Tri-armed abietic-based s-apg phenolic acid esters, methods of making and uses thereof

Abstract

The present application relates to the technical field of oil and gas field development, and is a kind of three-arm rosin-based S-APG phenolic acid ester and its preparation method and application, the present application takes natural rosin derivative dehydroabietinol as starting material, and is prepared by bromination, thio reaction to obtain dehydroabietyl methyl mercaptan;Again, acetylation bromide glucose is carried out glycosidation, deprotection to obtain thio glucose intermediate;Through 1,3,5-benzene triformyl chloride, three-arm skeleton is constructed, and esterification, catalytic hydrogenation deprotection of benzyl protected gallic acid, synthesis three-arm rosin-based S-APG phenolic acid ester.The product is compounded with co-surfactant and water to obtain gas-soluble foaming agent system.The foaming agent has the characteristics of good CO2 solubility, excellent foaming and stable foaming performance, green environmental protection and the like, and is suitable for low permeability, dense and water-sensitive reservoirs, and can effectively inhibit gas channeling and improve CO2 oil displacement efficiency.

Description

Technical Field

[0001] This invention relates to the field of oil and gas field development technology, and is a three-arm rosin-based S-APG phenolic ester, its preparation method and application. Background Technology

[0002] CCUS (Carbon Capture, Utilization, and Storage) is a new development trend of CCS (Carbon Capture and Storage) technology. It involves capturing and purifying CO2 emitted during production processes and then reusing it in new production processes, allowing for recycling rather than simple storage. Compared to CCS, it can realize CO2 resources, generate economic benefits, and is more practically feasible. CO2 flooding is a key step in the carbon utilization and storage of CCUS technology in oil and gas field development, and its development has spanned several decades. CO2 flooding technology improves oil recovery through mechanisms such as reducing crude oil viscosity, increasing formation energy, reducing oil-water interfacial tension, and, under certain conditions, miscibility with crude oil. It has become a highly promising enhanced oil recovery technology. However, due to the low density and viscosity of CO2, as well as the heterogeneity of formations, viscous fingering, gravity overtrapping, and gas channeling can occur, affecting the effectiveness of CO2 flooding and even causing ineffective CO2 recycling. Therefore, controlling its mobility is crucial for improving CO2 injection effectiveness.

[0003] CO2 foam is a commonly used flow control agent in oil and gas fields. It is a multiphase dispersion system formed by CO2 dispersed in a liquid phase with the assistance of surfactants. The resulting liquid film disperses the gas, reduces the flowability of the gas phase, and weakens the flowability difference between CO2 and crude oil, thus effectively improving fingering at the displacement front. Simultaneously, due to the foam's inherent characteristic of "blocking large pores but not small ones, blocking water but not oil," it effectively mitigates gas channeling. During the plugging process, the foam preferentially enters high-permeability large pores. Due to the high apparent viscosity of the foam system during flow and the Jamin effect in the pores, the flow resistance increases with the amount of foam injected, causing the displacing fluid to gradually flow into low-permeability small pores, expanding the swept volume. However, conventional CO2 foam is mainly a water-based system, with high adsorption and retention of surfactants on the rock surface. Injected water may affect the contact between CO2 and crude oil. For water-sensitive reservoirs, this can easily cause hydration collapse, pore throat blockage, and matrix damage, significantly reducing reservoir permeability. Therefore, research was conducted on CO2 foam systems with strong inhibition / non-aqueous properties for tight reservoirs and water-sensitive reservoirs.

[0004] Aerosol foam is a newly emerging CO2 foam system. Its foaming agent is soluble in CO2 and can be carried into the designated target layer, reducing the impact of reservoir damage in water-based systems on CO2 flooding. It also exhibits good foaming and foam-stabilizing properties, promoting the formation of foam from CO2 and formation water, achieving a "foam generation wherever gas is present" effect. This allows for effective control of CO2 mobility, significantly improving sweep efficiency, making it one of the most effective systems for mobility control in tight and water-sensitive reservoirs. Currently, aerosol foams often contain silicone and fluorine, posing significant environmental hazards. Therefore, it is necessary to research a non-toxic, harmless, highly soluble, and foaming agent.

[0005] Chinese patent document CN114316939A discloses a carbon dioxide aerosol foaming agent suitable for tight reservoirs. Its specific components include the following raw materials by mass percentage: 0.03–6.5% foaming agent main agent, 0.01–5% foam stabilizer, 0.01–5% foam promoter, 0.01–5% liquid film strengthening agent, 0.01–3% alkaline substance, 0.01–10% co-solvent, and the balance being water. It exhibits good solubility in supercritical carbon dioxide and good thermal stability, resistance to high salinity, and temperature resistance. This foaming agent also features a long foaming half-life and a strong overall foam index. The component ratios can be adjusted to optimize costs according to different geological conditions.

[0006] Chinese patent document CN119264411A discloses an amidoylated polymethyl hydrocarbon ether aerosol foaming agent and its preparation method. This invention uses an amidoylated polymethyl hydrocarbon ether surfactant as an amidoylated polymethyl hydrocarbon ether aerosol foaming agent, which is not only low in cost and suitable for large-scale industrial application in tertiary oil recovery, but also has excellent aerosolization and foam stability under high temperature and high salinity conditions. At the same time, it has good solubility in CO2 and is well carried and transported to the reservoir.

[0007] Chinese patent document CN119286493A discloses a hydrocarbon-based carbon dioxide aerosol blowing agent composition and its preparation method. The hydrocarbon-based carbon dioxide aerosol blowing agent composition comprises: 0.2-0.5% aerosolizing agent, 0.1-0.3% aerosolizing accelerator, and 0.3-1.0% aerosolizing stabilizer. This hydrocarbon-based carbon dioxide aerosol blowing agent composition is inexpensive, non-toxic, has excellent aerosolization, and good foam stability; it also has a simple composition, is easy to prepare, exhibits good solubility, high stability, good temperature and salt resistance in a CO2 environment, and low transportation costs.

