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CN-122011282-A - Polyacrylamide based on molecular chain topological structure regulation and synthesis method thereof

CN122011282ACN 122011282 ACN122011282 ACN 122011282ACN-122011282-A

Abstract

The invention belongs to the technical field of oil and gas exploitation, and particularly relates to a temperature-resistant and salt-resistant polyacrylamide based on molecular chain topological structure regulation and control and a synthesis method thereof. 130-146 parts of acrylamide, 10-22 parts of acrylic acid, 120-140 parts of 2-acrylamide-2-methylpropanesulfonic acid, 55.5-60 parts of sodium hydroxide, 6.5-10 parts of topological structure functional monomers, 0.5-1 part of surfactant, 16-32 parts of initiator No. 1, 0.8-1.7 parts of initiator No.2 and 600-720 parts of deionized water. By introducing topological structure functional monomers to participate in copolymerization, a linear long-chain structure with a rigid side chain or chain segment is constructed, and the temperature resistance and the salt resistance are cooperatively improved while the good solubility of the linear polymer is maintained. The polyacrylamide is used as an oil displacement agent in exploitation of high-temperature and high-salt oil and gas reservoirs.

Inventors

  • CHEN LILI
  • GUAN XIAOXU
  • WAN YUJIA
  • ZHANG TINGTING
  • SUN ANSHUN

Assignees

  • 黑龙江吉地油田服务股份有限公司

Dates

Publication Date
20260512
Application Date
20260203

Claims (9)

