CO2 chemical reaction tackifying polymer surfactant for offshore CO2 flooding thick oil and gas channeling control as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of oilfield chemistry, and discloses a CO2 chemical reaction tackifying poly-surfactant for offshore CO2 flooding thick oil and gas channeling control and a preparation method and application thereof, and the CO2 reaction tackifying poly-surfactant comprises structural units provided by a formula (1), a formula (2) and a formula (3); in the formula (1), R1, R2, R3, R4 and R5 are respectively one or more of H, F and C1-C4 alkyl alcohols, and at least one of the R1, R2, R3, R4 and R5 is F; in the formula (2), R6, R7 and R8 are respectively one or more of H and C1-C4 alkyl groups; in the formula (3), R is one or more of C10-C16 alkyl groups; the CO2 reaction tackifying poly-surfactant has the advantages of high CO2 gas channeling plugging strength, good chemical stability and good thickened oil viscosity reduction performance; # imgabs0 #

Description

Technical Field

[0001] The invention belongs to the technical field of oilfield chemistry and specifically relates to a method for offshore CO 2 CO2 for heavy oil and gas breakthrough control 2 Chemical reaction viscosity-increasing polymer surface active agent and its preparation method and application. Background Art

[0002] As the global demand for crude oil energy increases year by year and conventional crude oil is gradually depleted, the rational exploitation of heavy oil is particularly important. Due to the long-term exploitation of conventional crude oil worldwide, the proportion of offshore heavy oil resources in the total oil volume has increased, exceeding 70% of the world's total remaining offshore oil reserves. 2 It has good miscibility with crude oil, effectively reduces crude oil viscosity, reduces interfacial tension, volume expansion, and extracts light hydrocarbons. 2 Oil recovery technology has become the key to the efficient development of heavy oil reservoirs. However, compared with offshore heavy oil water drive development, offshore heavy oil CO 2 Oil recovery faces the following challenges: ① Most offshore heavy oil reservoirs are loose sandstone reservoirs, which have the characteristics of loose rock cementation, high reservoir permeability, and severe heterogeneity. 2 / The difference in heavy oil mobility ratio is too large, and CO injection 2 The inevitable cross-flow will result in poor energy replenishment and low degree of influence. ② Control gas cross-flow is CO 2 The key to efficient oil recovery and storage is the displacement agent, which is the core, but is affected by CO 2 Due to the strong acidity of soluble water and the high intensity of gas injection, conventional displacement agents "cannot withstand the test and cannot be controlled for long".

[0003] Therefore, it is urgent to develop efficient CO 2 Gas channeling control system to improve CO 2 Oil displacement effect. 2 Responsive materials have become a hot topic in the field of gas channeling control because their properties can change with the environment and space. Among them, the most mature research is the amino, amidine, guanidine and nitrogen-containing heterocyclic CO 2 Responsive viscosity-enhancing polymers or surfactants. 2 Protonation reaction, counter-ion electrostatic shielding and self-assembly effect occur, and the aggregation morphology of polymers or surfactants changes from spherical to worm-like micelles. The worm-like micelles entangle with each other to form a highly viscoelastic three-dimensional network structure, which blocks the gas channel and expands the CO 2 The swept volume increases the oil recovery efficiency. 2Sensitive response thickening polymers / surfactants mainly block gas channeling channels through non-covalent physical association thickening, which is easily affected by external factors, such as water front intrusion dilution, charge shielding of high-mineralization formation water, and residual oil dissolution, which leads to system instability and uncontrollable gas channeling. Therefore, it is necessary to transform the unstable non-covalent physical association thickening into stable chemical covalent thickening, that is, from responsive thickening to direct chemical reaction thickening.

[0004] Therefore, for offshore heavy oil CO 2 Due to the particularity of oil displacement and storage environment, a CO2-based oil recovery system with good stability, high sealing strength and excellent heavy oil viscosity reduction performance is urgently needed. 2 Reaction thickening polymer surfactant is used to improve the development efficiency of offshore heavy oil reservoirs. Summary of the invention

[0005] The purpose of the present invention is to overcome the CO 2 Response to viscosity-enhancing polymers or surfactants to block CO 2 The gas channeling strength is low and it is easy to fail. 2 CO2 for heavy oil and gas breakthrough control 2 Chemical reaction viscosity-increasing polymer surface agent and its preparation method and application, the CO 2 Reactive viscosity enhancing agent CO 2 It has high gas channeling plugging strength, good chemical stability, and good heavy oil viscosity reduction performance.

[0006] In order to achieve the above object, the present invention provides a CO 2 Reaction thickening agent, wherein the CO 2 The reactive viscosity-increasing polymerizing agent includes a structural unit provided by a Lewis acid monomer shown in formula (1), a structural unit provided by a Lewis base monomer shown in formula (2), a structural unit provided by a hydrophilic monomer, and a structural unit provided by an interfacial active monomer shown in formula (3);

[0007]

[0008] In formula (1), R 1 , R 2 , R 3 , R 4 and R 5 The same or different, each is H, F, C 1 -C 4 One or more of the alkyl alcohols of , and at least one of them is F;

[0009]

[0010] In formula (2), R6 , R 7 and R 8 The same or different, each is H, C 1 -C 4 One or more of the alkyl groups of

[0011]

[0012] Wherein, in formula (3), R is C 10 -C 16 One or more of the alkyl groups.

[0013] The second aspect of the present invention provides a CO 2 A method for preparing a reactive thickening polymerizing agent, wherein the preparation method comprises:

[0014] (F1) contacting and mixing a Lewis acid monomer represented by formula (1), a Lewis base monomer represented by formula (2), a hydrophilic monomer, an interfacial active monomer represented by formula (3) and a solvent to obtain a mixture;

[0015] (F2) contacting the mixture with an initiator under the protection of an inert gas to react;

[0016] (F3) contacting the product obtained in step (F2) with an alcohol solvent and then subjecting the product to precipitation, filtration and drying to obtain CO 2 Reactive viscosity enhancing agent.

[0017] The third aspect of the present invention provides a CO 2 Application of reactive thickening polymer in offshore heavy oil CO 2 Application in purge gas blowby control.

[0018] Through the above technical solution, the CO 2 The reaction thickening agent is introduced into the 2 After that, CO 2 It can react with the polymerizing agent to form a stable covalent bond, significantly increasing the viscosity of the system, thereby achieving the effect of blocking channeling. It is not easily affected by external factors, has good chemical stability, high blocking strength, and can achieve long-term effective blocking. At the same time, CO 2 Reactive thickening polymer surfactant can significantly reduce the viscosity of heavy oil and improve the efficiency of heavy oil washing. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 CO prepared in Example 1 2 Reactive viscosity enhancing agent 1 H NMR spectrum;

[0020] Figure 2The Lewis acid monomer prepared in Preparation Example 1 1 H NMR spectrum;

[0021] Figure 3 The Lewis acid monomer prepared in Preparation Example 1 11 B NMR spectrum;

[0022] Figure 4 The Lewis base monomer prepared in Preparation Example 6 1 H NMR spectrum;

[0023] Figure 5 The Lewis base monomer prepared in Preparation Example 6 31 P NMR spectrum. DETAILED DESCRIPTION

[0024] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0025] As mentioned above, the first aspect of the present invention provides a CO 2 Reaction thickening agent, wherein the CO 2 The reactive viscosity-increasing polymerizing agent includes a structural unit provided by a Lewis acid monomer shown in formula (1), a structural unit provided by a Lewis base monomer shown in formula (2), a structural unit provided by a hydrophilic monomer, and a structural unit provided by an interfacial active monomer shown in formula (3);

[0026]

[0027] In formula (1), R 1 , R 2 , R 3 , R 4 and R 5 The same or different, each is H, F, C 1 -C 4 One or more of the alkyl alcohols of , and at least one of them is F;

[0028]

[0029] In formula (2), R 6 , R 7 and R 8 The same or different, each is H, C 1 -C 4One or more of the alkyl groups of

[0030]

[0031] Wherein, in formula (3), R is C 10 -C 16 One or more of the alkyl groups.

