Temporary plugging agent based on glycolic acid toughening modification as well as preparation method and application of temporary plugging agent
Through the polymerization of glycolic acid and specific compounds, a toughening temporary plugging agent was developed, which solved the shortcomings of existing temporary plugging agents in terms of mechanical strength, degradation time and temperature resistance, and achieved more efficient petroleum gas mining applications.
Patent Information
- Application Number
- CN202311807586.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2023-12-26
- Publication Date
- 2025-06-27
Smart Images
Figure CN120208915A_ABST
Abstract
Description
Technical Field
[0001] The present invention belongs to the technical field of petroleum gas production, and relates to a temporary plugging agent based on glycolic acid toughening modification, its preparation method and application. Background Art
[0002] Temporary plugging agents are important materials for increasing production in petroleum gas production. The temporary plugging and diversion fracturing technology developed in the 1990s improved the deficiencies of repeated fracturing in changing the fracture extension direction and constructing new fractures. This technology has been deeply studied and applied in many domestic oil fields and has now developed into a very mature technology. Currently, the commonly used temporary plugging agents in China can be divided into water-soluble temporary plugging agents, oil-soluble temporary plugging agents, and acid-soluble temporary plugging agents. Among them, water-soluble temporary plugging agents are suitable for medium-high water cut oil wells, gas wells, and injection wells; oil-soluble temporary plugging agents are suitable for non-high water cut oil wells; and acid-soluble temporary plugging agents are suitable for high-temperature and high-pressure wells. With the continuous improvement of the country's requirements for green environmental protection in oil fields and the increasing attention to reservoir protection, self-degrading temporary plugging agents are becoming more and more popular due to their characteristics of environmental protection, pollution-free, self-cleaning, and less formation damage. At present, the research on self-degrading temporary plugging agents in China has just started, mainly including polyesters, polylactic acid, etc. Most self-degrading temporary plugging agents have disadvantages such as low mechanical strength, long degradation time, and poor temperature resistance, and it is difficult to meet the on-site requirements. Among them, polyglycolic acid has good degradability, is not affected by salinity and medium concentration, and has the same degradation rate in pure water and various salt waters (NaCl\KCl\CaCl2\NaHCO3\Na2SO3). In particular, the degradation rate of PGA (polyglycolic acid) is not affected by various chemical additives (surfactants, bactericides) in the fracturing fluid. Therefore, PGA has great potential as a new type of temporary plugging agent material. Although the strength of PGA material is very high, its toughness is insufficient, so it is very difficult to be processed and used alone and needs to be modified to enhance certain functions. Summary of the Invention
[0003] Aiming at the deficiencies of the prior art, the purpose of the present invention is to provide a temporary plugging agent based on glycolic acid toughening modification, its preparation method and application.
[0004] To achieve the purpose of this invention, the following technical solutions are adopted:
[0005] On the one hand, the present invention provides a temporary plugging agent based on glycolic acid toughening modification, and the temporary plugging agent based on glycolic acid toughening modification has a structure shown in the following formula I:
[0006]
[0007] Where n is from 1 to 100, such as 1, 3, 5, 8, 10, 15, 18, 20, 25, 30, 35, 38, 40, 45, 48, 50, 55, 58, 60, 65, 68, 70, 75, 78, 80, 85, 88, 90, 95, 98 or 100.
[0008] When the temporary plugging agent of the present invention is subjected to a relatively large stress, the four-membered ring in the chain segment will be preferentially reduced and broken, while the carbon chain structure in the structure is relatively stable and will not continue to break. Therefore, the toughness of the overall chain segment is improved, achieving the purpose of toughening.
[0009] On the other hand, the present invention provides a preparation method of the temporary plugging agent based on glycolic acid toughening modification as described above. The preparation method includes the following steps:
[0010] The compound shown in Formula II undergoes a polymerization reaction with glycolic acid to obtain the glycolic acid toughening modified temporary plugging agent. The reaction formula is as follows:
[0011]
[0012] Preferably, the molar ratio of the compound shown in Formula II to glycolic acid is 1:(0.9 - 1.2), such as 1:0.9, 1:1.0, 1:1.1 or 1:1.2.
[0013] Preferably, the polymerization reaction is carried out in the presence of a catalyst.
[0014] Preferably, the catalyst is selected from the C 16 H 30 O4Sn / ZnCl2 composite catalyst.
[0015] Preferably, the polymerization reaction is carried out in the presence of a molecular sieve.
[0016] Preferably, the molecular sieve is selected from ZSM-5 type molecular sieves.
