CN111393570B - Hyperbranched polyvinylpyrrolidone natural gas hydrate inhibitor with inner salt structure and preparation method and application thereof - Google Patents
Hyperbranched polyvinylpyrrolidone natural gas hydrate inhibitor with inner salt structure and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a hyperbranched polyvinylpyrrolidone natural gas hydrate inhibitor with an inner salt structure and a preparation method and application thereof. The method comprises the following steps: (1) under the action of hydrochloric acid, 4-vinylpyridine and 1, 3-propane sultone undergo a ring-opening reaction to obtain a monomer containing zwitterions, (2) vinylpyrrolidone and the monomer containing zwitterions are dissolved in water, and cerium salt is added for reaction; (3) adding hydroxyl polyether ester polyol and cerium salt into the reaction system in the step (2) and continuing to react; (4) continuously adding the vinylpyrrolidone and the fluorocarbon amphiphilic surfactant into the reaction system in the step (3) to continuously react; (5) and (4) drying the reaction system in the step (4), and performing alkaline hydrolysis. The product of the invention has stable performance, can be used as a natural gas hydrate inhibitor, and can obviously delay the induction time.
Description
Technical Field
The invention relates to a hyperbranched polyvinylpyrrolidone natural gas hydrate inhibitor with an inner salt structure and a preparation method and application thereof, belonging to the technical field of natural gas hydrate inhibitors and preparation thereof.
Background
The formation of hydrates can cause plugging of natural gas, oil production facilities and gathering lines. Particularly at offshore fields where temperature and pressure conditions are suitable for hydrate formation, the economic losses due to formation can be as high as several billion dollars. Therefore, how to prevent the formation of hydrates has been a difficult point and focus of attention in the oil and gas industry.
At present, two control methods, namely a kinetic control method and a thermodynamic inhibition method, are shared worldwide, wherein the method which is most widely applied is the thermodynamic inhibition method and is characterized in that dehydration, depressurization and addition of an inhibitor are carried out. Common inhibitors are methanol, ethanol, ethylene glycol, triethylene glycol, etc., which can increase the pressure conditions required for hydrate formation above the operating pressure in the pipeline, or reduce the temperature required for hydrate formation below the operating temperature of the pipeline, thereby avoiding hydrate formation. The concentration of the inhibitor in water needs to reach 10% -60%, so the consumption of the traditional inhibitor is very large, and the development and production of oil and gas fields need to be carried out with high-efficiency hydrate inhibitors.
Disclosure of Invention
The invention aims to provide a hyperbranched polyvinylpyrrolidone natural gas hydrate inhibitor with an inner salt structure and a preparation method and application thereof, wherein the hyperbranched polyvinylpyrrolidone natural gas hydrate inhibitor with the inner salt structure is obtained by introducing a monomer containing zwitterions while replacing the traditional linear structure with the hyperbranched structure; the inhibition effect of the natural gas hydrate inhibitor is improved, and the use concentration of the natural gas hydrate inhibitor is reduced.
The hyperbranched polyvinylpyrrolidone with the inner salt structure is prepared by the method comprising the following steps:
(1) under the acidic condition, 4-vinylpyridine and 1, 3-propane sultone undergo a ring-opening reaction to obtain a monomer containing zwitterions, the structural formula of which is shown as a formula I,
(2) in the presence of cerium salt, vinyl pyrrolidone and a monomer containing zwitterion shown as a formula I are reacted,
(3) adding hydroxyl polyether ester polyol and the cerium salt into the reaction system in the step (2) and continuing to react;
(4) continuously adding the vinylpyrrolidone, the monomer containing zwitterions shown in the formula I and the fluorocarbon amphiphilic surfactant into the reaction system in the step (3) to continuously react;
(5) and (4) drying the reaction system in the step (4), and hydrolyzing under an alkaline condition to obtain the hyperbranched polyvinylpyrrolidone with the inner salt structure.
In the step (1) of the preparation method, the acidic condition is provided by hydrochloric acid;
the mass ratio of the 4-vinylpyridine to the 1, 3-propane sultone to the hydrochloric acid can be as follows: 12-16: 10-14: 2-4, specifically 12: 10: 2. 14: 14: 4. 15: 12: 3 or 16: 14: 4;
the temperature of the ring-opening reaction can be 80-90 ℃, and specifically can be 85-85 ℃, 80 ℃, 85 ℃ or 90 ℃;
The ring-opening reaction time can be 6-8 hours, and specifically can be 6 hours, 7 hours or 8 hours.
