molar ratio of the compound represented by Formula A, the compound represented by Formula B, and the compound represented by Formula C is 1:1-15:5-100, more preferably 1:1-12:6-90, and even more preferably 1:1-10:7-80. The method according to any one of claims 7-10, wherein, The temperature of the condensation reaction is 120-300℃, preferably 150-250℃; Preferably, the condensation reaction takes 0.5-16 hours, more preferably 2-12 hours. The formulation prepared by the method according to any one of claims 7-11. The use of the compound according to any one of claims 1-6 and / or the formulation according to claim 12 in drilling fluids.

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