  1. 1. The polyacrylamide based on molecular chain topological structure regulation is characterized in that the polyacrylamide based on molecular chain topological structure regulation is of a linear long-chain structure, the molecular chain of the polyacrylamide comprises topological structure functional monomers introduced through copolymerization, and the topological structure functional monomers are used as a part of a polymer side chain or a main chain to endow the molecular chain with rigidity and enhance the hydration capability; 130-146 parts of acrylamide, 10-22 parts of acrylic acid, 120-140 parts of 2-acrylamide-2-methylpropanesulfonic acid, 55.5-60 parts of sodium hydroxide, 6.5-10 parts of a topological structure functional monomer, 0.5-1 part of a surfactant, 16-32 parts of a No.1 initiator, 0.85-1.7 parts of a No.2 initiator and 600-720 parts of deionized water; The initiator No. 1 is one of soybean peroxidase, alkaline phosphatase or horseradish peroxidase, the initiator No. 2 is one of sodium peroxide, hydrogen peroxide or peracetic acid, and the surfactant is one of glucamide, sucrose ester or alkyl glycoside; The structural general formula of the topological structure functional monomer is a cyclic core- (connecting arm-functional arm) n, wherein the cyclic core is beta-cyclodextrin, the connecting arm is C 2 -C 12 alkylene, the functional arm is a pentaerythritol triacrylate derivative, 3 acrylate groups are reserved, and n is an integer of 3-7.
  2. 2. The polyacrylamide based on molecular chain topology control according to claim 1, wherein the linker arm is an adipic acid-derived C 5 alkylene chain.
  3. 3. The polyacrylamide according to claim 1, wherein n in the cyclic core- (linker-functional arm) n is 4.
  4. 4. The instant sewage-resistant low-viscosity high-elastic polymer according to claim 1 to 3, wherein the components and parts by weight of the polyacrylamide based on molecular chain topology regulation are 130 parts of acrylamide, 10 parts of acrylic acid, 120 parts of 2-acrylamide-2-methylpropanesulfonic acid, 55.5 parts of sodium hydroxide, 6.5 parts of a topology functional monomer, 0.5 part of a surfactant, 16 parts of a No. 1 initiator, 0.85 part of a No. 2 initiator and 600 parts of deionized water.
  5. 5. The polyacrylamide based on molecular chain topology regulation according to any one of claims 1 to 3, wherein the components and parts by weight of the polyacrylamide based on molecular chain topology regulation are 138 parts of acrylamide, 16 parts of acrylic acid, 130 parts of 2-acrylamide-2-methylpropanesulfonic acid, 57.75 parts of sodium hydroxide, 8.25 parts of topology functional monomer, 0.75 part of surfactant, 24 parts of initiator No. 1, 1.275 parts of initiator No. 2 and 660 parts of deionized water.
  6. 6. The polyacrylamide based on molecular chain topology regulation according to any one of claims 1 to 3, wherein the components and parts by weight of the polyacrylamide based on molecular chain topology regulation are 146 parts of acrylamide, 22 parts of acrylic acid, 140 parts of 2-acrylamide-2-methylpropanesulfonic acid, 60 parts of sodium hydroxide, 10 parts of topology functional monomer, 1 part of surfactant, 32 parts of initiator No. 1, 1.7 parts of initiator No. 2 and 720 parts of deionized water.
  7. 7. The polyacrylamide based on molecular chain topology regulation according to any one of claims 1-3, wherein the synthesis method of the topology functional monomer comprises the following steps: Step one, synthesizing adipic acid monopentafluorophenol ester Adding 100 parts of adipic acid, 100 parts of pentafluorophenol and anhydrous methylene dichloride into a 250ml flask, cooling the flask to 0 ℃ in an ice bath, dropwise adding 110 parts of condensing agent into the flask at constant speed through a constant pressure dropping funnel under the ice bath condition, continuously stirring, removing the ice bath from the flask after the dropwise adding is finished, naturally heating the reaction liquid in the flask to room temperature, continuously stirring at the room temperature for 4 hours, filtering white precipitate in the reaction liquid after the reaction is finished, concentrating the filtrate after the filtering precipitate under reduced pressure, purifying the concentrated crude product through silica gel column chromatography, and obtaining white fixed adipic acid monopentafluorophenol ester, wherein the synthetic chemical structural reaction formula is as follows: The condensing agent is one of N, N ‌' -diisopropylcarbodiimide DIC, dicyclohexylcarbodiimide DCC, 1-ethyl-3-carbodiimide hydrochloride or 3-dimethylaminopropyl carbodiimide hydrochloride; step two, synthesizing pentaerythritol monoadipate triacrylate PETA-C5-COOH Adding 100 parts of pentaerythritol triacrylate, 5 parts of catalyst and anhydrous acetonitrile into a dry three-port bottle, introducing nitrogen for protection, stirring to completely dissolve solids, slowly adding 95 parts of adipic acid monopentafluorophenol ester into the three-port bottle under the conditions of nitrogen atmosphere and light shielding, stirring and reacting for 3 hours under the conditions of room temperature and light shielding, dissolving residues into ethyl acetate after the reaction is finished, washing the residues with 5% dilute hydrochloric acid and saturated saline water in sequence, drying an organic phase with anhydrous sodium sulfate, filtering the dried organic phase, concentrating the filtrate to obtain a crude product, and purifying the crude