In the above-mentioned production method, step (2), the reaction is carried out in water;
the cerium salt is CeCl3、Ce(NO3)3And Ce2(SO4)3At least one of (a) and (b);
the mass ratio of the vinylpyrrolidone, the water and the cerium salt may be: 68-72: 390 to 420: 0.03 to 0.04, specifically 68: 390: 0.04, 69: 400: 0.03, 71: 400: 0.03 or 72: 400: 0.035;
in the step (2), the mass ratio of the addition amount of the vinylpyrrolidone to the monomer containing zwitterions shown in the formula I is 68-72: 128-136, specifically 68: 128. 69: 130. 71: 134 or 72: 136.
the reaction temperature can be 45-50 ℃, and specifically can be 45-48 ℃, 45 ℃, 48 ℃ or 50 ℃;
the reaction time may be 1.5 to 2.0 hours, specifically 1.5 or 2.0 hours.
In the step (3), the structural formula of the hydroxyl-terminated polyether ester polyol is shown as a formula II:
the mass ratio of the added amount of the hydroxyl-terminated polyether ester polyol and the cerium salt to the added vinyl pyrrolidone in the step (2) can be 0.005-0.006: 0.03 to 0.04: 68-72, specifically 0.005: 0.04: 68. 0.005: 0.04: 69. 0.0054: 0.03: 71 or 0.006: 0.035: 72;
The reaction temperature can be 45-50 ℃, and specifically can be 45-48 ℃, 45 ℃, 48 ℃ or 50 ℃;
the reaction time may be 1.5 to 2.0 hours, specifically 1.5 or 2.0 hours.
In the step (4) of the preparation method, the mass ratio of the addition amount of the vinylpyrrolidone, the monomer containing zwitterion and the fluorocarbon amphiphilic surfactant shown in the formula I to the mass ratio of the vinylpyrrolidone added in the step (2) can be 2-3: 1-3: 2-3: 68-72, specifically can be: 2:1:2:71, 3:1.5:3:68, 2.5:1.25:2.5:72 or 2:1.4:2.75: 69;
the reaction temperature can be 45-50 ℃, and specifically can be 45-48 ℃, 45 ℃, 48 ℃ or 50 ℃;
the reaction time may be 1.5 to 2.0 hours, specifically 1.5 or 2.0 hours.
The fluorocarbon amphiphilic surfactant is prepared by the following steps:
1) dissolving perfluorooctyl sulfonyl fluoride in ethyl acetate, mixing with polyethylene polyamine, heating, adding sodium hydroxide or potassium hydroxide, and obtaining the difluoride octyl sulfonamide after the reaction is finished;
2) mixing the bi-per-fluoro octyl sulfonamide and 2-chloroethanol in an organic solvent, and then adding sodium hydroxide or potassium hydroxide for reaction to obtain N, N-ethanol bi-per-fluoro octyl sulfonamide;
3) And mixing the N, N-ethanol bis-perfluorooctylsulfamide with hydrogen peroxide, and adding sodium hydroxide or potassium hydroxide for reaction to obtain the fluorocarbon amphiphilic surfactant.
The above method for preparing the fluorocarbon amphiphilic surfactant can be referred to the method for preparing fluorocarbon gemini surfactant described in chinese patent 200910077705.2, and the specific conditions are as follows:
in the step 1), the molar ratio of the sodium hydroxide or the potassium hydroxide to the perfluorooctylsulfonyl fluoride may be 0.05 to 0.1: 0.8 to 2.0;
the final temperature of the heating step is 70-80 ℃, and the reaction time is 6-8 hours;
the polyethylene polyamine can be at least one of 1, 3-propane diamine, ethylene diamine, 1, 4-butane diamine and triethylene tetramine;
in the step 2), the molar ratio of the sodium hydroxide or the potassium hydroxide to the 2-chloroethanol is 0.08-0.1: 0.8 to 2.0;
the reaction temperature is 70-80 ℃, and the reaction time is 6-8 hours;
in the step 3), the molar ratio of the sodium hydroxide or the potassium hydroxide to the hydrogen peroxide is 0.08-0.1: 0.8 to 2.0;
the reaction temperature is 70-80 ℃, and the reaction time is 2-4 hours;
in the steps 1) to 3), the molar ratio of the perfluorooctyl sulfonyl fluoride, the polyethylene polyamine, the 2-chloroethanol and the hydrogen peroxide is 2-2.5: 0.8-1.0: 2-2.5: 2 to 2.5.