[0017] Preferably, the temperature of the polymerization reaction is 180°C - 220°C, such as 180°C, 190°C, 200°C, 210°C or 220°C, and the reaction time is 5h - 10h, such as 5h, 6h, 7h, 8h, 9h or 10h.
[0018] Preferably, the compound shown in Formula II is prepared by the following preparation method:
[0019] (1) 4-Bromomethylcinnamic acid is added to boiling acetone to obtain crystals. The crystals are suspended in deionized water and irradiated with 365 nm ultraviolet light overnight to obtain Compound 1. The reaction formula is as follows:
[0020]
[0021] (2) Mix compound 1 with acetonitrile, dropwise add EDC·HCl (1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride), then add DMAP (4-dimethylaminopyridine) and 8-nonen-1-ol for reaction to obtain compound 2. The reaction formula is as follows:
[0022]
[0023] (3) Compound 2 undergoes a ring-closure reaction in the presence of a catalyst to obtain compound 3. The reaction formula is as follows:
[0024]
[0025] (4) Compound 3 undergoes a hydrogenation reaction with hydrogen to obtain compound 4. The reaction formula is as follows:
[0026]
[0027] (5) Compound 4 reacts with bis(pinacolato)diboron to obtain compound 6. The reaction formula is as follows:
[0028]
[0029] (6) Compound 5 and acetic acid are dissolved in tetrahydrofuran, and hydrogen peroxide is added for reaction to obtain compound 6. The reaction formula is as follows:
[0030]
[0031] (7) In the presence of a catalyst, O2 is introduced into the reaction solution containing compound 6 and sodium hydroxide to obtain compound 7, that is, the compound shown in formula II. The reaction formula is as follows:
[0032]
[0033] Preferably, the amount of acetone used in step (1) is 3 - 4 times the mass of 4-bromomethylcinnamic acid, such as 3 times, 3.3 times, 3.5 times, 3.7 times or 4 times.
[0034] Preferably, the amount of EDC·HCl used in step (2) is 1 - 2 times the mass of compound 1, such as 1 time, 1.2 times, 1.5 times, 1.8 times or 2 times.
[0035] Preferably, the amount of DMAP used in step (2) is 5% - 10% of the mass of compound 1, such as 5%, 6%, 7%, 8%, 9% or 10%.
[0036] Preferably, the molar ratio of the 8-nonen-1-ol to Compound 1 in step (2) is (0.8 - 1.2):1, such as 0.8:1, 0.9:1, 1:1, 1.1:1 or 1.2:1.
[0037] Preferably, the temperature of the reaction in step (2) is 140°C - 180°C, such as 140°C, 145°C, 150°C, 155°C, 160°C, 165°C, 170°C, 175°C or 180°C, and the reaction time is 10h - 20h, such as 10h, 12h, 15h, 18h or 20h.
[0038] Preferably, the catalyst in step (3) is selected from Grubbs II.
[0039] Preferably, the dosage of the catalyst in step (3) is 1% - 5% of the mass of Compound 2, such as 1%, 2%, 3%, 4% or 5%.
[0040] Preferably, the ring-closing reaction in step (3) is carried out under reflux, and the reaction time is 10h - 20h, such as 10h, 12h, 15h, 18h or 20h.
[0041] Preferably, the hydrogenation reaction in step (4) is carried out under the catalysis of Pd / C.
[0042] Preferably, the dosage of the Pd / C is 0.5% - 1% of the mass of Compound 3, such as 0.5%, 0.6%, 0.7%, 0.8%, 0.9% or 1%.
[0043] Preferably, the hydrogenation reaction in step (4) is carried out in a solvent, and the solvent is tetrahydrofuran.
[0044] Preferably, the hydrogenation reaction in step (4) is carried out at room temperature, and the reaction time is 5h - 20h, such as 5h, 8h, 10h, 12h, 15h, 18h or 20h.
[0045] Preferably, the molar ratio of Compound 4 to bis(pinacolato)diboron in step (5) is (0.8 - 1.2):1, such as 0.8:1, 0.9:1, 1:1, 1.1:1 or 1.2:1.
[0046] Preferably, the reaction in step (5) is carried out in the presence of a catalyst;
[0047] Preferably, the catalyst is selected from Pd(dppf)Cl2.
[0048] Preferably, the reaction in step (5) is carried out in the presence of a basic substance, and the basic substance is selected from potassium acetate.
[0049] Preferably, the reaction in step (5) is carried out in a solvent selected from dimethyl sulfoxide.
[0050] Preferably, the reaction in step (5) is carried out under nitrogen protection.