[0032] According to the present invention, in formula (1), R 1 , R 2 , R 3 , R 4 and R 5 The same or different, each is H, F, C 1 -C 3 One or more of the alkyl alcohols of , and at least one of them is F.

[0033] According to the present invention, preferably, the Lewis acid monomer is selected from one or more of formula (1-1), formula (1-2), formula (1-3), formula (1-4) and formula (1-5);

[0034]

[0035] That is, in the present invention, the structure of formula (1-1) represents di(3,4,5-trifluorophenyl)(4-vinylphenyl)boron; the structure of formula (1-2) represents di(3,5-difluorophenyl)(4-vinylphenyl)boron; the structure of formula (1-3) represents dipentafluorophenyl(4-vinylphenyl)boron; the structure of formula (1-4) represents di(3-fluorophenyl)(4-vinylphenyl)boron; the structure of formula (1-5) represents di[3,5-difluoro(4-hydroxymethyl)phenyl](4-vinylphenyl)boron.

[0036] According to the present invention, more preferably, the Lewis acid monomer is selected from one or more of dipentafluorophenyl(4-vinylphenyl)boron, di(3,5-difluorophenyl)(4-vinylphenyl)boron and di(3,4,5-trifluorophenyl)(4-vinylphenyl)boron.

[0037] According to the present invention, in formula (2), R 6 , R 7 and R 8 The same or different, each is H, C 1 -C 3 One or more of the alkyl groups.

[0038] According to the present invention, preferably, the Lewis base monomer is selected from one or more of formula (2-1), formula (2-2), formula (2-3), formula (2-4) and formula (2-5);

[0039]

[0040] That is, in the present invention, the structure of formula (2-1) represents di-mesityl (4-vinylphenyl) phosphorus; the structure of formula (2-2) represents diphenyl (4-vinylphenyl) phosphorus; the structure of formula (2-3) represents di(2,4,6-triethylphenyl) (4-vinylphenyl) phosphorus; the structure of formula (2-4) represents di(2,4,6-triisopropylphenyl) (4-vinylphenyl) phosphorus; the structure of formula (2-5) represents di(2,4,6-tri-tert-butylphenyl) (4-vinylphenyl) phosphorus.

[0041] According to the present invention, more preferably, the Lewis base monomer is selected from one or more of di-mesityl(4-vinylphenyl)phosphine, di(2,4,6-triethylphenyl)(4-vinylphenyl)phosphine and di(2,4,6-triisopropylphenyl)(4-vinylphenyl)phosphine.

[0042] According to the present invention, the purity of the Lewis acid monomer is 82-98%, preferably 82.06-97.88%, preferably 90-98%.

[0043] According to the present invention, the purity of the Lewis base monomer is 80-99%, preferably 80.3-98.82%, and more preferably 92.38-98.82%.

[0044] According to the present invention, the hydrophilic monomer is selected from one or more of acrylamide, N-vinylamide, acrylic acid, and methacrylic acid.

[0045] According to the present invention, in formula (3), R is C 10 -C 16 One or more of the alkyl groups.

[0046] According to the present invention, the molar ratio of the structural unit provided by the Lewis acid monomer represented by formula (1), the structural unit provided by the Lewis base monomer represented by formula (2), the structural unit provided by the hydrophilic monomer, and the structural unit provided by the interfacial active monomer represented by formula (3) is 1: (0.4-2.5): (10-100): (0.5-10), preferably 1: (0.5-2): (25-80): (0.7-6), more preferably 1: (0.7-1.5): (30-70): (1-4), and further preferably 1: (0.8-1.3): (40-60): (1.5-3);

[0047] According to the present invention, the CO 2 The number average molecular weight of the reactive thickening polymer is 100,000-2,000,000, preferably 500,000-1,500,000, more preferably 800,000-1,200,000, and even more preferably 900,000-1,100,000.

[0048] In the present invention, the preparation of the Lewis acid monomer represented by formula (1) comprises:

[0049] (S1) under nitrogen protection, adding dropwise a solution containing a compound having a structure represented by formula (S-1) to a solution containing a boron halogen compound and an anhydrous solvent to carry out a first reaction;

[0050]

[0051] Wherein, X in the structures represented by formula (S-1) and formula (S-2) is each halogen;

[0052] Among them, R 1 , R 2 , R 3 , R 4 and R 5 The same or different, each is H, F, C 1 -C 4 One or more of the alkyl alcohols of , and at least one of them is F;

[0053] (S2) adding a solution containing a compound having a structure represented by formula (S-2) dropwise to the reaction solution after step (S1) to carry out a second reaction, thereby preparing a Lewis acid monomer.

[0054] According to the present invention, the inventors of the present invention have found that the reaction process must be carried out under anhydrous and oxygen-free conditions. In the preparation method of the Lewis acid monomer of the present invention, the raw materials (S-1) and (S-2) used are both Grignard reagents, which react violently with water to generate combustible hydrocarbons RH and Mg(OH)X (wherein R represents a hydrocarbon group and X represents a halogen), resulting in impure products or reaction failure, so it is necessary to be carried out under anhydrous conditions; and the presence of oxygen will cause boron to be oxidized, resulting in impure products and reduced yields, so it is necessary to be carried out under oxygen-free conditions.

[0055] According to the present invention, the anhydrous solvent is anhydrous tetrahydrofuran and / or anhydrous ether; in the present invention, the solvent needs to be anhydrous before use to prevent the influence of moisture on the reaction process during the reaction.

[0056] Specifically, the treatment method of anhydrous tetrahydrofuran can be: adding shredded sodium blocks into tetrahydrofuran, refluxing under moisture isolation to remove water and peroxide therein, and then distilling and collecting fractions to obtain anhydrous tetrahydrofuran.

[0057] Similarly, the method for treating anhydrous ether can be: adding chopped sodium blocks into tetrahydrofuran, reflux in a moisture-proof environment to remove water and peroxide therein, and then distilling and collecting the fractions to obtain anhydrous ether.

[0058] According to the present invention, the weight ratio of the total amount of the anhydrous solvent to the compound of the structure represented by formula (S-1), the boron halogen compound and the compound of the structure represented by formula (S-2) is (100-500):100, preferably (150-400):100.

[0059] According to the present invention, X in the structures represented by formula (S-1) and formula (S-2) is each selected from one or more of Cl, Br, F and I.

[0060] According to the present invention, preferably, the compound having the structure represented by formula (S-1) is selected from one or more of pentafluorophenylmagnesium bromide, pentafluorophenylmagnesium chloride, 3,5-difluorophenylmagnesium bromide and 3,4,5-trifluorophenylmagnesium chloride.

[0061] According to the present invention, preferably, the compound having the structure represented by formula (S-2) is p-styrene magnesium bromide and / or p-styrene magnesium chloride.

[0062] According to the present invention, preferably, the boron halogen compound is selected from BCl 3 , BBr 3 , BF 3 and B.I. 3 One or more of .

[0063] According to the present invention, the molar ratio of the compound with the structure represented by formula (S-1), the boron halogen compound and the compound with the structure represented by formula (S-2) is 1: (0.1-1.5): (0.05-1.5), preferably 1: (0.2-1.5): (0.1-1.5), and more preferably 1: (0.3-0.7): (0.2-0.6).

[0064] In the present invention, in the solution of step (S1), the concentration of the solution containing the compound with the structure represented by formula (S-1) is 1 mol / L-4 mol / L; in addition, in the present invention, there is no particular limitation on the solvent in the solution containing the compound with the structure represented by formula (S-1), and tetrahydrofuran or diethyl ether may be used as the solvent, preferably diethyl ether is used as the solvent, that is, the diethyl ether solution containing the compound with the structure represented by formula (S-1).

[0065] In the present invention, in the solution of step (S2), the concentration of the solution containing the compound with the structure represented by formula (S-2) is 1 mol / L-3 mol / L; in addition, in the present invention, there is no particular limitation on the solvent in the solution containing the compound with the structure represented by formula (S-2), and tetrahydrofuran or diethyl ether may be used as the solvent, preferably diethyl ether is used as the solvent, that is, the diethyl ether solution containing the compound with the structure represented by formula (S-2).