In the step (5) of the preparation method, the drying can be performed in an oven, the temperature of the oven can be 80-90 ℃, and the drying time can be 4-6 hours;
the alkaline conditions may be provided by sodium hydroxide,
the mass ratio of the added amount of the sodium hydroxide to the added vinyl pyrrolidone in the step (2) can be 16-18: 68-72, specifically 16: 71. 16.8:68, 17:72 or 16: 69;
the hydrolysis temperature can be 120-140 ℃, and specifically can be 120 ℃, 130 ℃ or 140 ℃;
the hydrolysis time may be 2 hours to 4 hours, specifically 2 hours, 3 hours, or 4 hours.
The application of the hyperbranched polyvinylpyrrolidone with the inner salt structure as the natural gas hydrate inhibitor also belongs to the protection scope of the invention.
The application is as follows: for hydrate inhibition in wellbores, pipelines, and production processes.
When the hyperbranched polyvinylpyrrolidone with the inner salt structure is used as the natural gas hydrate inhibitor, the concentration of the hyperbranched polyvinylpyrrolidone with the inner salt structure is 1-3% (relative to the mass of natural gas).
The invention also provides a natural gas hydrate inhibitor which comprises the hyperbranched polyvinylpyrrolidone with the internal salt structure.
The hyperbranched polyvinylpyrrolidone with the inner salt structure and the preparation method thereof provided by the invention have the following characteristics:
1) the method comprises the steps of preparing a zwitterion-containing monomer (VPPS) by a ring-opening reaction of vinylpyridine and 1, 3-propane sultone under an acidic condition;
2) the invention utilizes cerium salt and terminal hydroxyl to form an oxidation-reduction initiation system to prepare water-soluble hyperbranched polymer, and then directly initiates the free radical copolymerization of the vinylpyrrolidone and the VPPS to obtain the hyperbranched polyvinylpyrrolidone with an inner salt structure.
3) The preparation method of the hyperbranched polyvinylpyrrolidone with the inner salt structure adopts post-curing and post-hydrolysis processes, and the product performance is stable.
4) The hyperbranched polyvinylpyrrolidone with the inner salt structure provided by the invention has higher inhibition performance and lower use concentration.
Drawings
FIG. 1 is a graph showing the induction time of hyperbranched polyvinylpyrrolidone having an internal salt structure prepared in example 1 of the present invention.
FIG. 2 is a graph showing the induction time of hyperbranched polyvinylpyrrolidone having an internal salt structure prepared in example 2 of the present invention.
FIG. 3 is a graph showing the induction time of the hyperbranched polyvinylpyrrolidone having an inner salt structure prepared in example 3 of the present invention.
FIG. 4 is a graph of the induction time of the inner salt hyperbranched polyvinylpyrrolidone prepared in example 4 of the present invention.
Detailed Description
The present invention will be described below with reference to specific examples, but the present invention is not limited thereto.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; reagents, materials and the like used in the following examples are commercially available unless otherwise specified.
The fluorocarbon amphiphilic surfactant used in the following examples was prepared according to the method described in the Chinese patent application (patent No. ZL200910077705.2) (example 1) and specifically prepared as follows:
1) 100.4g (0.2mol) of perfluorooctylsulfonyl fluoride was dissolved in ethyl acetate, and mixed with 5.92g (0.08mol) of 1, 3-propanediamine, heated to 70 ℃ and then reacted with 1.12g (0.02mol) of potassium hydroxide under stirring for 8 hours; and after drying, mixing the dried product with a sodium hydroxide aqueous solution with the mass percentage concentration of 1.0%, extracting organic matters, and removing water to obtain a tan solid which is the bi-per-fluoro octyl sulfonamide.