[0051] Preferably, the temperature of the reaction in step (5) is 90°C - 130°C, such as 90°C, 100°C, 110°C, 120°C or 130°C, and the reaction time is 10 h - 20 h, such as 5 h, 8 h, 10 h, 12 h, 15 h, 18 h or 20 h.
[0052] Preferably, the molar ratio of compound 5 to acetic acid in step (6) is (0.8 - 1.2):1, such as 0.8:1, 0.9:1, 1:1, 1.1:1 or 1.2:1
[0053] Preferably, the temperature of adding hydrogen peroxide in step (6) is 0 - 5°C, such as 0°C, 2°C, 4°C or 5°C, and the reaction time is 5 h - 20 h, such as 5 h, 8 h, 10 h, 12 h, 15 h, 18 h or 20 h.
[0054] Preferably, the catalyst in step (7) is Fe-MCM-41.
[0055] Preferably, the temperature of the reaction in step (7) is 50°C - 100°C, such as 50°C, 60°C, 70°C, 80°C, 90°C or 100°C, and the reaction time is 2 h - 10 h, such as 2 h, 4 h, 6 h, 8 h or 10 h.
[0056] On the other hand, the present invention provides the application of the temporary plugging agent based on glycolic acid toughening modification as described above in petroleum gas exploitation.
[0057] Compared with the prior art, the present invention has the following beneficial effects:
[0058] When the temporary plugging agent of the present invention is subjected to a relatively large stress, the four-membered ring in the chain segment will be preferentially reduced and broken, while the carbon chain structure in the structure is relatively stable and will not continue to break. Therefore, the toughness of the overall chain segment is improved, achieving the purpose of toughening. BRIEF DESCRIPTION OF THE DRAWINGS
[0059] Figure 1 1H NMR spectrum of the temporary plugging agent prepared in Example 1.
[0060] Figure 2 Test result graph of the degradation rate of the temporary plugging agent prepared in Example 1. DETAILED DESCRIPTION OF THE INVENTION
[0061] The technical solution of the present invention will be further described below through specific embodiments. Those skilled in the art should understand that the embodiments are only for helping to understand the present invention and should not be regarded as specific limitations on the present invention.
[0062] Example 1
[0063] In this embodiment, the temporary plugging agent is prepared by the following preparation method:
[0064] 1. In a 1000 mL round-bottom flask, add about 500 mL of acetone and heat to boiling. Add about 150 g of 4-bromomethylcinnamic acid proportionally to the boiling acetone. The crystals remain at the bottom of the flask, and the acetone is poured into another conical flask for subsequent experiments. Add 400 mL of deionized water to a 500 ml high-temperature flask and stir. The collected crystals are suspended in deionized water. The suspension is irradiated with 365 nm ultraviolet light overnight to obtain a turbid suspension, and 80 g of white powder is obtained after filtration.
[0065] 2. Take a 250 mL round-bottom flask, mix the above white powder (50 g) with 100 mL of acetonitrile. Add EDC·HCl (70 g). Then add DMAP (3.8 g) and 8-nonen-1-ol (88 mL), and react for 12 h. After the reaction is completed, filter the solution to obtain a yellow solution. Concentrate the yellow solution with a rotary evaporator and dilute it with 200 mL of DCM. Wash the solution with deionized water (100 mL×5) and brine (100 mL×3). Collect the DCM phase and dry it with Na2SO4. After filtration, concentrate the solution onto silica gel. Column chromatography (SiO2, 0-10% ethyl acetate / hexane gradient eluent) gives a colorless oil (72.8 g).
[0066] 3. Dissolve the above product (60 g) in 1.3 L of dichloromethane, transfer it to a 2 L flask. Heat the solution to reflux, add Grubbs II (1.12 g) proportionally, and react for 12 h. After the reaction is completed, cool the solution to room temperature, and then open the air. Purify by flash column chromatography (SiO2, 0-10% ethyl acetate / hexane gradient eluent) to obtain 90 g of white solid with a yield of 95%.
[0067] 4. Dissolve the above white solid (80 g) in 100 mL of tetrahydrofuran, place it in a 250 mL three-necked round-bottom flask, and purge with argon for 15 minutes. Then add 0.4 g of palladium supported on carbon entropy (10 wt% loading), and further purge the suspension with argon for 15 minutes. Then place the suspension under vacuum for 10 seconds and introduce hydrogen through a balloon. Then purge the suspension with hydrogen for 6 hours. Remove the outlet needle, and stir the suspension under a hydrogen atmosphere for 8 h. Repeat for another day to ensure complete reaction. Remove the hydrogen balloon, purge the suspension with argon for 10 minutes, pour it onto diatomaceous earth, and wash with DCM (600 mL). Purify by flash column chromatography (SiO2, 0 - 10% ethyl acetate / hexane gradient eluent) to obtain 65 g of white solid with a yield of 60%.