[0008] In summary, existing CO2-driven foam systems generally suffer from high adsorption in conventional water-based foam reservoirs, significant water-sensitive damage, and are prone to causing formation hydration collapse and pore throat blockage. At the same time, most aerosol foaming agents contain silicone and fluorine components, resulting in serious environmental pollution. Furthermore, existing products have simple molecular structures, poor CO2 solubility, weak foam stability, limited raw material sources, and high costs, making them difficult to adapt to the flow regulation requirements of low-permeability, dense, and water-sensitive reservoirs. Summary of the Invention

[0009] This invention provides a three-armed rosin-based S-APG phenolic ester, its preparation method, and its application, overcoming the shortcomings of the prior art. It can effectively solve the problems of limited sources, high prices, and the fact that conventional aerosol foam systems usually contain silicon and fluorine, causing serious environmental pollution.

[0010] One of the technical solutions of the present invention is achieved through the following measures: a three-armed rosin-based S-APG phenolic ester having the following chemical structure: .

[0011] The following are further optimizations and / or improvements to one of the above-mentioned technical solutions: The above-mentioned three-armed rosin-based S-APG phenolic ester is used as an aerosol-soluble foaming agent.

[0012] The above-mentioned three-armed rosin-based S-APG phenolic ester was prepared according to the following steps: Step 1, Preparation of dehydroabscisic acid methanethiol intermediate: The required amount of dehydroabscisic acid is reacted with a brominating reagent to produce bromodehydroabscisic acid; bromodehydroabscisic acid is reacted with thiourea under reflux, and the resulting reaction product is hydrolyzed with sodium hydroxide aqueous solution. After separation and purification, the dehydroabscisic acid methanethiol intermediate is obtained. Step 2, Construction of thioglycoside intermediate A: Peracetylated-α-D-bromoglucose and dehydroabsinomethylthiol were reacted in a phase transfer catalyst and a weak base system to obtain crude peracetylated thioglycoside; the crude peracetylated thioglycoside was reacted with sodium methoxide, and the reaction product was purified to obtain thioglycoside intermediate A. Step 3, Synthesis of three-arm intermediate B: Thioglycoside intermediate A reacts with 1,3,5-benzenetricarboxyl chloride, and the reaction product is purified to obtain three-arm intermediate B; Step 4, preparation of the target phenolic ester product: the three-arm intermediate B reacts with tri-O-benzylgalloyl chloride to obtain a benzyl protected intermediate; the benzyl protected intermediate is debenzyl protected and purified to obtain the three-arm rosinyl S-APG phenolic ester.

[0013] In step one above, the brominating reagent is phosphorus tribromide; the reaction temperature of the bromination reaction is 20°C to 30°C, and the reaction time is 3h to 5h.

[0014] In step one above, the reflux reaction temperature of brominated dehydroabiane and thiourea is 50°C to 80°C, and the reaction time is 6h to 10h.

[0015] In step one above, the mass ratio of dehydroabscisic acid, phosphorus tribromide (PBr3), thiourea, and sodium hydroxide is (0.7 to 1): (0.2 to 0.4): (0.6 to 1.2): (1.2 to 2.5).

[0016] In step two above, the reaction process of peracetylated α-D-bromoglucose and dehydroabimethylthiol is as follows: A mixture of acetylated α-D-bromoglucose, dehydroabsinomethylthiol, a phase transfer catalyst, and dichloromethane was added, followed by the addition of an aqueous solution of sodium bicarbonate. The mixture was stirred and reacted at 20°C to 30°C for 6 to 10 hours under inert gas protection. The phase transfer catalyst was tetrabutylammonium bromide.

[0017] In step two above, the reaction temperature of the crude peracetylated thioglycoside with sodium methoxide is 20°C to 30°C, and the reaction time is 3h to 5h.

[0018] In step two above, the mass ratio of peracetylated-α-D-bromoglucose, dehydroammonium thiosulfate, tetrabutylammonium bromide, sodium bicarbonate, and sodium methoxide is (0.8 to 1): (0.2 to 1.1): (0.08 to 0.1): (1.5 to 2): (0.03 to 0.05).

[0019] In step three above, thioglycoside intermediate A and 1,3,5-benzenetricarboxyl chloride react under an acid-binding agent and anhydrous conditions, with a reaction temperature of 0 to 5°C and a reaction time of 5 to 8 hours; the acid-binding agent is anhydrous pyridine.

[0020] In step three above, the mass ratio of 1,3,5-benzenetricarboxyl chloride, thioglycoside intermediate A, and anhydrous pyridine is (0.7 to 1): (1.9 to 3.2): (6 to 10).

[0021] In step four above, the three-arm intermediate B and tri-O-benzylgallic acid chloride react under anhydrous conditions with an organic acid binder, an acylation catalyst, and an organic acid binder at a temperature of 20°C to 30°C for a duration of 10 to 15 hours. The organic acid binder is triethylamine, and the acylation catalyst is 4-dimethylaminopyridine.

[0022] In step four above, the benzyl protected intermediate undergoes catalytic hydrogenation to remove the benzyl protecting group under the action of a hydrogenation catalytic deprotection catalyst; the hydrogenation catalytic deprotection catalyst is 10% Pd / C.

[0023] In step four above, the mass ratio of the three-arm intermediate B, tri-O-benzylgalloyl chloride, triethylamine, 4-dimethylaminopyridine and 10% Pd / C (10% loaded palladium / activated carbon catalyst) is (0.5 to 1): (2 to 6.5): (3 to 7): (0.1 to 0.3): (0.1 to 0.2).