[0066] According to the present invention, in step (S1), the first reaction conditions include: temperature of -10°C to 15°C, time of 1-6h; preferably, temperature of -5°C to 5°C, time of 2-4h.

[0067] According to the present invention, in step (S2), the second reaction conditions include: first reacting at a temperature of -10°C to 10°C for 1-4 hours, and then rising to 20-35°C for reaction for 8-16 hours; more preferably, first reacting at a temperature of 0-5°C for 1-2 hours, and then rising to 20-35°C for reaction for 12-15 hours.

[0068] In the present invention, in step (S1), preferably, the reaction is carried out under stirring conditions, and the stirring rate is 200-800 rpm, more preferably, the stirring rate is 400-500 rpm.

[0069] In the present invention, in step (S2), preferably, the reaction is carried out under stirring conditions, and the stirring rate is 300-800 rpm, more preferably, the stirring rate is 400-600 rpm.

[0070] In the present invention, in step (S1), more preferably, a solution containing a compound with a structure shown in formula (S-1) is added dropwise to a solution containing a boron halogen compound and an anhydrous solvent to carry out a first reaction; wherein the dripping rate of the addition can be 0.5-2 drops / second. In the present invention, the dripping method is adopted, which has the advantage of effectively controlling the reaction rate, avoiding an overly violent reaction process, reducing the generation of side reaction products, and improving the purity and yield of the product.

[0071] In the present invention, in step (S2), more preferably, a solution containing a compound with a structure shown in formula (S-2) is added dropwise to the reaction solution after step (S1) to carry out a second reaction; wherein the dripping rate of the addition can be 0.5-2 drops / second. In the present invention, the dripping method is adopted, which has the advantage of effectively controlling the reaction rate, avoiding the reaction process being too intense, reducing the generation of side reaction products, and improving the purity and yield of the product.

[0072] According to the present invention, the preparation method further comprises: separating and purifying the crude product mixed solution after step (S2); preferably, the separation and purification method comprises: removing the solvent from the crude product mixed solution after the reaction in step (S2) under vacuum, and then chopping the obtained residue and sublimating it to obtain a Lewis acid monomer.

[0073] According to the present invention, the method for removing the solvent under vacuum adopts a vacuum distillation method; preferably, the conditions of the vacuum distillation include: a temperature of 120-150°C, a pressure of -0.1 MPa to 1×10 -7MPa.

[0074] According to the present invention, the residue is cut into pieces and then sublimated, and the sublimation is preferably carried out by vacuum sublimation. Preferably, the conditions of the vacuum sublimation include: a temperature of 120-150°C and a pressure of -0.1-1×10 -7 MPa.

[0075] In the present invention, the preparation of the Lewis base monomer represented by formula (2) comprises:

[0076] (J1) under nitrogen protection, adding dropwise a solution containing a compound having a structure represented by formula (J-1) to a solution containing a phosphorus halogen compound and an anhydrous solvent to carry out a first reaction;

[0077]

[0078] Wherein, X in the structures represented by formula (J-1) and formula (J-2) is each a halogen;

[0079] Among them, R 1 , R 2 and R 3 The same or different, each is H, C 1 -C 4 One or more of the alkyl groups of

[0080] (J2) Adding a solution containing a compound having a structure represented by formula (J-2) dropwise to the reaction solution after step (J1) to carry out a second reaction, thereby preparing a Lewis base monomer.

[0081] According to the present invention, the inventors of the present invention have found that the reaction process must be carried out under anhydrous and oxygen-free conditions. In the reaction of synthesizing Lewis base monomers in the present invention, raw materials (J-1) and (J-2) are both Grignard reagents, which react violently with water to generate combustible hydrocarbons RH and Mg(OH)X (wherein R represents a hydrocarbon group and X represents a halogen), resulting in impure products or reaction failure, so it is necessary to be carried out under anhydrous conditions; and the presence of oxygen will cause phosphorus to be oxidized, resulting in impure products and reduced yields, so it is necessary to be carried out under oxygen-free conditions.

[0082] According to the present invention, the anhydrous solvent is anhydrous tetrahydrofuran and / or anhydrous ether; in the present invention, the solvent needs to be anhydrous before use to prevent the influence of moisture on the reaction process during the reaction.

[0083] Specifically, the treatment method of anhydrous tetrahydrofuran can be: adding shredded sodium blocks into tetrahydrofuran, refluxing under moisture isolation to remove water and peroxide therein, and then distilling and collecting fractions to obtain anhydrous tetrahydrofuran.

[0084] Similarly, the method for treating anhydrous ether can be: adding chopped sodium blocks into tetrahydrofuran, reflux in a moisture-proof environment to remove water and peroxide therein, and then distilling and collecting the fractions to obtain anhydrous ether.

[0085] According to the present invention, the weight ratio of the total amount of the anhydrous solvent to the compound of the structure represented by formula (J-1), the phosphorus halogen compound and the compound of the structure represented by formula (J-2) is (100-500):100, preferably (150-400):100.

[0086] According to the present invention, X in the structures represented by formula (J-1) and formula (J-2) is each selected from one or more of Cl, Br, F and I.

[0087] According to the present invention, preferably, the compound of the structure shown in formula (J-1) is selected from one or more of mesitylene magnesium chloride, mesitylene magnesium bromide, 2,4,6-triethylphenyl magnesium chloride, 2,4,6-triisopropylphenyl magnesium bromide and 2,4,6-tri-tert-butylphenyl magnesium bromide.

[0088] According to the present invention, preferably, the compound having the structure represented by formula (J-2) is p-styrene magnesium bromide and / or p-styrene magnesium chloride.

[0089] According to the present invention, preferably, the phosphorus halogen compound is selected from PCl 3 , PBr 3 PF 3 and PI 3 One or more of .

[0090] According to the present invention, the molar ratio of the compound with the structure represented by formula (J-1), the phosphorus halogen compound and the compound with the structure represented by formula (J-2) is 1: (0.1-2): (0.05-2), preferably 1: (0.2-1): (0.1-0.8), more preferably 1: (0.2-0.6): (0.1-0.5), and further preferably 1: (0.4-0.6): (0.3-0.5).

[0091] In the present invention, in the solution of step (J1), the concentration of the solution containing the compound with the structure represented by formula (J-1) is 0.5 mol / L-4 mol / L; in addition, in the present invention, there is no particular limitation on the solvent in the solution containing the compound with the structure represented by formula (J-1), and tetrahydrofuran or diethyl ether is preferably used as the solvent, that is, a tetrahydrofuran solution containing the compound with the structure represented by formula (J-1) and a diethyl ether solution containing the compound with the structure represented by formula (J-1).

[0092] In the present invention, in the solution of step (J2), the concentration of the solution containing the compound with the structure represented by formula (J-2) is 0.5 mol / L-2 mol / L; in addition, in the present invention, there is no particular limitation on the solvent in the solution containing the compound with the structure represented by formula (J-2), and tetrahydrofuran or diethyl ether is preferably used as the solvent, that is, a tetrahydrofuran solution containing the compound with the structure represented by formula (J-2) and a diethyl ether solution containing the compound with the structure represented by formula (J-2).

[0093] According to the present invention, in step (J1), the first reaction conditions include: temperature of 0-25°C, time of 10-16h; preferably, temperature of 0-10°C, time of 12-14h.

[0094] According to the present invention, in step (J2), the second reaction conditions include: temperature of 0-35°C, time of 10-18h; preferably, temperature of 0-15°C, time of 13-16h.

[0095] In the present invention, in step (J1), preferably, the first reaction is carried out under stirring conditions, and the stirring rate is 200-700 rpm, more preferably, the stirring rate is 300-400 rpm.

[0096] In the present invention, in step (J2), preferably, the second reaction is carried out under stirring conditions, and the stirring rate is 300-700 rpm, more preferably, the stirring rate is 400-500 rpm.

[0097] In the present invention, in step (J1), more preferably, a solution containing a compound of the structure shown in formula (J-1) is added dropwise to a solution containing a phosphorus halogen compound and an anhydrous solvent to carry out a first reaction; wherein the dripping rate of the addition can be 0.5-2 drops / second. In the present invention, the dripping method is adopted, which has the advantage of effectively controlling the reaction rate, avoiding the reaction process being too intense, reducing the generation of side reaction products, and improving the purity and yield of the product.