[0068] 5. Mix the above product (65 g), (Bpin)2 (77 g), Pd(dppf)Cl2·DCM (10.7 g), KOAc (85.3 g) with 300 mL of anhydrous DMSO in a 1000 mL round-bottom flask. Purge the mixture with N2 for 10 minutes, heat to 110 °C, and stir the reaction overnight at 110 °C. After the reaction is complete, cool the solution to room temperature and dilute with DCM (600 mL). Filter the diluted solution through diatomaceous earth. Wash the filtrate with deionized water (200 mL × 6) and brine (200 mL × 3). Collect the DCM phase and dry it with Na2SO4. After filtration, concentrate the solution onto silica. Column chromatography (SiO2, 0 - 25% ethyl acetate / hexane gradient eluent) gives 55 g of blue-white solid.
[0069] 6. Dissolve the above compound (55 g) and acetic acid (50 mL) in 200 mL of THF, transfer it to a 500 round-bottom flask. Cool the solution in an ice-water bath. Slowly add 30% H2O2 (30 ml) dropwise, and react for 8 h. After the reaction is complete, concentrate it with a rotary evaporator and dilute with ethyl acetate (600 mL). Wash the solution with deionized water (100 mL × 6) and brine (100 mL × 3). Collect the ethyl acetate phase and dry it with Na2SO4. After filtration, concentrate the solution onto silica. Column chromatography (SiO2, 0 - 40% ethyl acetate / hexane gradient eluent) gives the product as a colorless viscous oil, which becomes a solid under vacuum. Store it in the refrigerator.
[0070] 7. Prepare Fe-MCM-41 according to the molar ratio TEOS:CTAB:NH3·H2O:Fe(NO3)3 = 1:0.2:100:70. Dissolve CATB in NH3·H2O, stir well and slowly drop it into the mixed solution of TEOS and Fe(NO3)3 to form a gel. Stir for 30 min, crystallize for 4 h, filter and dry (90 °C, 2 h), and calcine (550 °C, 6 h). Obtain Fe-MCM-41.
[0071] 8. Take 2 g of Fe-MCM-41, add 50 mL of water, stir in a water bath at 30 °C for 10 min, dropwise add 6 mL of an aqueous solution of H2PtCl6·6H2O, stir for 0.5 h, add an aqueous solution of sodium borohydride for reduction for 6 h, centrifuge to remove the supernatant, wash, and dry (at 120 °C for 12 h) to obtain Pt / Fe-MCM-41.
[0072] 9. Take 1 g of Pt / Fe-MCM-4, 30 mL of the aqueous solution of the product obtained in step 6, and 2 g of NaOH (adjust the pH to about 13) in a 100 mL flask, heat to 70 °C under magnetic stirring, and blow O2 into the aqueous solution at a gas flow rate of 60 mL / min for 4 h to obtain the product.
[0073] 10 Add the above product and GA to a 100 mL three-necked flask in a molar ratio of 1:1, add 0.25% C 16 H 30 O4Sn / ZnCl2 composite catalyst and molecular sieve, react under vacuum at 200 °C for 8 h to obtain a crude product, dissolve it with chloroform, filter off the insoluble matter, add methanol to precipitate, and obtain the polymer, which is the temporary plugging agent, with a molecular weight of about 50,000 and a yield of 64%. The 1H NMR spectrum of the product is as Figure 1 shown. 1 1H NMR (300 MHz, DMSO): ppm, 1H: 5.27; 2H: 4.61; 3H: 7.18; 4H: 7.19; 5H: 4.2; 6H: 4.06; 7H: 1.55; 8H: 1.25; 9H: 7.43; 10H: 7.93; 11H: 5.21; 12H: 5.20; 13H: 12.80.
[0074] Degradation rate test
[0075] Test method: Weigh 50 g of the knot sample, put the sample into a 200 mL stoppered reagent bottle, add 95 g of distilled water, place the stoppered reagent bottle containing the sample and distilled water in an electronic constant temperature oven, and set the dissolution temperature to the actual use temperature of the sample. Take out a stoppered reagent bottle every 12 h, filter the liquid and the sample with a glass crucible. After filtration, dry it until it reaches a constant weight. When the mass change is greater than 5%, the corresponding time is regarded as the start dissolution time; when the difference in the remaining solid mass of the sample is not more than 5%, the corresponding time before the mass does not change is the final dissolution time, see Figure 2 .