[0024] The second technical solution of the present invention is achieved through the following measures: a method for preparing a three-armed rosin-based S-APG phenolic ester, comprising the following steps: Step 1, Preparation of dehydroabscisic acid methanethiol intermediate: The required amount of dehydroabscisic acid is reacted with a brominating reagent to produce bromodehydroabscisic acid; bromodehydroabscisic acid is reacted with thiourea under reflux, and the resulting reaction product is hydrolyzed with sodium hydroxide aqueous solution. After separation and purification, the dehydroabscisic acid methanethiol intermediate is obtained. Step 2, Construction of thioglycoside intermediate A: Peracetylated-α-D-bromoglucose and dehydroabsinomethylthiol were reacted in a phase transfer catalyst and a weak base system to obtain crude peracetylated thioglycoside; the crude peracetylated thioglycoside was reacted with sodium methoxide, and the reaction product was purified to obtain thioglycoside intermediate A. Step 3, Synthesis of three-arm intermediate B: Thioglycoside intermediate A reacts with 1,3,5-benzenetricarboxyl chloride, and the reaction product is purified to obtain three-arm intermediate B; Step 4, preparation of the target phenolic ester product: the three-arm intermediate B reacts with tri-O-benzylgalloyl chloride to obtain a benzyl protected intermediate; the benzyl protected intermediate is debenzyl protected and purified to obtain the three-arm rosinyl S-APG phenolic ester.

[0025] The third technical solution of the present invention is achieved through the following measures: the application of a three-armed rosin-based S-APG phenolic ester as an additive for CO2 flooding.

[0026] The fourth technical solution of the present invention is achieved through the following measures: a CO2 oil displacement aerosol foaming agent system, wherein the raw materials include, by mass percentage: 3% to 5% aerosol foaming agent (three-arm rosin-based S-APG phenolic ester), 0.1% to 2% co-surfactant, and the balance being water.

[0027] The following are further optimizations and / or improvements to the fourth technical solution of the invention described above: The aforementioned co-surfactant is at least one selected from ethanol, n-propanol, isopropanol, n-butanol, and isobutanol. Co-surfactants are used to synergistically regulate interfacial tension and increase the solubility of aerosol foaming agents in CO2.

[0028] This invention provides a compound, three-arm rosin-based S-APG phenolic ester, which can be used as a gas-soluble foaming agent for CO2 flooding. It is suitable for low-permeability, dense, and water-sensitive reservoirs and can strongly support the company's main business development in oil and gas exploration. Detailed Implementation

[0029] This invention is not limited to the following embodiments, and specific implementation methods can be determined according to the technical solutions and actual conditions of this invention. Unless otherwise specified, all chemical reagents and chemicals mentioned in this invention are well-known and commonly used chemical reagents and chemicals in the prior art; unless otherwise specified, all percentages in this invention are mass percentages; unless otherwise specified, all solutions in this invention are aqueous solutions with water as the solvent, for example, hydrochloric acid solution is an aqueous solution of hydrochloric acid; room temperature in this invention generally refers to a temperature between 15°C and 25°C, generally defined as 25°C.

[0030] The present invention will be further described below with reference to embodiments: Example 1: The three-armed rosin-based S-APG phenolic ester has the following chemical structural formula: .

[0031] Example 2: As an optimization of the above example, the three-armed rosin-based S-APG phenolic ester is used as an aerosol-soluble foaming agent.

[0032] Example 3: As an optimization of the above examples, the three-armed rosin-based S-APG phenolic ester was prepared according to the following steps: Step 1, Preparation of dehydroabscisic acid methanethiol intermediate: The required amount of dehydroabscisic acid is reacted with a brominating reagent to produce bromodehydroabscisic acid; bromodehydroabscisic acid is reacted with thiourea under reflux, and the resulting reaction product is hydrolyzed under alkaline conditions, separated and purified to obtain dehydroabscisic acid methanethiol intermediate. Step 2, Construction of thioglycoside intermediate A: Peracetylated-α-D-bromoglucose and dehydroabsinomethylthiol were reacted in a phase transfer catalyst and a weak base system to obtain crude peracetylated thioglycoside; the crude peracetylated thioglycoside was reacted with sodium methoxide, and the reaction product was purified to obtain thioglycoside intermediate A. Step 3, Synthesis of three-arm intermediate B: Thioglycoside intermediate A reacts with 1,3,5-benzenetricarboxyl chloride, and the reaction product is purified to obtain three-arm intermediate B; Step 4, preparation of the target phenolic ester product: the three-arm intermediate B reacts with tri-O-benzylgalloyl chloride to obtain a benzyl protected intermediate; the benzyl protected intermediate is debenzyl protected and purified to obtain the three-arm rosinyl S-APG phenolic ester.

[0033] Example 4: As an optimization of the above example, in step one, the brominating agent is phosphorus tribromide; the reaction temperature of the bromination reaction is 20°C to 30°C, and the reaction time is 3h to 5h.

[0034] Example 5: As an optimization of the above example, in step one, the reflux reaction temperature of brominated dehydroabiane and thiourea is 50°C to 80°C, and the reaction time is 6h to 10h.

[0035] Example 6: As an optimization of the above example, in step one, the mass ratio of dehydroabscisic acid, phosphorus tribromide (PBr3), thiourea, and sodium hydroxide is (0.7 to 1): (0.2 to 0.4): (0.6 to 1.2): (1.2 to 2.5).

[0036] Example 7: As an optimization of the above example, in step two, the reaction process of fully acetylated α-D-bromoglucose and dehydroabimethylthiol is as follows: A mixture of acetylated α-D-bromoglucose, dehydroabsinomethylthiol, a phase transfer catalyst, and dichloromethane was added, followed by the addition of an aqueous solution of sodium bicarbonate. The mixture was stirred and reacted at 20°C to 30°C for 6 to 10 hours under inert gas protection. The phase transfer catalyst was tetrabutylammonium bromide.

[0037] Example 8: As an optimization of the above example, in step two, the reaction temperature of the crude peracetylated thioglycoside with sodium methoxide is 20°C to 30°C, and the reaction time is 3h to 5h.