product by silica gel column chromatography to obtain colorless transparent viscous liquid, namely pentaerythritol triacrylate PETA-C5-COOH, wherein the synthetic chemical structural reaction formula is as follows: The catalyst is one of 4-dimethylaminopyridine, triethylamine or 1-methylimidazole; Step three, synthesizing primary hydroxyl full sulfonyl beta-cyclodextrin beta-CD- (OTs) 7 Reacting the beta-cyclodextrin with a sulfonylating agent to obtain primary hydroxyl-fully sulfonylated beta-cyclodextrin (beta-CD- (OTs) 7 ); Suspending 100 parts of beta-cyclodextrin in anhydrous pyridine in a three-mouth bottle, placing the three-mouth bottle of a reaction system in an ice salt bath, cooling the temperature in the bottle to below 5 ℃ under intense stirring, slowly adding 700 parts of sulfonylating reagent for a plurality of times under the condition of keeping the temperature in the bottle to be not higher than 10 ℃, removing the ice salt bath, continuously stirring and reacting for 48 hours after the reaction liquid slowly rises to room temperature; the sulfonylation reagent is one of benzenesulfonyl chloride, naphthalenesulfonyl chloride or p-toluenesulfonyl chloride; Step four, connecting and synthesizing a topological structure functional monomer CD-PETA 4 (1) Activated pentaerythritol triacrylate of monoadipic acid PETA-C5-COOH Dissolving 100 parts of pentaerythritol monoadipate triacrylate PETA-C5-COOH in anhydrous dichloromethane in a flask, adding 100 parts of pentafluorophenol into the flask, cooling the flask to 0 ℃ in an ice bath, dropwise adding 110 parts of condensing agent into the flask at a constant speed through a constant pressure dropping funnel under the ice bath condition, continuously stirring, removing the ice bath after the dropwise adding is finished, naturally heating the reaction solution in the flask to room temperature, continuously stirring at the room temperature for 4 hours, filtering the reaction solution after the reaction is finished, and concentrating the filtrate under reduced pressure to obtain a crude product of pentaerythritol monoadipate triacrylate PETA-C5-PFP ester; (2) Nucleophilic substitution ligation Dissolving 10 parts of primary hydroxyl full sulfonyl beta-cyclodextrin beta-CD- (OTs) 7 in anhydrous N, N-dimethylformamide DMF (dimethyl formamide) in a dry three-mouth bottle, adding 300 parts of anhydrous pyridine as an acid binding agent, slowly dropwise adding 1050 parts of N, N-dimethylformamide DMF solution of a PETA-C5-PFP crude product into a reaction bottle under the conditions of nitrogen protection and mechanical stirring, and after dropwise adding, placing the three-mouth bottle of the reaction system into an oil bath and heating to 55 ℃, and stirring and reacting for 36 hours at the temperature; (3) Purification of After the reaction in the step (2) is finished, cooling the reaction liquid to room temperature, concentrating, dropwise adding glacial ethyl ether into the concentrated liquid under intense stirring for precipitation, centrifugally collecting the precipitate, washing the precipitate by using ethyl ether to obtain a crude product, separating and purifying the crude product by using a preparative high performance liquid chromatography, and freeze-drying the crude product to obtain the white immobilized topological structure functional monomer CD-PETA 4 .
  8. 8. The polyacrylamide based on molecular chain topology regulation according to any one of claims 1 to 3, wherein the preparation method of the polyacrylamide based on molecular chain topology regulation comprises the following steps: Step 1, adding 600-720 parts of deionized water into a reaction kettle, and then sequentially adding 130-146 parts of acrylamide, 120-140 parts of 2-acrylamide-2-methylpropanesulfonic acid, 10-22 parts of acrylic acid, 55.5-60 parts of sodium hydroxide and 6.5-10 parts of topological structure functional monomer CD-PETA 4 ; Step 2, starting a stirring mechanism of the reaction kettle, introducing nitrogen into the reaction kettle for bubbling, dissolving the mixture in the step 1 in water under the protection of inert gas, adjusting the pH value to 7-7.5 by using alkali liquor after all components are completely dissolved, forming a homogeneous monomer solution, and continuously introducing nitrogen for deoxidization; Step 3, controlling the temperature in the reaction kettle at 20-40 ℃, dissolving 16-32 parts of No.1 initiator in phosphate buffer solution, adding the enzyme solution into a reaction system of the reaction kettle, then dripping 0.85-1.7 parts of No.2 initiator into the reaction kettle at a constant speed, and obtaining a high-viscoelasticity polymerization product after the reaction is finished; Step 4, preparing an ethanol solution containing 0.5-1 part of surfactant, mixing the polymerization product prepared in the step3 with the ethanol solution, and then putting the mixture into a granulator for granulation; And 5, drying the particles prepared in the step 4 to constant weight in a 60 ℃ vacuum drying oven, and crushing and sieving to obtain white powder, namely the temperature-resistant and salt-resistant polyacrylamide based on molecular chain topological structure regulation.
  9. 9. The polyacrylamide based on molecular chain topological structure regulation and control according to claim 8, wherein the prepared temperature-resistant and salt-resistant polyacrylamide based on molecular chain topological structure regulation and control is used as an oil displacement agent in oil and gas exploitation.