[0098] In the present invention, in step (J2), more preferably, a solution containing a compound of the structure shown in formula (J-2) is added dropwise to the reaction solution after step (J1) to carry out a second reaction; wherein the dripping rate of the addition can be 0.5-2 drops / second. In the present invention, the dripping method is adopted, which has the advantage of effectively controlling the reaction rate, avoiding the reaction process being too intense, reducing the generation of side reaction products, and improving the purity and yield of the product.

[0099] According to the present invention, the preparation method further comprises: separating and purifying the crude product mixture after step (J2); preferably, the separation and purification method comprises:

[0100] (i) contacting the crude product mixture after the reaction in step (J2) with a saturated salt solution, then extracting with ether, and collecting the organic phase;

[0101] (ii) drying, distilling, concentrating and precipitating the organic phase to obtain a crude product;

[0102] (iii) subjecting the crude product to chromatography to prepare a Lewis base monomer.

[0103] According to the present invention, in step (i), the salt solution may be NaCl, NH 4 Cl, MgCl 2 , CaCl 2 One of the following, preferably NaCl or NH 4 Cl.

[0104] According to the present invention, in step (i), the weight ratio of the crude product mixture, the saturated salt solution and diethyl ether is 1:(0.5-2):(1-4), preferably 1:(0.5-2):(1.5-4), and more preferably 1:(0.5-1.5):(1-3).

[0105] In the present invention, in step (ii), the distillation and concentration is carried out by rotary evaporation; preferably, the conditions of the rotary evaporation include: a temperature of 25-40° C. and a pressure of -0.08 MPa to -0.1 MPa;

[0106] According to the present invention, the viscous oily liquid obtained after distillation and concentration is contacted with an alcohol solvent for precipitation treatment; in the present invention, in step (ii), the alcohol solvent can be one of methanol, isopropanol, n-butanol, and isobutanol, preferably methanol.

[0107] According to the present invention, preferably, the weight ratio of the viscous oily liquid to the alcohol solvent is 1:(2-4).

[0108] In the present invention, in step (iii), the filling material of the chromatography column can be one of silica gel, alumina and ion exchange resin, preferably alumina.

[0109] The second aspect of the present invention provides a CO 2 A method for preparing a reactive thickening polymerizing agent, wherein the preparation method comprises:

[0110] (F1) contacting and mixing a Lewis acid monomer represented by formula (1), a Lewis base monomer represented by formula (2), a hydrophilic monomer, an interfacial active monomer represented by formula (3) and a solvent to obtain a mixture;

[0111] (F2) contacting the mixture with an initiator under the protection of an inert gas to react;

[0112] (F3) contacting the product obtained in step (F2) with an alcohol solvent and then subjecting the product to precipitation, filtration and drying to obtain CO 2 Reactive viscosity enhancing agent.

[0113] According to the present invention, the molar ratio of the Lewis acid monomer represented by formula (1), the Lewis base monomer represented by formula (2), the hydrophilic monomer and the interfacial active monomer represented by formula (3) is 1: (0.5-2): (20-100): (1-10), preferably 1: (0.6-1.5): (30-80): (1-6), more preferably 1: (0.7-1.3): (40-70): (2-5), and further preferably 1: (0.8-1.2): (50-70): (2-3).

[0114] According to the present invention, the amount of the initiator is 0.1-0.8 wt %, preferably 0.2-0.5 wt %, based on the total weight of the Lewis acid monomer represented by formula (1), the Lewis base monomer represented by formula (2), the hydrophilic monomer and the interfacial active monomer represented by formula (3).

[0115] According to the present invention, the solvent can be selected from at least two of toluene, chloroform, dimethyl sulfoxide, N,N-dimethylformamide and cyclohexane.

[0116] According to the present invention, the concentrations of the Lewis acid monomer represented by formula (1), the Lewis base monomer represented by formula (2), the hydrophilic monomer and the interfacial active monomer represented by formula (3) in the solvent are the same or different, and each is 10-30wt%, for example, 10wt%, 12wt%, 15wt%, 17.5wt%, 20wt%, 25wt%, 30wt%, and a range consisting of any two of the above values.

[0117] According to the present invention, the initiator is selected from one or more of azo initiators, organic peroxide initiators, inorganic peroxide initiators and oil-soluble redox initiators, and an azo initiator is preferred.

[0118] Specifically, the initiator is selected from one or more of azobisisobutylimidazoline hydrochloride, azoisobutylcyanoformamide, azobisisobutyronitrile, azobiscarboxyethyl-2-isobutylamidine hydrate, azodimethyl N-2-hydroxybutylacrylamide, azobiscyclohexylcarbonitrile, and azobisisovaleronitrile, preferably azobisisobutyronitrile.

[0119] According to the present invention, in step (F2), the reaction conditions include: reaction temperature of 40-100°C, reaction time of 12-28h; preferably, reaction temperature of 60-80°C, reaction time of 16-24h.

[0120] In the present invention, preferably, the free radical polymerization reaction is carried out under stirring conditions, and the stirring rate is 100-500 rpm, more preferably, the stirring rate is 200-400 rpm.

[0121] According to the present invention, in preparing the CO 2 During the reaction of the thickening polymerizing agent, the separation and purification method is not particularly limited. The reaction material obtained by the free radical polymerization reaction can be precipitated, filtered and dried to obtain the CO 2 For example, the reaction material obtained by the free radical polymerization reaction is precipitated in an alcohol solvent, filtered, and then vacuum dried to constant weight to obtain the CO 2 Reactive viscosity enhancing agent.

[0122] Among them, preferably, the alcohol solvent is selected from one or more of methanol, ethanol, isopropanol, and n-butanol, and more preferably methanol; preferably, the drying condition is vacuum drying at 30-50°C, and more preferably vacuum drying at 40°C.

[0123] The third aspect of the present invention provides a CO 2 Application of reactive thickening polymer in offshore heavy oil CO 2 Application in purge gas blowby control.

[0124] In the present invention, the offshore heavy oil originates from the Bohai oil field.

[0125] The present invention will be described in detail below through examples.

[0126] In the following examples and comparative examples:

[0127] 1 H NMR spectrum parameters were measured by nuclear magnetic resonance hydrogen spectroscopy; polymer molecular weight was measured by gel permeation chromatography; viscosity parameters were measured by Anton paar MCR 72 rheometer according to the test process specified in standard GB / T 16321-2008; plugging rate was measured by core physical simulation flow test method. The reagents and raw materials used were commercially available products of Shanghai Aladdin Biochemical Technology Co., Ltd.

[0128] Preparation Example 1

[0129] This preparation example is a Lewis acid prepared according to the present invention.

[0130] (S1) at 0°C and under nitrogen protection, a 2 mol / L ether solution of pentafluorophenylmagnesium bromide was added dropwise to a boron trifluoride ether solution at a drop rate of 0.5 drops / second, and then the reaction was continued at 0°C and a stirring rate of 400 rpm for 3 hours;

[0131] (S2) adding ethyl ether solution of p-styrene magnesium bromide dropwise to the mixed solution of step (S1) at a dropping rate of 0.5 drops / second at 0°C and a stirring rate of 500 rpm, and after the dropwise addition, stirring the reaction mixture at 0°C for 2 hours, then heating to room temperature and stirring for 14 hours to obtain a crude product mixed solution containing the target product; wherein the concentration of the ethyl ether solution of p-styrene magnesium bromide is 2 mol / L;

[0132] Wherein, the molar ratio of pentafluorophenylmagnesium bromide, boron trifluoride and p-phenylenemagnesium bromide is 1:0.4:0.4;

[0133] (S3) The crude product mixture obtained in step (S2) was subjected to reduced pressure distillation (25°C, -0.08MPa), and the residue was shredded and sublimed (130°C, 1×10 -7 MPa), and the Lewis acid monomer dipentafluorophenyl (4-vinylphenyl) boron was obtained, and its structure is shown below:

[0134]

[0135] Results The yield and purity of the prepared Lewis acid monomers are shown in Table 1.