[0076] From Figure 2 it can be seen that the degradation rate of the sample can reach 90% at 30 h and can be completely degraded at 40 h.
[0077] Example 2
[0078] In this embodiment, a temporary plugging agent is prepared by the following preparation method:
[0079] 1. Add about 500 mL of acetone to a 1000 mL round-bottom flask and heat it to the boiling point. Add about 150 g of 4-bromomethylcinnamic acid proportionally to the boiling acetone. The crystals remain at the bottom of the flask, and the acetone is poured into another conical flask for subsequent experiments. Add 400 mL of deionized water to a 500 ml high-temperature flask and stir. The collected crystals are suspended in deionized water. The suspension is irradiated with 365 nm ultraviolet light overnight to obtain a turbid suspension, and 80 g of white powder is obtained after filtration.
[0080] 2. Take a 250 mL round-bottom flask, mix the above white powder (50 g) with 100 mL of acetonitrile. Add EDC·HCl (70 g). Then add DMAP (3.8 g) and 8-nonen-1-ol (88 mL), and react for 12 h. After the reaction is completed, the solution is filtered to obtain a yellow solution. The yellow solution is concentrated with a rotary evaporator and diluted with 200 mL of DCM. The solution is washed with deionized water (100 mL × 5) and brine (100 mL × 3). The DCM phase is collected and dried with Na2SO4. After filtration, the solution is concentrated onto silica gel. Column chromatography (SiO2, 0-10% ethyl acetate / hexane gradient eluent) gives a colorless oil (72.8 g).
[0081] 3. Dissolve the above product (60 g) in 1.3 L of dichloromethane, transfer it to a 2 L flask. Heat the solution to reflux, add Grubbs II (1.12 g) proportionally, and react for 12 h. After the reaction is completed, cool the solution to room temperature, and then open the air. Purify by flash column chromatography (SiO2, 0-10% ethyl acetate / hexane gradient eluent) to obtain 90 g of white solid with a yield of 88%.
[0082] 4. Dissolve the above white solid (80 g) in 100 mL of tetrahydrofuran, place it in a 250 mL three-necked round-bottom flask, and purge with argon for 15 minutes. Then add 0.4 g of palladium supported on carbon entropy (10 wt% loading), and further purge the suspension with argon for 15 minutes. Then place the suspension under vacuum for 10 seconds and introduce hydrogen through a balloon. Then purge the suspension with hydrogen for 6 hours. Remove the outlet needle, and stir the suspension under a hydrogen atmosphere for 8 h. Repeat for another day to ensure complete reaction. Remove the hydrogen balloon, purge the suspension with argon for 10 minutes, pour it onto diatomaceous earth, and wash with DCM (600 mL). Purify by flash column chromatography (SiO2, 0-10% ethyl acetate / hexane gradient eluent) to obtain 65 g of white solid with a yield of 60%.
[0083] 5. Mix the above product (65 g), (Bpin)2 (77 g), Pd(dppf)Cl2·DCM (10.7 g), KOAc (85.3 g) with 300 mL of anhydrous DMSO in a 1000 mL round-bottom flask. Purge the mixture with N2 for 10 minutes, heat to 110 °C, and stir the reaction overnight at 110 °C. After the reaction is complete, cool the solution to room temperature and dilute with DCM (600 mL). Filter the diluted solution through diatomaceous earth. Wash the filtrate with deionized water (200 mL × 6) and brine (200 mL × 3). Collect the DCM phase and dry it over Na2SO4. After filtration, concentrate the solution onto silica gel. Column chromatography (SiO2, 0 - 25% ethyl acetate / hexane gradient eluent) gives 55 g of a blue-white solid.
[0084] 6. Dissolve the above compound (55 g) and acetic acid (50 mL) in 200 mL of THF, transfer it to a 500 round-bottom flask. Cool the solution in an ice-water bath. Slowly add 30% H2O2 (30 ml) dropwise and react for 8 h. After the reaction is complete, concentrate it with a rotary evaporator and dilute with ethyl acetate (600 mL). Wash the solution with deionized water (100 mL × 6) and brine (100 mL × 3). Collect the ethyl acetate phase and dry it over Na2SO4. After filtration, concentrate the solution onto silica gel. Column chromatography (SiO2, 0 - 40% ethyl acetate / hexane gradient eluent) gives the product as a colorless viscous oil, which becomes a solid under vacuum. Store it in the refrigerator.