Description

Polyacrylamide based on molecular chain topological structure regulation and synthesis method thereof Technical Field The invention belongs to the technical field of oil and gas exploitation, and particularly relates to a temperature-resistant and salt-resistant polyacrylamide based on molecular chain topological structure regulation and control and a synthesis method thereof. Background Polyacrylamide (PAM) and derivatives thereof are key chemicals widely applied to tertiary oil recovery, and can be used as oil displacement agents to effectively improve the recovery ratio of crude oil. However, conventional polyacrylamides can experience dramatic performance decay in harsh reservoir environments at high temperatures (> 60 ℃) and high salts (total mineralization ≡10000mg/L, especially rich in divalent ions). The high temperature can cause chain breakage and excessive shrinkage of the molecular chains, so that the hydrodynamic volume is reduced, and the hypersalinity can seriously compress the electric double layer of the molecular chains, shield electrostatic repulsive force among chain segments and intensify the shrinkage of the molecular chains. The synergistic effect of high temperature and high salinity leads to the substantial decrease of the apparent viscosity of the polymer solution, even loss of the tackifying and oil displacement capabilities, which severely restricts the application of the polymer solution under severe oil reservoir conditions. In the prior art, although the three-dimensional network structure formed by crosslinking can improve certain stability, the solubility and the shearing resistance of the polymer are often sacrificed, and the problem of non-uniform network structure still exists. On the premise of keeping good solubility and processability of the linear structure, the temperature resistance and salt resistance of the linear structure are obviously improved, and the technical problem to be solved in the field is still urgent. Disclosure of Invention In order to solve the technical problems, the invention provides a temperature-resistant and salt-resistant polyacrylamide based on molecular chain topological structure regulation and a synthesis preparation method. On one hand, the polymer constructs a linear long-chain structure with a rigid side chain or chain segment by introducing a unique topological structure functional monomer to participate in copolymerization, so that the temperature resistance and the salt resistance are cooperatively improved from the molecular chain level while the good solubility of the linear polymer is maintained, and the topological structure functional monomer and a mild and efficient synthesis method thereof are provided. On the other hand, a synthesis method of the temperature-resistant and salt-resistant polyacrylamide is provided, and an environment-friendly enzyme catalysis initiation system is adopted in the method. The heat-resistant and salt-resistant polyacrylamide is used as an oil displacement agent in exploitation of high-temperature and high-salt oil and gas reservoirs. The technical scheme adopted by the invention is that the polyacrylamide based on molecular chain topological structure regulation is of a linear long-chain structure, the molecular chain of the polyacrylamide based on molecular chain topological structure regulation comprises topological structure functional monomers introduced through copolymerization, and the topological structure functional monomers are used as a part of a polymer side chain or a main chain, so that the molecular chain rigidity is endowed and the hydration capacity of the polyacrylamide is enhanced. An environmentally friendly enzyme-catalyzed priming system is employed. Based on components and parts by weight of molecular chain topological structure regulation polyacrylamide, 130-146 parts of acrylamide, 10-22 parts of acrylic acid, 120-140 parts of 2-acrylamide-2-methylpropanesulfonic acid, 55.5-60 parts of sodium hydroxide, 6.5-10 parts of topological structure functional monomer, 0.5-1 part of surfactant, 16-32 parts of initiator No. 1, 0.85-1.7 parts of initiator No. 2 and 600-720 parts of deionized water. The initiator No. 1 is one of soybean peroxidase, alkaline phosphatase or horseradish peroxidase, the initiator No. 2 is one of sodium peroxide, hydrogen peroxide or peracetic acid, and the surfactant is one of glucose amide, sucrose ester or alkyl glycoside. The structural general formula of the topological structure functional monomer is a cyclic core- (connecting arm-functional arm) n, wherein the cyclic core is beta-cyclodextrin, the connecting arm is C 2-C12 alkylene, the functional arm is a pentaerythritol triacrylate derivative, 3 acrylate groups are reserved and used as anchor points for subsequent copolymerization with vinyl monomers, and n is an integer of 3-7. Further, the linker arm is an adipic acid-derived C 5 alkylene chain. Further, n in the cyclic core- (linker-functional