[0136] Figure 2 The Lewis acid monomer prepared in Preparation Example 1 1 H NMR spectrum, from Figure 2 The nuclear magnetic resonance spectrum shows that the chemical shift at the abscissa of 7.49-7.81 (m, 4H) ppm indicates the peak of a (H on the styrene group); the chemical shift at 6.91 (d, 1H) ppm indicates the peak of b (H on -CH=C-); the chemical shift at 5.42-5.97 (d, 2H) ppm indicates the peak of c (-C=CH 2 H) peak on.

[0137] Figure 3 The Lewis acid monomer prepared in Preparation Example 1 11 B NMR spectrum, from Figure 3 It can be seen that: B: 74.3 (br) ppm indicates the appearance of B (boron group) peak.

[0138] Preparation Example 2

[0139] This preparation example is a Lewis acid prepared according to the present invention.

[0140] The Lewis acid was prepared in the same manner as in Preparation Example 1, except that "pentafluorophenylmagnesium bromide" was replaced by "3,5-difluorophenylmagnesium bromide".

[0141] Results The Lewis acid monomer prepared was di(3,5-difluorophenyl)(4-vinylphenyl)borane, the structure of which is shown in the formula below, and the yield and purity are shown in Table 1.

[0142]

[0143] Preparation Example 3

[0144] This preparation example is a Lewis acid prepared according to the present invention.

[0145] The Lewis acid was prepared in the same manner as in Preparation Example 1, except that "pentafluorophenylmagnesium bromide" was replaced by "3,4,5-trifluorophenylmagnesium bromide".

[0146] Results The Lewis acid monomer prepared was di(3,4,5-trifluorophenyl)(4-vinylphenyl)borane, the structure of which is shown below, and the yield and purity are shown in Table 1.

[0147]

[0148] Preparation Example 4

[0149] This preparation example is a Lewis acid prepared according to the present invention.

[0150] The Lewis acid was prepared in the same manner as in Preparation Example 1, except that "pentafluorophenylmagnesium bromide" was replaced by "3-fluorophenylmagnesium bromide".

[0151] Results The Lewis acid monomer prepared was di(3-fluorophenyl)(4-vinylphenyl)borane, the structure of which is shown below, and the yield and purity are shown in Table 1.

[0152]

[0153] Preparation Example 5

[0154] This preparation example is a Lewis acid prepared according to the present invention.

[0155] A Lewis acid was prepared in the same manner as in Preparation Example 1, except that "pentafluorophenylmagnesium bromide" was replaced by "4-methoxy-3,5-difluorophenylmagnesium bromide".

[0156] Results The Lewis acid monomer prepared was di[3,5-difluoro(4-hydroxymethyl)phenyl](4-vinylphenyl)borane, the structure of which is shown below, and the yield and purity are shown in Table 1.

[0157]

[0158] Table 1

[0159]

[0160]

[0161] Preparation Example 6

[0162] This preparation example is to illustrate the Lewis base prepared by the present invention.

[0163] (J1) under nitrogen protection, phosphorus trichloride was dissolved in anhydrous tetrahydrofuran, and then the mesitylene magnesium bromide tetrahydrofuran solution was slowly added dropwise at a drop rate of 1 drop / second, and the reaction was carried out at 0°C and a stirring rate of 400 rpm for 12 hours; wherein the concentration of the mesitylene magnesium bromide tetrahydrofuran solution was 1 mol / L;

[0164] (J2) slowly adding a tetrahydrofuran solution of p-styrene magnesium bromide to the mixed solution of step (J1) at a rate of 1 drop / second at 0°C and a stirring rate of 500 rpm, and after the addition is completed, stirring the reaction mixture at 0°C for 15 hours to obtain a crude product mixed solution containing the target product; wherein the concentration of the tetrahydrofuran solution of p-styrene magnesium bromide is 1 mol / L;

[0165] The molar ratio of mesitylene magnesium bromide, phosphorus trichloride and p-phenylene magnesium bromide is 1:0.5:0.5.

[0166] (J3) Add saturated NaCl solution to the crude product mixture obtained in step (J2), then extract with ether, collect the organic phase and dry it with anhydrous magnesium sulfate, then perform rotary evaporation (30°C, -0.08MPa), and add the concentrated liquid to methanol to obtain a crude product.

[0167] The weight ratio of the crude product mixture, the saturated NaCl solution and diethyl ether is 1:0.5:1.5; the weight ratio of the concentrated liquid and methanol is 1:3.

[0168] (J4) The crude product obtained in step (J3) is passed through a neutral alumina chromatography column to obtain a Lewis base monomer di-mesitylene (4-vinylphenyl) phosphine, the structure of which is shown below:

[0169]

[0170] Results The yield and purity of the prepared Lewis base monomer are shown in Table 2.

[0171] Figure 4 The Lewis base monomer prepared in Preparation Example 6 1 H NMR spectrum, from Figure 4 The nuclear magnetic resonance spectrum shows that: the chemical shift of the abscissa at 7.17-7.35 (m, 4H) ppm indicates the appearance of a (H on the benzene ring of the mesitylene group) peak; the chemical shift of 6.85 (m, 4H) ppm indicates the appearance of b (H on the benzene ring of the styrene group) peak; the chemical shift of 6.64 (d, 1H) ppm indicates the appearance of c (H on -C=CH-) peak; the chemical shift of 5.28-5.75 (d, 2H) ppm indicates the appearance of d (CH 2 =H) peak on C-; chemical shift 2.10-2.24 (s, 18H) ppm indicates the presence of e(-CH 3 H) peak on the group.

[0172] Figure 5 The Lewis base monomer prepared in Preparation Example 6 31 P NMR spectrum, from Figure 5 It can be seen that: P: -22.1(s) ppm indicates the appearance of P (phosphorus group) peak.

[0173] Preparation Example 7

[0174] This preparative example is intended to illustrate the preparation of a Lewis base monomer.

[0175] A Lewis base was prepared in the same manner as in Preparation Example 6, except that "mesitylene magnesium chloride" was replaced by "2,4,6-triethylphenyl magnesium chloride".

[0176] Results The Lewis base monomer prepared was di(2,4,6-triethylphenyl)(4-vinylphenyl)phosphine, the structure of which is shown below, and the yield and purity are shown in Table 2.

[0177]

[0178] Preparation Example 8

[0179] This preparative example is intended to illustrate the preparation of a Lewis base monomer.

[0180] A Lewis base was prepared in the same manner as in Preparation Example 6, except that "mesitylene magnesium chloride" was replaced by "2,4,6-triisopropylphenyl magnesium chloride".

[0181] Results The Lewis base monomer prepared was di(2,4,6-triisopropylphenyl)(4-vinylphenyl)phosphine, the structure of which is shown below, and the yield and purity are shown in Table 2.

[0182]

[0183] Preparation Example 9

[0184] This preparative example is intended to illustrate the preparation of a Lewis base monomer.

[0185] A Lewis base was prepared in the same manner as in Preparation Example 6, except that "mesitylene magnesium chloride" was replaced by "phenyl magnesium chloride".

[0186] Results The Lewis base monomer prepared was diphenyl (4-vinylphenyl) phosphine, the structure of which is shown below, and the yield and purity are shown in Table 2.

[0187]

[0188] Preparation Example 10

[0189] This preparative example is intended to illustrate the preparation of a Lewis base monomer.

[0190] A Lewis base was prepared in the same manner as in Preparation Example 6, except that "mesitylene magnesium chloride" was replaced by "2,4,6-tri-tert-butylphenyl magnesium chloride".

[0191] Results The Lewis base monomer prepared was di(2,4,6-tri-tert-butylphenyl)(4-vinylphenyl)phosphine, the structure of which is shown below, and the yield and purity are shown in Table 2.

[0192]

[0193] Table 2

[0194]

[0195]

[0196] Example 1

[0197] This example is to illustrate the CO prepared by the method of the present invention. 2 Reactive viscosity enhancing agent.