2) Mixing 103.8g (0.1mol) of perfluoro octyl sulfonamide and 16.1g (0.2mol) of 2-chloroethanol in an ethanol solution, adding 0.56g (0.01mol) of potassium hydroxide, and reacting for 8 hours under the condition of stirring at 80 ℃ to obtain N-N-ethanol perfluoro octyl sulfonamide;
3) 112.6g (0.1mol) of N, N-ethanol bis-perfluorooctylsulfonamide is mixed with 6.8g (0.2mol) of hydrogen peroxide, 0.56g (0.01mol) of potassium hydroxide is added, and the mixture reacts for 2 hours at 70 ℃ under the stirring condition to obtain the fluorocarbon amphiphilic surfactant (fluorocarbon gemini surfactant).
The hydroxyl-terminated polyetherester polyol (HPG) of formula ii used in the following examples was prepared according to the method described in chinese patent application No. 96101119. X.
Example 1 preparation of an inner salt structured hyperbranched polyvinylpyrrolidone Natural gas hydrate inhibitor
(1) Preparation of zwitterionic monomer: preparing VPPS (formula I) by ring-opening polymerization of 12g of 4-vinylpyridine and 10g of 1, 3-propane sultone under the action of 2g of hydrochloric acid at the reaction temperature of 80 ℃ for 8 hours;
(2) 71g NVP (vinyl pyrrolidone) and 134g VPPS were dissolved in 400g H2O, mechanically stirring, introducing condensed water and introducing N2(ii) a Heating to 45 deg.C, and injecting CeCl330mg, reaction for 1.5 hours;
(3) 5.4mg HPG was injected and 30mg CeCl was added3Reacting for 1.5 hours, and keeping the temperature at 45 ℃;
(4) supplementing 2g of NVP and 1g of VPPS, adding 2g of fluorocarbon amphiphilic surfactant, and reacting for 1.5 hours;
(5) the reactor was placed in an oven at 80 ℃ for 4 hours.
(6) The reactor was taken out and charged with 16.0g of NaOH, and was hydrolyzed at 140 ℃ for 2 hours with mechanical stirring by introducing condensed water.
Evaluation of the hyperbranched polyvinylpyrrolidone having an inner salt structure natural gas hydrate inhibitor prepared in this example is performed by referring to a temperature-induction time method in evaluation method of a natural gas hydrate kinetic inhibitor (natural gas chemical industry-C1 chemical and chemical industry 2017.5(42): 126-.
The use concentration of the hyperbranched polyvinylpyrrolidone with the inner salt structure is 1 percent.
Fig. 1 is an induction time curve of the hyperbranched polyvinylpyrrolidone natural gas hydrate inhibitor with an internal salt structure prepared in this embodiment, and it can be known from the figure that the induction time curve of the hyperbranched polyvinylpyrrolidone natural gas hydrate inhibitor with an internal salt structure can significantly delay the induction time.
Because the generation of the hydrate is an exothermic process, the generation condition of the hydrate is measured by testing the change of the temperature of the system, and compared with a blank experiment, the generation temperature and the generation time (endothermic peak) of the hydrate are obviously reduced after the hydrate inhibitor is added.
Example 2 preparation of hyperbranched polyvinylpyrrolidone with inner salt Structure Natural gas hydrate inhibitor
(1) Preparation of a monomer containing zwitterion: 14g of vinylpyridine and 14g of 1, 3-propane sultone are subjected to ring-opening polymerization under the action of 4g of hydrochloric acid at the reaction temperature of 90 ℃ for 6 hours to prepare VPPS;
(2) dissolve 68gNVP and 128gVPPS in 390g H2O, mechanically stirring, introducing condensed water and introducing N2(ii) a Heating to 50 deg.C, and injecting CeCl340mg, reaction for 2 hours;
(3) 5.0mg HPG was injected and 40mg CeCl was added3Reacting for 2 hours, and keeping the temperature at 50 ℃;
(4) supplementing 3g of NVP and 1.5g of VPPS, adding 3g of fluorocarbon amphiphilic surfactant, and reacting for 2 hours;
(5) the reactor was placed in a 90 ℃ oven for 6 hours.
(6) The reactor was taken out and charged with 16.8g of NaOH, passed through with condensed water, mechanically stirred, and hydrolyzed at 120 ℃ for 4 hours.
Evaluation of the natural gas hydrate inhibitor of the hyperbranched polyvinylpyrrolidone having an inner salt structure prepared in this example was performed by referring to a temperature-induction time method in evaluation method of kinetic inhibitor of natural gas hydrate (natural gas chemical industry-C1 chemical and chemical industry 2017.5(42): 126-.