[0085] 7. Prepare Fe-MCM-41 according to the molar ratio TEOS:CTAB:NH3·H2O:Fe(NO3)3 = 1:0.2:100:70. Dissolve CATB in NH3·H2O, stir evenly and then slowly drop it into the mixed solution of TEOS and Fe(NO3)3 to form a gel. Stir for 30 min, crystallize for 4 h, filter and dry (90 °C, 2 h), and calcine (550 °C, 6 h). Obtain Fe-MCM-41.
[0086] 8. Take 2 g of Fe-MCM-41, add 50 mL of water, stir in a water bath at 50 °C for 10 min, dropwise add 6 mL of an aqueous solution of H2PtCl6·6H2O, stir for 0.5 h, add an aqueous solution of sodium borohydride to reduce for 6 h, centrifuge to remove the supernatant, wash, and dry (120 °C, 12 h) to obtain Pt / Fe-MCM-41.
[0087] 9. Take 1 g of Pt / Fe-MCM-4, 30 mL of the aqueous solution of the product obtained in step 6, and 2 g of NaOH (adjust the pH to about 13) in a 100 mL flask, heat to 70 °C under magnetic stirring, and blow O2 into the aqueous solution at a gas flow rate of 60 mL / min for 4 h to obtain the product.
[0088] 10 Add the above product and GA to a 100 mL three-necked flask at a molar ratio of 2:1, and add 0.5% of C 16 H 30 O4Sn / ZnCl2 composite catalyst and molecular sieve, and react under vacuum at 200 °C for 8 h to obtain a crude product. Dissolve it in chloroform, filter off the insoluble matter, add methanol to precipitate, and obtain a polymer, which is the temporary plugging agent. The molecular weight is about 60,000 and the yield is 78%.
[0089] Example 3
[0090] In this example, a temporary plugging agent is prepared by the following preparation method:
[0091] 1. Add about 500 mL of acetone to a 1000 mL round-bottom flask and heat it to boiling. Add about 150 g of 4-bromomethylcinnamic acid to the boiling acetone in proportion. The crystals remain at the bottom of the flask, and the acetone is poured into another conical flask for subsequent experiments. Add 400 mL of deionized water to a 500 ml high-temperature flask and stir. The collected crystals are suspended in deionized water. The suspension is irradiated with 365 nm ultraviolet light overnight to obtain a turbid suspension, and 80 g of white powder is obtained after filtration.
[0092] 2. Take a 250 mL round-bottom flask, mix the above white powder (50 g) with 100 mL of acetonitrile. Add EDC·HCl (70 g). Then add DMAP (3.8 g) and 8-nonen-1-ol (88 mL), and react for 12 h. After the reaction is completed, filter the solution to obtain a yellow solution. Concentrate the yellow solution with a rotary evaporator and dilute it with 200 mL of DCM. Wash the solution with deionized water (100 mL × 5) and brine (100 mL × 3). Collect the DCM phase and dry it with Na2SO4. After filtration, concentrate the solution onto silica gel. Column chromatography (SiO2, 0-10% ethyl acetate / hexane gradient eluent) gives a colorless oil (72.8 g).
[0093] 3. Dissolve the above product (60 g) in 1.3 L of dichloromethane, transfer it to a 2 L flask. Heat the solution to reflux, add Grubbs II (1.12 g) in proportion, and react for 12 h. After the reaction is completed, cool the solution to room temperature, and then open the air. Purify by flash column chromatography (SiO2, 0-10% ethyl acetate / hexane gradient eluent) to obtain 90 g of white solid with a yield of 88%.
[0094] 4. Dissolve the above white solid (80 g) in 100 mL of tetrahydrofuran, place it in a 250 mL three-necked round-bottom flask, and purge with argon for 15 minutes. Then add 0.4 g of palladium supported on carbon entropy (10 wt% loading), and further purge the suspension with argon for 15 minutes. Then place the suspension under vacuum for 10 seconds and introduce hydrogen through a balloon. Then purge the suspension with hydrogen for 6 hours. Remove the outlet needle and stir the suspension under a hydrogen atmosphere for 8 h. Repeat for another day to ensure complete reaction. Remove the hydrogen balloon, purge the suspension with argon for 10 minutes, pour it onto diatomaceous earth, and wash with DCM (600 mL). Purify by flash column chromatography (SiO2, 0 - 10% ethyl acetate / hexane gradient eluent) to obtain 65 g of white solid with a yield of 60%.