[0198] (1) In a reactor equipped with a temperature control device and a reflux condenser, dipentafluorophenyl (4-vinylphenyl) boron prepared in Preparation Example 1, di-mesitylene (4-vinylphenyl) phosphorus prepared in Preparation Example 6, acrylamide and C 14 Sodium olefin sulfonate is added into a mixed solvent of toluene and dimethyl sulfoxide, and the mixture is mixed and stirred.

[0199] Among them, dipentafluorophenyl (4-vinylphenyl) boron, di-mesityl (4-vinylphenyl) phosphorus, acrylamide and C 14 The molar ratio of sodium olefin sulfonate is 1:1:60:2, the concentration of the monomer mixture in the mixed solvent is 15 wt %, and the volume ratio of toluene and dimethyl sulfoxide is 2:3.

[0200] (2) After nitrogen was passed through for 30 min, azobisisobutyronitrile (DIBN) was added to the mixture, the temperature was raised to 62° C., and the mixture was stirred at 300 rpm for 24 h.

[0201] Wherein, the amount of azobisisobutyronitrile used is 0.5 weight % of the total weight of the monomer mixture.

[0202] (3) Methanol was added to the above reaction material, solid was precipitated and filtered, and then vacuum dried at 40°C to constant weight to obtain CO 2 The reaction viscosity increasing agent, the parameter characterization is shown in Table 3.

[0203] The volume ratio of methanol to the mixed solvent of toluene and dimethyl sulfoxide is 2:1.

[0204] Figure 1 CO prepared in Example 1 2 Reactive viscosity enhancing agent 1 H NMR spectrum, from Figure 1 The NMR spectrum shows that the chemical shift at the abscissa of 1.22-2.75 ppm indicates the presence of ad(-CH 3 、-CH 2 The chemical shift at 6.99 ppm indicates the appearance of the e (H on the benzene ring of the mesitylene group) peak; the chemical shift at 7.17-7.38 ppm indicates the appearance of the f (H on the benzene ring connected to P) peak; the chemical shift at 7.56-7.78 ppm indicates the appearance of the g (H on the benzene ring connected to B) peak.

[0205] Example 2

[0206] This example is to illustrate the CO prepared by the method of the present invention. 2 Reactive viscosity enhancing agent.

[0207] (1) In a reactor equipped with a temperature control device and a reflux condenser, dipentafluorophenyl (4-vinylphenyl) boron prepared in Preparation Example 1, di-mesitylene (4-vinylphenyl) phosphorus prepared in Preparation Example 6, acrylamide and C 16 Sodium olefin sulfonate is added to a mixed solvent of chloroform and dimethyl sulfoxide, and the mixture is mixed and stirred.

[0208] Among them, dipentafluorophenyl (4-vinylphenyl) boron, di-mesityl (4-vinylphenyl) phosphorus, acrylamide and C 16 The molar ratio of sodium olefin sulfonate is 1:0.8:50:3, the concentration of the monomer mixture in the mixed solvent is 20 wt %, and the volume ratio of chloroform and dimethyl sulfoxide is 1:3.

[0209] (2) After nitrogen was introduced for 30 min, the initiator azobisisobutylimidazoline hydrochloride was added to the mixed solution, the temperature was raised to 60° C., and the mixture was stirred at a stirring rate of 400 rpm for 20 h.

[0210] Wherein, the amount of azobisisobutylimidazoline hydrochloride used is 0.3 weight % of the total weight of the monomer mixture.

[0211] (3) Methanol was added to the above reaction material, solid was precipitated and filtered, and then vacuum dried at 30°C to constant weight to obtain CO 2 The reaction viscosity increasing agent, the parameter characterization is shown in Table 3.

[0212] The volume ratio of methanol to the mixed solvent of chloroform and dimethyl sulfoxide is 1:1.

[0213] Example 3

[0214] This example is to illustrate the CO prepared by the method of the present invention. 2 Reactive viscosity enhancing agent.

[0215] (1) In a reactor equipped with a temperature control device and a reflux condenser, dipentafluorophenyl (4-vinylphenyl) boron prepared in Preparation Example 1, di-mesitylene (4-vinylphenyl) phosphorus prepared in Preparation Example 6, acrylic acid and C 16 Sodium olefin sulfonate is added into a mixed solvent of toluene and N,N-dimethylformamide, and the mixture is mixed and stirred.

[0216] Among them, dipentafluorophenyl (4-vinylphenyl) boron, di-mesitylene (4-vinylphenyl) phosphorus, acrylic acid and C 16 The molar ratio of sodium olefin sulfonate is 1:1.2:70:2, the concentration of the monomer mixture in the mixed solvent is 25 wt %, and the volume ratio of toluene and N,N-dimethylformamide is 1:2.

[0217] (2) After nitrogen was introduced for 60 min, azobisisobutyronitrile as an initiator was added to the mixed solution, the temperature was raised to 70° C., and the mixture was stirred at a stirring rate of 200 rpm for 16 h.

[0218] Wherein, the amount of azobisisobutyronitrile used is 0.5 weight % of the total weight of the monomer mixture.

[0219] (3) Add ethanol to the above reaction material, precipitate the solid, filter it, and then vacuum dry it at 40°C to constant weight to obtain CO 2 The reaction viscosity increasing agent, the parameter characterization is shown in Table 3.

[0220] The volume ratio of ethanol to the mixed solvent of toluene and N,N-dimethylformamide is 3:1.

[0221] Example 4

[0222] This example is to illustrate the CO prepared by the method of the present invention. 2 Reactive viscosity enhancing agent.

[0223] (1) In a reactor equipped with a temperature control device and a reflux condenser, dipentafluorophenyl (4-vinylphenyl) boron prepared in Preparation Example 1, di-mesitylene (4-vinylphenyl) phosphorus prepared in Preparation Example 6, methacrylic acid and C 14 Sodium olefin sulfonate is added into a mixed solvent of cyclohexane and dimethyl sulfoxide, and the mixture is mixed and stirred.

[0224] Among them, dipentafluorophenyl (4-vinylphenyl) boron, di-mesitylene (4-vinylphenyl) phosphorus, methacrylic acid and C 14 The molar ratio of sodium olefin sulfonate is 1:0.6:40:1, the concentration of the monomer mixture in the mixed solvent is 10 wt %, and the volume ratio of cyclohexane and dimethyl sulfoxide is 1:1.

[0225] (2) After passing argon for 30 minutes, the initiator azoisobutylcyanamide was added to the mixed solution, the temperature was raised to 80° C., and the mixture was stirred at a stirring rate of 500 rpm for 28 hours.

[0226] Wherein, the amount of azoisobutylcyanamide used is 0.2 weight % of the total weight of the monomer mixture.

[0227] (3) Add ethanol to the above reaction material, precipitate the solid, filter it, and then vacuum dry it at 50°C to constant weight to obtain CO 2 The reaction viscosity increasing agent, the parameter characterization is shown in Table 3.

[0228] The volume ratio of ethanol to the mixed solvent of cyclohexane and dimethyl sulfoxide is 3:1.

[0229] Example 5

[0230] This example is to illustrate the CO prepared by the method of the present invention. 2 Reactive viscosity enhancing agent.

[0231] (1) In a reactor equipped with a temperature control device and a reflux condenser, dipentafluorophenyl (4-vinylphenyl) boron prepared in Preparation Example 1, di-mesitylene (4-vinylphenyl) phosphorus prepared in Preparation Example 6, N-vinyl amide and C 16 Sodium olefin sulfonate is added into a mixed solvent of toluene and dimethyl sulfoxide, and the mixture is mixed and stirred.

[0232] Among them, dipentafluorophenyl (4-vinylphenyl) boron, di-mesityl (4-vinylphenyl) phosphorus, N-vinyl amide and C16 The molar ratio of sodium olefin sulfonate is 1:1.8:80:4, the concentration of the monomer mixture in the mixed solvent is 30 wt %, and the volume ratio of toluene and dimethyl sulfoxide is 1:2.

[0233] (2) After nitrogen was passed through for 45 min, azodimethyl N-2-hydroxybutyl acrylamide as an initiator was added to the mixed solution, the temperature was raised to 50° C., and the mixture was stirred at a stirring rate of 400 rpm for 12 h.

[0234] Wherein, the amount of azodimethyl N-2-hydroxybutyl acrylamide used is 0.6 weight % of the total weight of the monomer mixture.