Please indicate that the concentration of the hyperbranched polyvinylpyrrolidone having an inner salt structure is 1.5%.
Fig. 2 is a curve of induction time of the natural gas hydrate inhibitor with hyperbranched polyvinylpyrrolidone having an internal salt structure prepared in this embodiment, and it can be known from the graph that the induction time of the natural gas hydrate inhibitor with hyperbranched polyvinylpyrrolidone having an internal salt structure can be significantly delayed.
Example 3 preparation of an inner salt structured hyperbranched polyvinylpyrrolidone natural gas hydrate inhibitor
(1) Preparation of a monomer containing zwitterion: 16g of vinylpyridine and 14g of 1, 3-propane sultone are subjected to ring-opening polymerization under the action of 4g of hydrochloric acid at the reaction temperature of 90 ℃ for 7 hours to prepare VPPS;
(2) 72g of NVP and 136g of VPPS were dissolved in 400g H2O, mechanically stirring, introducing condensed water and introducing N2(ii) a Heating to 48 deg.C, and injecting CeCl335mg, reaction for 2 hours;
(3) 6.0mg HPG was injected and 35mg CeCl was added3Reacting for 1.5 hours, and keeping the temperature at 48 ℃;
(4) supplementing 2.5g of NVP1.25gVPPS, adding 2.5g of fluorocarbon amphiphilic surfactant, and reacting for 1.5 hours;
(5) the reactor was placed in an oven at 85 ℃ for 5 hours.
(6) The reactor was taken out and 17g of NaOH was added thereto, and the mixture was subjected to hydrolysis at 130 ℃ for 3 hours with condensed water, mechanical stirring.
Evaluation of the hyperbranched polyvinylpyrrolidone having an inner salt structure natural gas hydrate inhibitor prepared in this example is performed by referring to a temperature-induction time method in evaluation method of a natural gas hydrate kinetic inhibitor (natural gas chemical industry-C1 chemical and chemical industry 2017.5(42): 126-.
The use concentration of the hyperbranched polyvinylpyrrolidone with the inner salt structure is 2 percent.
Fig. 3 is a curve of the induction time of the hyperbranched polyvinylpyrrolidone having an inner salt structure natural gas hydrate prepared in this embodiment, and it can be known from the graph that the hyperbranched polyvinylpyrrolidone having an inner salt structure natural gas hydrate can significantly delay the induction time.
Example 4 preparation of an inner salt structured hyperbranched polyvinylpyrrolidone Natural gas hydrate inhibitor
(1) Preparation of a monomer containing zwitterion: 15g of vinylpyridine and 12g of 1, 3-propane sultone are subjected to ring-opening polymerization under the action of 3g of hydrochloric acid at the reaction temperature of 85 ℃ for 7 hours to prepare VPPS;
(2) 69g of NVP and 130g of VPPS were dissolved in 400g H2O, mechanically stirring, introducing condensed water and introducing N2(ii) a Heating to 45 deg.C, and injecting CeCl330mg, reaction for 1.5 hours;
(3) 5.0mg HPG was injected and 40mg CeCl was added3Reacting for 2 hours, and keeping the temperature at 45 ℃;
(4) supplementing 2g of NVP and 1.4g of VPPS, adding 2.75g of fluorocarbon amphiphilic surfactant, and reacting for 2 hours;
(5) the reactor was placed in an oven at 80 ℃ for 6 hours.
(6) The reactor was taken out and charged with 16g of NaOH, passed through with condensed water, mechanically stirred, and hydrolyzed at 140 ℃ for 3 hours.
Evaluation of the hyperbranched polyvinylpyrrolidone having an inner salt structure natural gas hydrate inhibitor prepared in this example is performed by referring to a temperature-induction time method in evaluation method of a natural gas hydrate kinetic inhibitor (natural gas chemical industry-C1 chemical and chemical industry 2017.5(42): 126-.
The use concentration of the hyperbranched polyvinylpyrrolidone with the inner salt structure is 2.5%.
Fig. 4 is a curve of the induction time of the hyperbranched polyvinylpyrrolidone with an inner salt structure natural gas hydrate inhibitor prepared in this embodiment, and it can be known from the graph that the hyperbranched polyvinylpyrrolidone with an inner salt structure natural gas hydrate inhibitor can significantly delay the induction time.