[0095] 5. Mix the above product (65 g), (Bpin)2 (77 g), Pd(dppf)Cl2·DCM (10.7 g), KOAc (85.3 g) with 300 mL of anhydrous DMSO in a 1000 mL round-bottom flask. Purge the mixture with N2 for 10 minutes, heat to 110 °C, and stir the reaction overnight at 110 °C. After the reaction is complete, cool the solution to room temperature and dilute with DCM (600 mL). Filter the diluted solution through diatomaceous earth. Wash the filtrate with deionized water (200 mL × 6) and brine (200 mL × 3). Collect the DCM phase and dry it with Na2SO4. After filtration, concentrate the solution onto silica gel. Column chromatography (SiO2, 0 - 25% ethyl acetate / hexane gradient eluent) gives 55 g of blue-white solid.
[0096] 6. Dissolve the above compound (55 g) and acetic acid (50 mL) in 200 mL of THF, transfer it to a 500 round-bottom flask. Cool the solution in an ice-water bath. Slowly add 30% H2O2 (30 ml)), and react for 8 h. After the reaction is complete, concentrate it with a rotary evaporator and dilute with ethyl acetate (600 mL). Wash the solution with deionized water (100 mL × 6) and brine (100 mL × 3). Collect the ethyl acetate phase and dry it with Na2SO4. After filtration, concentrate the solution onto silica gel. Column chromatography (SiO2, 0 - 40% ethyl acetate / hexane gradient eluent) gives the product as a colorless viscous oil, which becomes a solid under vacuum. Store it in the refrigerator.
[0097] 7. Prepare Fe-MCM-41 according to the molar ratio TEOS:CTAB:NH3·H2O:Fe(NO3)3 = 1:0.2:100:70. Dissolve CATB in NH3·H2O, stir evenly, and slowly drop it into the mixed solution of TEOS and Fe(NO3)3 to form a gel. Stir for 30 min, crystallize for 4 h, filter and dry (90 °C, 2 h), and calcine (550 °C, 6 h). Obtain Fe-MCM-41.
[0098] 8. Take 2 g of Fe-MCM-41, add 50 mL of water, stir in a water bath at 60 °C for 10 min, dropwise add 6 mL of an aqueous solution of H2PtCl6·6H2O, stir for 0.5 h, add an aqueous solution of sodium borohydride for reduction for 6 h, centrifuge to remove the supernatant, wash, and dry (120 °C, 12 h) to obtain Pt / Fe-MCM-41.
[0099] 9. Take 1 g of Pt / Fe-MCM-4, 30 mL of the aqueous solution of the product obtained in step 6, and 2 g of NaOH (adjust the pH to about 13) in a 100 mL flask, heat to 70 °C under magnetic stirring, and blow O2 into the aqueous solution at a gas flow rate of 60 mL / min for 4 h to obtain the product.
[0100] 10. Add the above product and GA to a 100 mL three-necked flask in a molar ratio of 1:1, add 1% of the C 16 H 30 O4Sn / ZnCl2 composite catalyst and molecular sieve, react under vacuum at 200 °C for 8 h to obtain a crude product, dissolve it with chloroform, filter off the insoluble matter, add methanol to precipitate, and obtain the polymer, which is the temporary plugging agent, with a molecular weight of about 80,000 and a yield of 80%.
[0101] Compressive strength test:
[0102] Test method: Take 50 g of the sample and place it on a simulated device for borehole plugging. The diameter of the ball seat hole of the simulated device is 3.0 mm to 5.0 mm; place the simulated device in a core holder for fixation, preheat the instrument to the test temperature of the knot temporary plugging agent, inject liquid at a constant rate, continuously increase the pressure to the set pressure value after the pressure rises, maintain the pressure, and the highest pressure value during the experiment is the plugging strength. The time from the start of pressure increase to the end of steep pressure drop is the effective plugging time; the results are shown in Table 1.
[0103] Table 1 shows the compressive strength test results of Examples 1 - 3 at 80 - 120 °C
[0104]
[0105] The applicant declares that the present invention uses the above examples to illustrate the temporary plugging agent based on glycolic acid toughening modification, its preparation method and application, but the present invention is not limited to the above examples, that is, it does not mean that the present invention must rely on the above examples to be implemented. Those skilled in the art should understand that any improvement of the present invention, the equivalent replacement of the raw materials selected for the present invention, the addition of auxiliary components, the selection of specific methods, etc. all fall within the protection scope and the disclosure scope of the present invention.
Claims
1. A temporary plugging agent based on glycolic acid toughening modification, characterized in that The temporary plugging agent based on glycolic acid toughening modification has the structure shown in formula I below: Where n is 1 - 100.