[0235] (3) Add isopropanol to the above reaction material, filter the precipitated solid, and then vacuum dry at 50°C to constant weight to obtain CO 2 The reaction viscosity increasing agent, the parameter characterization is shown in Table 3.

[0236] The volume ratio of isopropanol to the mixed solvent of toluene and dimethyl sulfoxide is 1:2.

[0237] Example 6

[0238] This example is to illustrate the CO prepared by the method of the present invention. 2 Reactive viscosity enhancing agent.

[0239] The same method as in Example 1 was used to prepare CO 2 The reaction thickening and polymerizing agent is different in that: "dipentafluorophenyl (4-vinylphenyl) borane" is replaced by "di(3,5-difluorophenyl) (4-vinylphenyl) borane prepared in Preparation Example 2", and "di-mesitylene (4-vinylphenyl) phosphine" is replaced by "di(2,4,6-triethylphenyl) (4-vinylphenyl) phosphine prepared in Preparation Example 7".

[0240] As a result, CO 2 The reaction viscosity increasing agent, the parameter characterization is shown in Table 3.

[0241] Example 7

[0242] This example is to illustrate the CO prepared by the method of the present invention. 2 Reactive viscosity enhancing agent.

[0243] The same method as in Example 1 was used to prepare CO 2The reaction thickening and polymerizing agent is different in that: "dipentafluorophenyl (4-vinylphenyl) borane" is replaced by "di(3,4,5-trifluorophenyl) (4-vinylphenyl) borane prepared in Preparation Example 3", and "di-mesitylene (4-vinylphenyl) phosphine" is replaced by "di(2,4,6-triisopropylphenyl) (4-vinylphenyl) phosphine prepared in Preparation Example 8".

[0244] As a result, CO 2 The reaction viscosity increasing agent, the parameter characterization is shown in Table 3.

[0245] Example 8

[0246] This example is to illustrate the CO prepared by the method of the present invention. 2 Reactive viscosity enhancing agent.

[0247] The same method as in Example 1 was used to prepare CO 2 The reaction thickening and polymerizing agent is different in that: "dipentafluorophenyl (4-vinylphenyl) borane" is replaced by "di(3-fluorophenyl) (4-vinylphenyl) borane prepared in Preparation Example 4", and "di-mesitylene (4-vinylphenyl) phosphine" is replaced by "diphenyl (4-vinylphenyl) phosphine prepared in Preparation Example 9".

[0248] As a result, CO 2 The reaction viscosity increasing agent, the parameter characterization is shown in Table 3.

[0249] Example 9

[0250] This example is to illustrate the CO prepared by the method of the present invention. 2 Reactive viscosity enhancing agent.

[0251] The same method as in Example 1 was used to prepare CO 2 The reaction thickening and polymerizing agent is different in that: "dipentafluorophenyl (4-vinylphenyl) borane" is replaced by "di[3,5-difluoro(4-hydroxymethyl)phenyl](4-vinylphenyl) borane prepared in Preparation Example 5", and "di-mesitylene (4-vinylphenyl) phosphine" is replaced by "di(2,4,6-tri-tert-butylphenyl) (4-vinylphenyl) phosphine prepared in Preparation Example 10".

[0252] As a result, CO 2 The reaction viscosity increasing agent, the parameter characterization is shown in Table 3.

[0253] Example 10

[0254] This example is to illustrate the CO prepared by the method of the present invention. 2 Reactive viscosity enhancing agent.

[0255] The same method as in Example 1 was used to prepare CO 2 The reactive thickening polymerizing agent is different in that the "mixed solvent of toluene and dimethyl sulfoxide" is replaced by "single solvent of dimethyl sulfoxide".

[0256] As a result, CO 2 The reaction viscosity increasing agent, the parameter characterization is shown in Table 3.

[0257] Comparative Example 1

[0258] The same method as in Example 1 was used to prepare CO 2 The reactive viscosity-enhancing polymerizing agent is different in that no Lewis acid monomer dipentafluorophenyl (4-vinylphenyl) boron is added.

[0259] As a result, CO 2 The reaction viscosity increasing agent, the parameter characterization is shown in Table 3.

[0260] Comparative Example 2

[0261] The same method as in Example 1 was used to prepare CO 2 The reactive thickening polymerizing agent is different in that no Lewis base monomer di-mesitylene (4-vinylphenyl) phosphine is added.

[0262] As a result, CO 2 The reaction viscosity increasing agent, the parameter characterization is shown in Table 3.

[0263] Comparative Example 3

[0264] The same method as in Example 1 was used to prepare CO 2 Reaction viscosity enhancing agent, the difference is that no surface active monomer C is added 14 Sodium olefin sulfonate.

[0265] As a result, CO 2 The reaction viscosity increasing agent, the parameter characterization is shown in Table 3.

[0266] Comparative Example 4

[0267] The same method as in Example 1 was used to prepare CO 2 The difference between the reaction viscosity increasing and polymerizing agent is that the reaction temperature is set to 0°C.

[0268] As a result, CO 2 The reaction viscosity increasing agent, the parameter characterization is shown in Table 3.

[0269] Comparative Example 5

[0270] The same method as in Example 1 was used to prepare CO 2The difference between the reactive thickening and polymerizing agent is that no inert gas is introduced.

[0271] As a result, CO 2 The reaction viscosity increasing agent, the parameter characterization is shown in Table 3.

[0272] Comparative Example 6

[0273] The same method as in Example 1 was used to prepare CO 2 The difference between the reactive thickening agent and the reactive thickening agent is that: dipentafluorophenyl (4-vinylphenyl) boron, di-mesitylene (4-vinylphenyl) phosphorus, acrylamide and C 14 The molar ratio of sodium olefin sulfonate was changed from "1:1:60:2" to "1:20:60:2".

[0274] As a result, CO 2 The reaction viscosity increasing agent, the parameter characterization is shown in Table 3.

[0275] Comparative Example 7

[0276] The same method as in Example 1 was used to prepare CO 2 The difference between the reactive thickening agent and the reactive thickening agent is that: dipentafluorophenyl (4-vinylphenyl) boron, di-mesitylene (4-vinylphenyl) phosphorus, acrylamide and C 14 The molar ratio of sodium olefin sulfonate was changed from "1:1:60:2" to "1:1:2:2".

[0277] As a result, CO 2 The reaction viscosity increasing agent, the parameter characterization is shown in Table 3.

[0278] Table 3

[0279]

[0280]

[0281] Test Case

[0282] 1. CO 2 Reaction viscosity test

[0283] 0.5 g of CO prepared in Examples 1-10 and Comparative Examples 1-7 were added 2 The reactive thickening polymer was added to 50 mL of water and stirred at 10000 r / min for 30 min to obtain different polymer solutions. The rheometer Anton Paar MCR 72 was used to measure the viscosity of the polymer solution at 25 °C and 10 s -1 The initial viscosity of each polymer solution was measured at a shear rate of 100 mL / min. 2CO was passed into each polymer solution for 20 min. 2 After the injection is completed, let it stand for 2 hours, then heat it at 25℃ for 10 seconds. -1 The final viscosity of each polymer solution was measured at the shear rate. 2 The test results of viscosity before and after are shown in Table 4. 2 The viscosity before and after is shown.

[0284] Table 4

[0285]

[0286]

[0287] It can be seen from Table 4 that the CO prepared in Examples 1-10 2 The reaction thickening agent is introduced into the 2 The viscosity increasing effect is significant, while in the case of the lack of Lewis acid monomer or Lewis base monomer in Comparative Example 1 and Comparative Example 2, CO 2 The reaction thickening agent is introduced into the CO 2 After that, it is basically impossible to increase viscosity, indicating that the surfactant will react with CO only when Lewis acid and base monomers are present at the same time. 2 The reaction occurs, causing cross-linking between polymer chains, thereby increasing the viscosity of the solution.