[0038] Example 9: As an optimization of the above example, in step two, the mass ratio of fully acetylated-α-D-bromoglucose, dehydroabscisic acid methanethiol, tetrabutylammonium bromide, sodium bicarbonate, and sodium methoxide is (0.8 to 1): (0.2 to 1.1): (0.08 to 0.1): (1.5 to 2): (0.03 to 0.05).

[0039] Example 10: As an optimization of the above example, in step three, the thioglycoside intermediate A and 1,3,5-benzenetricarboxyl chloride react under an acid-binding agent and anhydrous conditions, the reaction temperature is 0 to 5°C, and the reaction time is 5 to 8 hours; the acid-binding agent is anhydrous pyridine.

[0040] Example 11: As an optimization of the above example, in step three, the mass ratio of 1,3,5-benzenetricarboxyl chloride, thioglycoside intermediate A and anhydrous pyridine is (0.7 to 1): (1.9 to 3.2): (6 to 10).

[0041] Example 12: As an optimization of the above example, in step four, the three-arm intermediate B and tri-O-benzylgallic chloride react under anhydrous conditions with an organic acid binder, an acylation catalyst, and an organic acid binder at a temperature of 20°C to 30°C for a reaction time of 10 to 15 hours; the organic acid binder is triethylamine and the acylation catalyst is 4-dimethylaminopyridine.

[0042] Example 13: As an optimization of the above example, in step four, the benzyl protected intermediate undergoes catalytic hydrogenation to remove the benzyl protecting group under the action of a hydrogenation catalytic deprotection catalyst; the hydrogenation catalytic deprotection catalyst is 10% Pd / C.

[0043] Example 14: As an optimization of the above example, in step four, the mass ratio of the three-arm intermediate B, tri-O-benzylgalloyl chloride, triethylamine, 4-dimethylaminopyridine and 10% Pd / C is (0.5 to 1): (2 to 6.5): (3 to 7): (0.1 to 0.3): (0.1 to 0.2).

[0044] Example 15: Application of the three-armed rosin-based S-APG phenolic ester as an additive for CO2 flooding.

[0045] Example 16: The CO2 oil displacement aerosol foaming agent system comprises, by mass percentage: 3% to 5% aerosol foaming agent (three-arm rosin-based S-APG phenolic ester), 0.1% to 2% co-surfactant, and the balance being water.

[0046] Example 17: As an optimization of Example 16 above, the co-surfactant is at least one selected from ethanol, n-propanol, isopropanol, n-butanol, and isobutanol. The co-surfactant is used to synergistically regulate interfacial tension and increase the solubility of the aerosol foaming agent in CO2.

[0047] In use, the aerosol-soluble foaming agent (three-arm rosin-based S-APG phenolic ester), co-surfactant, and water are mixed to obtain the aerosol-soluble foaming agent system for CO2 flooding. Compared with conventional foam systems, the aerosol-soluble foaming agent system for CO2 flooding of the present invention has improved solubility in CO2 and foaming and foam stabilization performance, and has less environmental pollution, making it applicable in CO2 flooding operations.

[0048] Example 18: The preparation process of this three-armed rosin-based S-APG phenolic ester is as follows: Step 1: Preparation of dehydroabsinomethylthiol intermediate: ① The required amount of dehydroabscisic acid is reacted with a brominating reagent to produce bromodehydroabscisic acid. The specific process is as follows: Add dehydroabietic alcohol and reaction solvent (anhydrous dichloromethane) to the reaction vessel, stir and dissolve under nitrogen atmosphere, cool to 0°C in an ice-water bath, and slowly add the brominating reagent PBr3 solution (solvent: anhydrous dichloromethane). After the addition is complete, stir at 25°C for 4 hours. Monitor the reaction by TLC until complete (evolving solvent: petroleum ether / ethyl acetate = 9:1, product Rf ≈ 0.8). Quench with water in an ice-water bath, separate the phases, wash the organic phase successively with saturated sodium bicarbonate and saturated brine, dry with anhydrous sodium sulfate, and concentrate to obtain a pale yellow oily dehydroabietic alcohol (no purification required, can be used directly in the next step).

[0049] ② The dehydroabirane bromide reacts with thiourea under reflux. The resulting product is hydrolyzed under alkaline conditions, and after separation and purification, the dehydroabirane methanethiol intermediate is obtained. The specific process is as follows: Add bromodehydroabiran, thiourea, and reaction solvent (anhydrous ethanol) to the reaction vessel. Under nitrogen protection, heat to 60°C and reflux for 8 hours. Monitor by TLC to ensure complete consumption of the brominated product. Cool to 25°C, add sodium hydroxide aqueous solution, and continue reflux for 2 hours. Cool to 25°C. Concentrate the resulting mixture under reduced pressure to remove ethanol. Add dichloromethane and adjust the pH to 4 with 1 mol / L hydrochloric acid. Separate the mixture. Wash the organic phase with saturated brine, dry with anhydrous sodium sulfate, and concentrate. Purify the crude product by silica gel column chromatography (eluent: petroleum ether / ethyl acetate = 95:5) to obtain colorless oily dehydroabiran methanethiol (structural formula shown below).

[0050] Step 2, constructing thioglycoside intermediate A: ①The crude product of fully acetylated α-D-bromoglucose and dehydroabsinomethylthiol was obtained by reacting them under a phase transfer catalyst and a weak base system; Allacetylated α-D-bromoglucose, dehydroabsinomethylthiol, phase transfer catalyst (tetrabutylammonium bromide), and dichloromethane were mixed and then an aqueous solution of sodium bicarbonate was added. The mixture was stirred and reacted at 25°C for 8 hours under inert gas protection. The phase transfer catalyst was tetrabutylammonium bromide.

[0051] After the reaction, the reaction was monitored by TLC until it was complete (evolving solvent: petroleum ether / ethyl acetate = 7:3, product Rf≈0.5, starting material bromosugar Rf≈0.6). The reaction was stopped, the liquid was separated, and the organic phase was washed successively with 1 mol / L hydrochloric acid, saturated sodium bicarbonate, and saturated brine. It was dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to obtain a pale yellow oily crude product of fully acetylated thioglycosides.