Claims (7)
1. Application of hyperbranched polyvinylpyrrolidone with an inner salt structure as a natural gas hydrate inhibitor,
the method for preparing the hyperbranched polyvinylpyrrolidone with the inner salt structure comprises the following steps:
(1) under the acidic condition, 4-vinylpyridine and 1, 3-propane sultone undergo a ring-opening reaction to obtain a monomer containing zwitterions, the structural formula of which is shown as a formula I,
(2) in the presence of cerium salt, vinyl pyrrolidone and a monomer containing zwitterion and shown as a formula I are reacted,
(3) adding hydroxyl polyether ester polyol and the cerium salt into the reaction system in the step (2) and continuing to react;
(4) continuously adding the vinylpyrrolidone, the monomer containing zwitterions shown in the formula I and the fluorocarbon amphiphilic surfactant into the reaction system in the step (3) to continuously react;
(5) Drying the reaction system in the step (4), and hydrolyzing under an alkaline condition to obtain hyperbranched polyvinylpyrrolidone with an inner salt structure;
in the step (2), the mass ratio of the addition amount of the vinylpyrrolidone to the monomer containing zwitterions and shown in the formula I is 68-72: 128 to 136;
in the step (3), the structural formula of the hydroxyl-terminated polyether ester polyol is shown as a formula II:
the mass ratio of the added amount of the hydroxyl-terminated polyether ester polyol and the cerium salt to the added amount of the vinyl pyrrolidone in the step (2) is 0.005-0.006: 0.03 to 0.04: 68-72;
in the step (4), the mass ratio of the addition amount of the vinylpyrrolidone, the monomer containing zwitterions and the fluorocarbon amphiphilic surfactant shown in the formula I to the addition amount of the vinylpyrrolidone in the step (2) is 2-3: 1-3: 2-3: 68-72.
2. Use according to claim 1, characterized in that: in step (1) of the process, the acidic conditions are provided by hydrochloric acid;
the mass ratio of the 4-vinylpyridine to the 1, 3-propane sultone to the hydrochloric acid is as follows: 12-16: 10-14: 2-4;
the temperature of the ring-opening reaction is 80-90 ℃;
the ring-opening reaction time is 6-8 hours.
3. Use according to claim 1, characterized in that: in the step (2), the reaction is carried out in water;
The cerium salt is CeCl3、Ce(NO3)3And Ce2(SO4)3At least one of (1);
the mass ratio of the vinylpyrrolidone to the water to the cerium salt is as follows: 68-72: 390 to 420: 0.03 to 0.04;
the reaction temperature is 45-50 ℃;
the reaction time is 1.5 to 2.0 hours.
4. Use according to claim 1, characterized in that: in the step (3), the reaction temperature is 45-50 ℃;
the reaction time is 1.5 to 2.0 hours.
5. Use according to claim 1, characterized in that: in the step (4), the reaction temperature is 45-50 ℃;
the reaction time is 1.5 to 2.0 hours.
6. Use according to claim 1, characterized in that: the application is as follows: for hydrate inhibition in wellbores, pipelines, and production processes.
7. Use according to claim 1, characterized in that: when the hyperbranched polyvinylpyrrolidone with the inner salt structure is used as a natural gas hydrate inhibitor, the use concentration of the hyperbranched polyvinylpyrrolidone with the inner salt structure is 1-3%.
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| WO2008017018A2 (en) * | 2006-08-03 | 2008-02-07 | Baker Hughes Incorporated | Kinetic gas hydrate inhibitors in completion fluids |
| US20140346117A1 (en) * | 2011-12-20 | 2014-11-27 | Ulfert Cornelis Klomp | Method for inhibitng the plugging of conduits by gas hydrates |
| CN103923254B (en) * | 2014-04-17 | 2016-01-13 | 中国海洋石油总公司 | A kind of salt thickening type water-soluble branched polymer and preparation method thereof and application |
| CN107759729B (en) * | 2016-08-17 | 2020-12-11 | 中国石油化工股份有限公司 | Temperature-resistant salt-resistant tackifier for drilling fluid, preparation method and application |
| CN108219154A (en) * | 2018-01-03 | 2018-06-29 | 中国海洋石油集团有限公司 | A kind of hyperbranched pour point depressant for crude oil with internal salt structure and preparation method and application |
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