[0288] 2. Plugging performance test

[0289] The injection pressure was 3.5 MPa. 2 Gas drive, stop gas drive after gas channeling stabilizes, and then 2 The reactive thickening polymer was injected into the simulated core fracture at a rate of 0.5 PV. 2 After the reaction viscosity enhancing polymer system is stable, CO is continuously injected 2 Then the gas flow rate at the core fractures was measured after being placed at 50°C for 3 months, and the gas flow rate at the core fractures was measured to calculate the plugging rate. The results are shown in Table 5. 2 The test results of gas channeling blocking of reactive thickening polymer are shown in Figure 2.

[0290] The calculation formula of the blocking rate is: blocking rate (%) = (flow rate before blocking - flow rate after blocking) / flow rate before blocking × 100%.

[0291] Table 5

[0292]

[0293]

[0294] It can be seen from Table 5 that the CO prepared by the method of the present invention 2 Under the optimal conditions, the reaction viscosity increasing agent has a great influence on CO 2 The blocking rate of gas channeling is above 91%. After being placed at 50°C for 3 months, the blocking rate remains basically unchanged, indicating that the CO prepared by the method of the present invention is 2 The reactive thickening polymer has good gas channeling blocking performance and chemical stability. However, the blocking rate of comparative examples 1-7 is significantly lower than that of the embodiment, because the method of the present invention is not used.

[0295] 3. Heavy oil viscosity reduction performance test

[0296] 0.5 g of CO prepared in Examples 1-10 and Comparative Examples 1-7 were added 2 The reaction thickening polymer was added to 50 mL of water and stirred at 10000 r / min for 30 min to obtain different polymer solutions. The polymer solutions were added to glass reagent bottles with a 1:1 oil-water ratio of 5:1. The bottles were sealed and placed in a 50°C constant temperature oven for aging for 3 h. The bottles were then taken out and inverted four times to mix the oil and water phases to form a uniform emulsion. The rheometer Anton paar MCR 72 was used to measure the emulsion at 25°C and 10 s -1 The viscosity of heavy oil and emulsion was measured at shear rate, and the viscosity reduction rate was calculated. The results are shown in Table 6. 2 The results of the viscosity reduction test of heavy oil using reactive thickening polymer surfactant are shown.

[0297] The viscosity reduction rate is calculated as follows: viscosity reduction rate (%) = (viscosity of heavy oil - viscosity of emulsion) / viscosity of heavy oil × 100%.

[0298] Table 6

[0299]

[0300]

[0301] It can be seen from Table 6 that the CO prepared by the method of the present invention 2 Under the optimal conditions, the viscosity reduction rate of the reactive thickening polymer is greater than 90%, indicating that it has good viscosity reduction ability for heavy oil. However, since no interfacial active monomer is added in Comparative Example 3, the product obtained has basically no emulsification viscosity reduction ability.

[0302] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A CO2 reactive thickening and polymerizing agent, characterized in that: The CO2 reaction viscosity-enhancing agent comprises a structural unit provided by a Lewis acid monomer as shown in formula (1), a structural unit provided by a Lewis base monomer as shown in formula (2), a structural unit provided by a hydrophilic monomer, and a structural unit provided by an interfacial active monomer as shown in formula (3); Wherein, in formula (1), R1, R2, R3, R4 and R5 are the same or different, and are each one or more of H, F, and C1-C4 alkyl alcohol, and at least one of them is F; Wherein, in formula (2), R6, R7 and R8 are the same or different, and each is one or more of H, C1-C4 alkyl; Wherein, in formula (3), R is C 10 -C 16 One or more of the alkyl groups.

2. The CO2 reactive thickening polymerizing agent according to claim 1, wherein In formula (1), R1, R2, R3, R4 and R5 are the same or different, and are each one or more of H, F, and C1-C3 alkyl alcohol, and at least one of them is F; Preferably, the Lewis acid monomer is selected from one or more of formula (1-1), formula (1-2), formula (1-3), formula (1-4) and formula (1-5); More preferably, the Lewis acid monomer is selected from one or more of dipentafluorophenyl(4-vinylphenyl)boron, di(3,5-difluorophenyl)(4-vinylphenyl)boron and di(3,4,5-trifluorophenyl)(4-vinylphenyl)boron.

3. The CO2 reactive thickening polymerizing agent according to claim 1, wherein In formula (2), R6, R7 and R8 are the same or different, and are each one or more of H, C1-C3 alkyl; Preferably, the Lewis base monomer is selected from one or more of formula (2-1), formula (2-2), formula (2-3), formula (2-4) and formula (2-5); More preferably, the Lewis base monomer is selected from one or more of di-mesityl(4-vinylphenyl)phosphine, di(2,4,6-triethylphenyl)(4-vinylphenyl)phosphine and di(2,4,6-triisopropylphenyl)(4-vinylphenyl)phosphine.

4. The CO2 reactive thickening agent according to any one of claims 1 to 3, wherein The purity of the Lewis acid monomer is 82-98%, preferably 82.06-97.88%, preferably 90-98%; And / or, the purity of the Lewis base monomer is 80-99%, preferably 80.3-98.82%, more preferably 92.38-98.82%.

5. The CO2 reactive thickening polymerizing agent according to claim 1, wherein The hydrophilic monomer is selected from one or more of acrylamide, N-vinylamide, acrylic acid and methacrylic acid; And / or, in formula (3), R is C 10 -C 16 One or more of the alkyl groups.

6. The CO2 reactive thickening and polymerization agent according to any one of claims 1 to 5, wherein: The molar ratio of the structural unit provided by the Lewis acid monomer represented by formula (1), the structural unit provided by the Lewis base monomer represented by formula (2), the structural unit provided by the hydrophilic monomer, and the structural unit provided by the interfacial active monomer represented by formula (3) is 1: (0.4-2.5): (10-100): (0.5-10), preferably 1: (0.5-2): (25-80): (0.7-6), more preferably 1: (0.7-1.5): (30-70): (1-4), and further preferably 1: (0.8-1.3): (40-60): (1.5-3); And / or, the number average molecular weight of the CO2 reaction thickening polymer is 100,000-2,000,000, preferably 500,000-1,500,000, more preferably 800,000-1,200,000, and further preferably 900,000-1,100,000.

7. A method for preparing the CO2 reactive thickening and polymerization agent according to any one of claims 1 to 6, characterized in that: The preparation method comprises: (F1) contacting and mixing a Lewis acid monomer represented by formula (1), a Lewis base monomer represented by formula (2), a hydrophilic monomer, an interfacial active monomer represented by formula (3) and a solvent to obtain a mixture; (F2) contacting the mixture with an initiator under the protection of an inert gas to react; (F3) contacting the product obtained in step (F2) with an alcohol solvent and then subjecting the product to precipitation, filtration and drying to obtain a CO2 reaction thickening and polymerizing agent.

8. The preparation method according to claim 7, wherein: The molar ratio of the Lewis acid monomer represented by formula (1), the Lewis base monomer represented by formula (2), the hydrophilic monomer and the interfacial active monomer represented by formula (3) is 1: (0.5-2): (20-100): (1-10), preferably 1: (0.6-1.5): (30-80): (1-6), more preferably 1: (0.7-1.3): (40-70): (2-5), and further preferably 1: (0.8-1.2): (50-70): (2-3).

9. The preparation method according to claim 7, wherein: Based on the total weight of the Lewis acid monomer represented by formula (1), the Lewis base monomer represented by formula (2), the hydrophilic monomer and the interfacial active monomer represented by formula (3), the amount of the initiator is 0.1-0.8 wt %, preferably 0.2-0.5 wt %; and / or, the solvent is selected from at least two of toluene, chloroform, dimethyl sulfoxide, N,N-dimethylformamide and cyclohexane; And / or, the concentrations of the Lewis acid monomer represented by formula (1), the Lewis base monomer represented by formula (2), the hydrophilic monomer and the interfacial active monomer represented by formula (3) in the solvent are the same or different, and are each 10-30 wt %.

10. The preparation method according to claim 7, wherein: In step (F2), the reaction conditions include: reaction temperature of 40-100°C, reaction time of 12-28h; preferably, reaction temperature of 60-80°C, reaction time of 16-24h.

11. Use of the CO2 reaction thickening polymerizing agent according to any one of claims 1 to 6 in controlling gas breakthrough during CO2 flooding of offshore heavy oil.

Images