[0052] ② After reacting the crude peracetylated thioglycoside with sodium methoxide, the reaction product was purified to obtain thioglycoside intermediate A; The above-mentioned crude fully acetylated thioglycoside was dissolved in anhydrous methanol under nitrogen protection. Sodium methoxide was added, and the mixture was stirred at 25°C for 4 hours. The reaction was monitored by TLC until complete (eluent: dichloromethane / methanol = 9:1, product Rf≈0.3, fully acetylated product Rf≈0.9). The product was neutralized to pH=7 with a strongly acidic cation exchange resin, the resin was removed by filtration, and methanol was removed by vacuum concentration. The crude product was purified by silica gel column chromatography (eluting agent: dichloromethane / methanol = 95:5 → 9:1 gradient elution) to obtain a white powdery thioglycoside intermediate A (1-dehydroabscisyl-1-thio-β-D-glucopyranose, structural formula as follows).

[0053] Step 3, synthesize the three-armed intermediate B: Thioglycoside intermediate A reacts with 1,3,5-benzenetricarboxyl chloride, and the reaction product is purified to give three-arm intermediate B. Thioglycoside intermediate A and anhydrous pyridine were added to the reaction vessel, protected with nitrogen, and cooled to 0°C in an ice-water bath. The mixture was stirred until completely dissolved, and an anhydrous dichloromethane solution of 1,3,5-benzenetricarboxyl chloride was slowly added dropwise. The internal temperature was strictly controlled to be ≤5°C during the dropwise addition. After the dropwise addition was completed, the mixture was kept at 0°C and stirred for 6 hours. The reaction was monitored by TLC to ensure complete reaction (developing solvent: dichloromethane / methanol = 85:15, product Rf≈0.4, thioglycoside intermediate A Rf≈0.3, mono / disubstituted impurities Rf≈0.6~0.7). The reaction was stopped, and excess acyl chloride was quenched with anhydrous methanol under ice-water bath. Most of the pyridine was removed by concentration under reduced pressure. Dichloromethane was added, and the mixture was washed successively with 1 mol / L hydrochloric acid, saturated sodium bicarbonate, and saturated brine. The organic phase was dried over anhydrous sodium sulfate, filtered, concentrated under reduced pressure, and the crude product was purified by silica gel column chromatography (eluting agent: dichloromethane / methanol = 9:1 → 85:15 gradient elution) to obtain a white powdery three-arm intermediate B (structural formula as follows).

[0054] Step 4: Preparation of the target phenolic ester product: ① The three-arm intermediate B reacts with tri-O-benzylgalloyl chloride to give a benzyl protected intermediate; Preparation of tri-O-benzylgallic chloride: Gallic acid and anhydrous dimethylformamide were added to the reaction vessel and stirred to dissolve. Potassium carbonate was added and stirred at 25°C for 30 min. Benzyl chloride was slowly added dropwise. After the addition was complete, the temperature was raised to 80°C and reacted for 12 h. The mixture was then cooled to 25°C, filtered to remove inorganic salts, and the filtrate was poured into ice water to precipitate a solid. The solid was filtered, and the filter cake was recrystallized from ethanol to obtain benzyl tri-O-benzyl gallate.

[0055] Tri-O-benzyl gallate benzyl ester was dissolved in a mixed solution of tetrahydrofuran / methanol = 1:1, and an aqueous solution of sodium hydroxide was added. The mixture was stirred at 25°C for 4 hours. The reaction was monitored by TLC until it was complete. The organic solvent was removed by concentration under reduced pressure, water was added, and the pH was adjusted to 2.5 with 1 mol / L hydrochloric acid. A white solid precipitated out. The solid was filtered and dried to obtain tri-O-benzyl gallic acid.

[0056] Tri-O-benzylgallic acid and anhydrous dichloromethane were added to the reaction vessel, and nitrogen gas was purged for protection. Oxaloyl chloride was added, followed by the dropwise addition of dimethylformamide. The mixture was stirred at 25°C for 4 hours. Excess oxaloyl chloride and solvent were removed by concentration under reduced pressure to obtain a pale yellow oily tri-O-benzylgallic acid chloride.

[0057] Three-arm intermediate B, anhydrous dichloromethane, triethylamine, and 4-dimethylaminopyridine were added to the reaction vessel. Under nitrogen protection, the mixture was cooled to 0°C in an ice-water bath. The mixture was stirred to dissolve the compounds. A solution of tri-O-benzylgalactoyl chloride in anhydrous dichloromethane, prepared above, was slowly added dropwise, maintaining the internal temperature ≤5°C during the addition. After the addition was complete, the mixture was stirred at 25°C for 12 hours. The reaction was monitored by TLC until complete (evolving solvent: petroleum ether / ethyl acetate = 6:4; product Rf ≈ 0.5; intermediate B Rf ≈ 0.1). The reaction was stopped, quenched with ice water, and separated. The organic phase was washed successively with 1 mol / L hydrochloric acid, saturated sodium bicarbonate, and saturated brine. The solution was dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to obtain the crude benzyl-protected intermediate, which was directly used for the next step of deprotection.

[0058] ②The benzyl protecting intermediate was debenzylated and purified to obtain a three-armed rosinyl S-APG phenolic ester.

[0059] The crude benzyl-protected intermediate was dissolved in a 1:1 mixture of tetrahydrofuran and methanol, and 10% Pd / C (10% of the crude benzyl-protected intermediate) was added. The air was purged three times with hydrogen, and the reaction was carried out at 25°C for 8 hours under a normal hydrogen atmosphere. TLC monitoring showed complete removal of the benzyl group (eluent: dichloromethane / methanol = 8:2; product Rf ≈ 0.4; benzyl-protected intermediate Rf ≈ 0.9). After the reaction was complete, Pd / C was removed by diatomaceous earth filtration. The filtrate was concentrated under reduced pressure, and the crude product was purified by reversed-phase silica gel column chromatography (C18 column, eluent: methanol / water = 7:3 → 9:1 gradient elution). The purified product was then freeze-dried to obtain a three-armed rosinyl S-APG phenolic ester.