2. The preparation method of the temporary plugging agent based on glycolic acid toughening modification according to claim 1, wherein, The preparation method includes the following steps: The compound shown in formula II undergoes a polymerization reaction with glycolic acid to obtain the temporary plugging agent with glycolic acid toughening modification. The reaction formula is as follows:
3. The preparation method according to claim 1, wherein, The molar ratio of the compound shown in formula II to glycolic acid is 1:(0.9 - 1.2); Preferably, the polymerization reaction is carried out in the presence of a catalyst; Preferably, the catalyst is selected from the C 16 H 30 O4Sn / ZnCl2 composite catalyst; Preferably, the polymerization reaction is carried out in the presence of a molecular sieve; Preferably, the molecular sieve is selected from ZSM-5 type molecular sieve; Preferably, the temperature of the polymerization reaction is 180°C - 220°C, and the reaction time is 5h - 10h.
4. The preparation method according to claim 2 or 3, characterized in that, The compound shown in formula II is prepared by the following preparation method: (1) 4-Bromomethylcinnamic acid is added to boiling acetone to obtain crystals. The crystals are suspended in deionized water and irradiated with 365nm ultraviolet light overnight to obtain compound 1. The reaction formula is as follows: (2) Compound 1 is mixed with acetonitrile, 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride is added dropwise, and then 4-dimethylaminopyridine and 8-nonen-1-ol are added for reaction to obtain compound 2. The reaction formula is as follows: (3) Compound 2 undergoes a ring-closure reaction in the presence of a catalyst to obtain compound 3. The reaction formula is as follows: (4) Compound 3 undergoes a hydrogenation reaction with hydrogen to obtain compound 4. The reaction formula is as follows: (5) Compound 4 reacts with bis(pinacolato)diboron to obtain compound 6. The reaction formula is as follows: (6) Compound 5 and acetic acid are dissolved in tetrahydrofuran, and hydrogen peroxide is added for reaction to obtain compound 6. The reaction formula is as follows: (7) In the presence of a catalyst, O2 is introduced into the reaction solution containing compound 6 and sodium hydroxide to react to obtain compound 7, that is, the compound shown in formula II. The reaction formula is as follows:
5. The preparation method according to claim 4, characterized in that, The amount of acetone used in step (1) is 3 - 4 times the mass of 4-bromomethylcinnamic acid; Preferably, the amount of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride used in step (2) is 1 - 2 times the mass of compound 1; Preferably, the amount of 4-dimethylaminopyridine used in step (2) is 5% - 10% of the mass of compound 1; Preferably, the molar ratio of 8-nonen-1-ol to compound 1 in step (2) is (0.8 - 1.2):1 Preferably, the temperature of the reaction in step (2) is 140°C - 180°C, and the reaction time is 10h - 20h.
6. The preparation method according to claim 4 or 5, characterized in that, The catalyst used in step (3) is selected from Grubbs II; Preferably, the amount of the catalyst used in step (3) is 1% - 5% of the mass of compound 2; Preferably, the ring-closure reaction in step (3) is carried out under reflux, and the reaction time is 10h - 20h.
7. The preparation method according to any one of claims 4-6, characterized in that The hydrogenation reaction in step (4) is carried out under the catalysis of Pd / C; Preferably, the amount of Pd / C used is 0.5% - 1% of the mass of compound 3; Preferably, the hydrogenation reaction in step (4) is carried out in a solvent, and the solvent is tetrahydrofuran; Preferably, the hydrogenation reaction in step (4) is carried out at room temperature, and the reaction time is 5h - 20h.
8. The preparation method according to any one of claims 4-7, characterized in that, The molar ratio of the compound 4 described in step (5) to bis(pinacolato)diboron is (0.8 - 1.2):1; Preferably, the reaction described in step (5) is carried out in the presence of a catalyst; Preferably, the catalyst is selected from Pd(dppf)Cl2; Preferably, the reaction described in step (5) is carried out in the presence of a basic substance, and the basic substance is selected from potassium acetate; Preferably, the reaction described in step (5) is carried out in a solvent, and the solvent is selected from dimethyl sulfoxide; Preferably, the reaction described in step (5) is carried out under nitrogen protection; Preferably, the temperature of the reaction described in step (5) is 90°C - 130°C, and the reaction time is 10 h - 20 h.
9. The preparation method according to any one of claims 4-8, characterized in that, The molar ratio of the compound 5 described in step (6) to acetic acid is (0.8 - 1.2):1; Preferably, the temperature of the reaction with the addition of hydrogen peroxide in step (6) is 0 - 5°C, and the reaction time is 5 h - 20 h; Preferably, the catalyst in step (7) is Fe-MCM-41; Preferably, the temperature of the reaction in step (7) is 50°C - 100°C, and the reaction time is 2 h - 10 h.
10. The application of the temporary plugging agent based on glycolic acid toughening modification according to claim 1 in petroleum gas production.