[0060] The chemical structure of the three-armed rosinyl S-APG phenolic ester of this invention possesses an ultra-large hydrophobic framework: a dehydroabiyl (rosinyl) tricyclic diterpene, which is rigid, nonpolar, and large in size, making it a naturally hydrophobic group with extremely high solubility in supercritical CO2, far superior to ordinary alkyl groups. The thioglycosidic bond (CSC) is more CO2-friendly than (COC) glycosides, and the sulfur atom is less polar than the oxygen atom, thus not forming strong hydrogen bonds and facilitating entry into supercritical CO2. Furthermore, this three-armed star structure is less prone to self-polymerization, resulting in stronger unimolecular solubility in supercritical CO2.

[0061] Example 19: The implementation steps of this embodiment are the same as those of Embodiment 18.

[0062] During the synthesis of three-armed rosin-based S-APG phenolic esters: In step one, the mass ratio of dehydroabscisic acid, phosphorus tribromide (PBr3), thiourea, and sodium hydroxide is 1:0.4:1.2:2.5.

[0063] In step two, the mass ratio of fully acetylated α-D-bromoglucose, dehydroabsinomethylthiol, tetrabutylammonium bromide, sodium bicarbonate, and sodium methoxide is 1:1.1:0.1:2.0:0.05.

[0064] In step three, the mass ratio of 1,3,5-benzenetriacyl chloride, thioglycoside intermediate A, and anhydrous pyridine is 1:3.2:10.

[0065] In step four, the mass ratio of the three-arm intermediate B, tri-O-benzylgalloyl chloride, triethylamine, 4-dimethylaminopyridine, and 10% Pd / C is 1:6.5:7.0:0.3:0.1.

[0066] Take 4% of the three-arm rosin-based S-APG phenolic ester and 1% of n-propanol from this embodiment, and stir until clear and transparent to form aerosol foaming agent 1.

[0067] Example 20: The implementation steps of this embodiment are the same as those of Embodiment 18.

[0068] During the synthesis of three-armed rosin-based S-APG phenolic esters: In step one, the mass ratio of dehydroabscisic acid, phosphorus tribromide (PBr3), thiourea, and sodium hydroxide is 0.8 : 0.2 : 0.6 : 1.5.

[0069] In step two, the mass ratio of fully acetylated α-D-bromoglucose, dehydroabsinomethylthiol, tetrabutylammonium bromide, sodium bicarbonate, and sodium methoxide is 0.8:0.2:0.08:1.8:0.03.

[0070] In step three, the mass ratio of 1,3,5-benzenetriacyl chloride, thioglycoside intermediate A, and anhydrous pyridine is 0.7:2.1:6.

[0071] In step four, the mass ratio of the three-arm intermediate B, tri-O-benzylgalloyl chloride, triethylamine, 4-dimethylaminopyridine, and 10% Pd / C is 0.5:2:3.8:0.1:0.1.

[0072] Take 4% of the three-arm rosin-based S-APG phenolic ester and 1% of n-propanol from this embodiment, and stir until clear and transparent to form aerosol foaming agent 2.

[0073] Example 21: The implementation steps of this embodiment are the same as those of Embodiment 18.

[0074] During the synthesis of three-armed rosin-based S-APG phenolic esters: In step one, the mass ratio of dehydroabscisic acid, phosphorus tribromide (PBr3), thiourea, and sodium hydroxide is 0.9:0.2:0.6:1.7.

[0075] In step two, the mass ratio of fully acetylated α-D-bromoglucose, dehydroabsinomethylthiol, tetrabutylammonium bromide, sodium bicarbonate, and sodium methoxide is 0.8:0.5:0.08:1.8:0.03.

[0076] In step three, the mass ratio of 1,3,5-benzenetriacyl chloride, thioglycoside intermediate A, and anhydrous pyridine is 0.8:2.1:8.

[0077] In step four, the mass ratio of the three-arm intermediate B, tri-O-benzylgalloyl chloride, triethylamine, 4-dimethylaminopyridine, and 10% Pd / C is 0.5:2:4:0.1:0.1.

[0078] Take 4% of the three-arm rosin-based S-APG phenolic ester and 1% of n-propanol from this embodiment, and stir until clear and transparent to form aerosol foaming agent 3.

[0079] Example 22: The implementation steps of this embodiment are the same as those of Embodiment 18.

[0080] During the synthesis of three-armed rosin-based S-APG phenolic esters: In step one, the mass ratio of dehydroabscisic acid, phosphorus tribromide (PBr3), thiourea, and sodium hydroxide is 0.8:0.2:0.8:1.8.

[0081] In step two, the mass ratio of fully acetylated α-D-bromoglucose, dehydroabsinomethylthiol, tetrabutylammonium bromide, sodium bicarbonate, and sodium methoxide is 0.9:0.2:0.08:1.8:0.03.

[0082] In step three, the mass ratio of 1,3,5-benzenetriacyl chloride, thioglycoside intermediate A, and anhydrous pyridine is 0.7:2.7:6.

[0083] In step four, the mass ratio of the three-arm intermediate B, tri-O-benzylgalloyl chloride, triethylamine, 4-dimethylaminopyridine, and 10% Pd / C is 0.5:2:4.8:0.1:0.1.

[0084] Take 4% of the three-armed rosin-based S-APG phenolic ester and 1% of n-propanol from this embodiment, and stir until clear and transparent to form aerosol foaming agent 4.

[0085] Example 23: The implementation steps of this embodiment are the same as those of Embodiment 18.

[0086] During the synthesis of three-armed rosin-based S-APG phenolic esters: In step one, the mass ratio of dehydroabscisic acid, phosphorus tribromide (PBr3), thiourea, and sodium hydroxide is 0.8:0.2:0.6:1.9.

[0087] In step two, the mass ratio of fully acetylated α-D-bromoglucose, dehydroabsinomethylthiol, tetrabutylammonium bromide, sodium bicarbonate, and sodium methoxide is 0.9:0.6:0.08:1.8:0.03.

[0088] In step three, the mass ratio of 1,3,5-benzenetriacyl chloride, thioglycoside intermediate A, and anhydrous pyridine is 0.7:2.5:7.

[0089] In step four, the mass ratio of the three-arm intermediate B, tri-O-benzylgalloyl chloride, triethylamine, 4-dimethylaminopyridine, and 10% Pd / C is 0.5:2:6:0.1:0.1.

[0090] Take 4% of the three-arm rosin-based S-APG phenolic ester and 1% of n-propanol from this embodiment, and stir until clear and transparent to form an aerosol-soluble foaming agent 5.

[0091] Example 24: The implementation steps of this embodiment are the same as those of Embodiment 18.

[0092] During the synthesis of three-armed rosin-based S-APG phenolic esters: In step one, the mass ratio of dehydroabscisic acid, phosphorus tribromide (PBr3), thiourea, and sodium hydroxide is 0.8:0.2:0.8:1.9.

[0093] In step two, the mass ratio of fully acetylated α-D-bromoglucose, dehydroabsinomethylthiol, tetrabutylammonium bromide, sodium bicarbonate, and sodium methoxide is 0.9:0.6:0.08:1.9:0.03.

[0094] In step three, the mass ratio of 1,3,5-benzenetriacyl chloride, thioglycoside intermediate A, and anhydrous pyridine is 0.7:2.5:7.

[0095] In step four, the mass ratio of the three-arm intermediate B, tri-O-benzylgalloyl chloride, triethylamine, 4-dimethylaminopyridine, and 10% Pd / C is 0.5:2:4.8:0.1:0.1.

[0096] Take 4% of the three-arm rosin-based S-APG phenolic ester and 1% of n-propanol from this embodiment, and stir until clear and transparent to form an aerosol-soluble foaming agent 6.

[0097] Test example: The solubility and foaming properties of the aerosolized foaming agents 1 to 6 in the above examples were evaluated in CO2. The solubility was determined using the cloud point method, and the foaming properties were determined using the Waring-Blender method. The results of the solubility determination are shown in Table 1, and the results of the foaming properties determination are shown in Table 2.

[0098] Table 1 .

[0099] Table 2 .

[0100] Currently, existing aerosol-soluble foaming agents (such as sodium diisooctyl succinate sulfonate and nonionic surfactants) generally have cloud point pressures between 15 MPa and 22 MPa, and their dissolved volume fraction in CO2 is typically 0.14% to 0.23%; their foaming rate is 160% to 400%, and their foam half-life is 540 s to 1140 s. As shown in Tables 1 and 2, the aerosol-soluble foaming agent system for CO2 flooding of this invention has a cloud point pressure of 8 MPa to 13 MPa, a dissolved volume fraction in CO2 of 0.5%, a foaming rate of 520% ​​to 575%, and a foam half-life of 1835 s to 1932 s. These results indicate that the three-armed rosin-based S-APG phenolic ester of this invention is significantly superior to existing commercially available aerosol-soluble foaming agents in terms of CO2 solubility, foaming performance, and foam stability.

[0101] The present invention has the following effects: (1) This invention synthesizes a three-armed rosin-based S-APG phenolic ester with excellent CO2 gas solubility. Based on the three-armed rosin-based S-APG phenolic ester, a new aerosol foaming agent formulation is constructed. The addition of foam stabilizer and co-surfactant further enhances the foam stabilization and solubility performance, and the stability is improved by several times compared with the conventional system. (2) The aerosol foaming agent provided by the present invention has a much higher solubility in CO2 environment than conventional surfactants, has good foaming and foam stabilizing performance, effectively controls the flow ratio, improves oil displacement efficiency, and effectively solves the problem of foaming agent injection. (3) The raw materials of the aerosol foaming agent provided by the present invention are readily available, widely sourced and environmentally friendly.

[0102] In summary, this invention provides a three-armed rosin-based S-APG phenolic ester and its preparation method. This three-armed rosin-based S-APG phenolic ester is a gas-soluble foaming agent for CO2 flooding. It contains sulfide bonds and a three-arm structure, exhibits strong solubility in CO2, and has excellent foaming and foam-stabilizing properties. It is suitable for low-permeability, dense, and water-sensitive reservoirs, and can effectively inhibit gas channeling and improve oil displacement efficiency. The raw materials are environmentally friendly, free from silicon and fluorine pollution, and are green and safe.

[0103] The above technical features constitute various embodiments of the present invention, which have strong adaptability and implementation effect. Unnecessary technical features can be added or removed according to actual needs to meet the needs of different situations.

Claims

1. A three-armed rosin-based S-APG phenolic ester, characterized in that... It has the following chemical structure: 。 2. The three-armed rosin-based S-APG phenolic ester according to claim 1, characterized in that... The three-armed rosin-based S-APG phenolic ester is used as an aerosol-soluble foaming agent.

3. The three-armed rosin-based S-APG phenolic ester according to claim 1 or 2, characterized in that... The three-armed rosin-based S-APG phenolic ester was prepared by the following steps: Step 1, Preparation of dehydroabscisic acid methanethiol intermediate: The required amount of dehydroabscisic acid is reacted with a brominating reagent to produce bromodehydroabscisic acid; bromodehydroabscisic acid is reacted with thiourea under reflux, and the resulting reaction product is hydrolyzed with sodium hydroxide aqueous solution. After separation and purification, the dehydroabscisic acid methanethiol intermediate is obtained. Step 2, Construction of thioglycoside intermediate A: Peracetylated-α-D-bromoglucose and dehydroabsinomethylthiol were reacted in a phase transfer catalyst and a weak base system to obtain crude peracetylated thioglycoside; the crude peracetylated thioglycoside was reacted with sodium methoxide, and the reaction product was purified to obtain thioglycoside intermediate A. Step 3, Synthesis of three-arm intermediate B: Thioglycoside intermediate A reacts with 1,3,5-benzenetricarboxyl chloride, and the reaction product is purified to obtain three-arm intermediate B; Step 4, preparation of the target phenolic ester product: the three-arm intermediate B reacts with tri-O-benzylgalloyl chloride to obtain a benzyl protected intermediate; the benzyl protected intermediate is debenzyl protected and purified to obtain the three-arm rosinyl S-APG phenolic ester.

4. The three-armed rosin-based S-APG phenolic ester according to claim 3, characterized in that... In step one, the brominating agent is phosphorus tribromide; the reaction temperature of the bromination reaction is 20°C to 30°C, and the reaction time is 3 hours to 5 hours. The reflux reaction temperature of the brominated dehydroabsine with thiourea is 50°C to 80°C, and the reaction time is 6h to 10h. The mass ratio of the dehydroabscisic acid, phosphorus tribromide, thiourea, and sodium hydroxide is (0.7 to 1): (0.2 to 0.4): (0.6 to 1.2): (1.2 to 2.5).

5. The three-armed rosin-based S-APG phenolic ester according to claim 3, characterized in that... In step two, the reaction process of peracetylated α-D-bromoglucose and dehydroabimethylthiol is as follows: A mixture of acetylated α-D-bromoglucose, dehydroabsinomethylthiol, a phase transfer catalyst, and dichloromethane was added, followed by the addition of an aqueous solution of sodium bicarbonate. The mixture was stirred and reacted at 20°C to 30°C for 6 to 10 hours under inert gas protection. The phase transfer catalyst was tetrabutylammonium bromide. The reaction temperature of the crude peracetylated thioglycoside with sodium methoxide is 20°C to 30°C, and the reaction time is 3h to 5h. The mass ratio of the fully acetylated α-D-bromoglucose, dehydroabscisic acid methanethiol, tetrabutylammonium bromide, sodium bicarbonate, and sodium methoxide is (0.8 to 1): (0.2 to 1.1): (0.08 to 0.1): (1.5 to 2): (0.03 to 0.05).

6. The three-armed rosin-based S-APG phenolic ester according to claim 3, characterized in that... In step three, thioglycoside intermediate A and 1,3,5-benzenetricarboxyl chloride react under an acid-binding agent and anhydrous conditions at a temperature of 0 to 5°C for a duration of 5 to 8 hours; the acid-binding agent is anhydrous pyridine. The mass ratio of 1,3,5-benzenetriacyl chloride, thioglycoside intermediate A, and anhydrous pyridine is (0.7 to 1):(1.9 to 3.2):(6 to 10). Or / and, in step four, the three-arm intermediate B and tri-O-benzylgallic chloride react under an organic acid-binding agent, an acylation catalyst, and anhydrous conditions at a reaction temperature of 20°C to 30°C for a reaction time of 10 to 15 hours; the organic acid-binding agent is triethylamine, and the acylation catalyst is 4-dimethylaminopyridine. The benzyl-protected intermediate undergoes catalytic hydrogenation to remove the benzyl protecting group in the presence of a hydrogenation catalytic deprotection catalyst; the hydrogenation catalytic deprotection catalyst is 10% Pd / C. The mass ratio of the three-arm intermediate B, tri-O-benzylgalloyl chloride, triethylamine, 4-dimethylaminopyridine, and 10% Pd / C is (0.5 to 1): (2 to 6.5): (3 to 7): (0.1 to 0.3): (0.1 to 0.2).

7. A method for preparing a three-armed rosin-based S-APG phenolic ester according to any one of claims 1 to 6, characterized in that... Follow these steps: Step 1, Preparation of dehydroabscisic acid methanethiol intermediate: The required amount of dehydroabscisic acid is reacted with a brominating reagent to produce bromodehydroabscisic acid; bromodehydroabscisic acid is reacted with thiourea under reflux, and the resulting reaction product is hydrolyzed with sodium hydroxide aqueous solution. After separation and purification, the dehydroabscisic acid methanethiol intermediate is obtained. Step 2, Construction of thioglycoside intermediate A: Peracetylated-α-D-bromoglucose and dehydroabsinomethylthiol were reacted in a phase transfer catalyst and a weak base system to obtain crude peracetylated thioglycoside; the crude peracetylated thioglycoside was reacted with sodium methoxide, and the reaction product was purified to obtain thioglycoside intermediate A. Step 3, Synthesis of three-arm intermediate B: Thioglycoside intermediate A reacts with 1,3,5-benzenetricarboxyl chloride, and the reaction product is purified to obtain three-arm intermediate B; Step 4, preparation of the target phenolic ester product: the three-arm intermediate B reacts with tri-O-benzylgalloyl chloride to obtain a benzyl protected intermediate; the benzyl protected intermediate is debenzyl protected and purified to obtain the three-arm rosinyl S-APG phenolic ester.

8. The use of a three-armed rosin-based S-APG phenolic ester according to any one of claims 1 to 6 as an additive for CO2 flooding.

9. A CO2-based gas-soluble foaming agent system using the tri-arm rosin-based S-APG phenolic ester as a raw material according to any one of claims 1 to 6, characterized in that... The raw materials, by mass percentage, include: 3% to 5% of three-arm rosin-based S-APG phenolic esters, 0.1% to 2% of co-surfactant, and the balance being water.

10. The CO2 flooding oil recovery system according to claim 9, characterized in that... The co-surfactant is at least one of ethanol, n-propanol, isopropanol, n-butanol, and isobutanol. The co-surfactant is used to synergistically regulate interfacial tension and increase the solubility of the aerosol foaming agent in CO2.

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