CN115677918B - Terpolymer and preparation method and application thereof - Google Patents
Terpolymer and preparation method and application thereof Download PDFInfo
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- CN115677918B CN115677918B CN202110857673.9A CN202110857673A CN115677918B CN 115677918 B CN115677918 B CN 115677918B CN 202110857673 A CN202110857673 A CN 202110857673A CN 115677918 B CN115677918 B CN 115677918B
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- 229920001897 terpolymer Polymers 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000178 monomer Substances 0.000 claims description 77
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 18
- 239000000084 colloidal system Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 15
- 239000003999 initiator Substances 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 238000006460 hydrolysis reaction Methods 0.000 claims description 13
- 239000004202 carbamide Substances 0.000 claims description 11
- 229920001577 copolymer Polymers 0.000 claims description 11
- 238000010528 free radical solution polymerization reaction Methods 0.000 claims description 10
- 239000008139 complexing agent Substances 0.000 claims description 7
- RGRJEERVXALLTH-UHFFFAOYSA-N 1,3-bis(4-methoxyphenyl)thiourea Chemical group C1=CC(OC)=CC=C1NC(=S)NC1=CC=C(OC)C=C1 RGRJEERVXALLTH-UHFFFAOYSA-N 0.000 claims description 6
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical group [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 6
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 5
- 239000007800 oxidant agent Substances 0.000 claims description 5
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 5
- 239000003638 chemical reducing agent Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 230000033116 oxidation-reduction process Effects 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000001804 emulsifying effect Effects 0.000 abstract description 9
- 150000003839 salts Chemical class 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 30
- 239000007864 aqueous solution Substances 0.000 description 22
- 239000003921 oil Substances 0.000 description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 238000006116 polymerization reaction Methods 0.000 description 16
- 229920000642 polymer Polymers 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- 238000004364 calculation method Methods 0.000 description 10
- 230000033558 biomineral tissue development Effects 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 238000012360 testing method Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- 238000007873 sieving Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000006073 displacement reaction Methods 0.000 description 4
- 230000001965 increasing effect Effects 0.000 description 4
- 230000000977 initiatory effect Effects 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 4
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 4
- 229920003169 water-soluble polymer Polymers 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 3
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 239000013043 chemical agent Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000003129 oil well Substances 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
- 230000037048 polymerization activity Effects 0.000 description 2
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 239000002332 oil field water Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- DJEHXEMURTVAOE-UHFFFAOYSA-M potassium bisulfite Chemical compound [K+].OS([O-])=O DJEHXEMURTVAOE-UHFFFAOYSA-M 0.000 description 1
- 235000010259 potassium hydrogen sulphite Nutrition 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Abstract
The invention relates to the field of oilfield chemicals, and discloses a terpolymer and a preparation method and application thereof. The terpolymer contains a structural unit A, a structural unit B and a structural unit C; the structural unit A has a structure shown in a formula (1), the structural unit B has a structure shown in a formula (2), and the structural unit C has a structure shown in a formula (3); based on the total weight of the terpolymer, the content of the structural unit A is 90-97 wt%, the content of the structural unit B is 2-8 wt%, and the content of the structural unit C is 1-4 wt%; wherein R 1、R2、R3 and R 4 are each independently H or-CH 3, and X is Br or F. The terpolymer has higher viscosity under the conditions of high temperature and high salt, can enter the deep part of an oil reservoir, can reduce the interfacial tension of an oil-water surface, and has better emulsifying property.
Description
Technical Field
The invention relates to the field of oilfield chemicals, in particular to a terpolymer and a preparation method and application thereof.
Background
In tertiary oil recovery, flooding with water-soluble polymers has been developed as an extremely important enhanced oil recovery technique. The water-soluble polymer has good water solubility and tackifying property, and when the water-soluble polymer is added into water, the viscosity of an aqueous solution can be obviously increased, the drainage/oil fluidity ratio of an oil reservoir can be reduced, the sweep volume and sweep efficiency of fluid can be further improved, and the oil saturation of a sweep area can be reduced, so that the aim of improving the oil recovery ratio can be fulfilled. In the prior art, the partially hydrolyzed polyacrylamide is a common water-soluble polymer for oil displacement, and the common polyacrylamide has excellent tackifying property under the condition of a conventional oil reservoir at present, shows good oil displacement effect, but the oil displacement effect is obviously reduced under the conditions of high temperature and high salt. This is because polymer molecular chains undergo polymer chain entanglement and rapid degradation under high temperature and high salt conditions, resulting in a large decrease in the viscosity of the aqueous solution.
In recent years, along with the continuous improvement of the development degree of oilfield water injection in China, the water content of an oil reservoir is also continuously increased, and the requirements of adjusting the water absorption profile in the deep part of the oil reservoir, forcing the liquid flow to turn and improving the recovery ratio of water injection development are proposed. In order to adapt to the purpose of deep oil reservoir profile control, novel chemical agents such as strong gel, weak gel, particle gel and the like are correspondingly developed. However, these chemical agents generally have poor fluidity, and especially face the problems of serious flooding of oil wells, complex oil-water relationship and the like in the ultra-high water-containing stage, and cannot achieve the purpose of deep oil reservoir flooding, and can only act in a short-distance zone of an implementation well, so that the on-site implementation period is short and the effect is poor.
Disclosure of Invention
The invention aims to overcome the problems in the prior art, and provides a terpolymer, a preparation method and application thereof, wherein the terpolymer has higher viscosity under the conditions of high temperature and high salt, can enter the deep part of an oil reservoir, can reduce the interfacial tension of an oil-water surface, and has better emulsifying property.
In order to achieve the above object, a first aspect of the present invention provides a terpolymer characterized in that the terpolymer contains a structural unit a, a structural unit B and a structural unit C;
The structural unit A has a structure shown in a formula (1), the structural unit B has a structure shown in a formula (2), and the structural unit C has a structure shown in a formula (3); the content of the structural unit A is 90-97 wt%, the content of the structural unit B is 2-8 wt% and the content of the structural unit C is 1-4 wt% based on the total weight of the terpolymer;
wherein R 1、R2、R3 and R 4 are each independently H or-CH 3, X is Br or F
In a second aspect, the present invention provides a process for preparing a terpolymer, the process comprising:
1) Under the condition of solution polymerization and in the presence of an initiator, carrying out polymerization reaction on the monomer mixture in water to obtain copolymer colloid; wherein the monomer mixture comprises (meth) acrylamide, a monomer X and a monomer Y, wherein the monomer X has a structure shown in a formula (4), and the monomer Y has a structure shown in a formula (5);
The amount of (meth) acrylamide is 90 to 97% by weight, the amount of monomer X is 2 to 8% by weight, and the amount of monomer Y is 1 to 4% by weight, based on the total amount of the monomer mixture;
2) Carrying out hydrolysis reaction on the copolymer colloid to obtain a terpolymer;
wherein R 2'、R3 ' and R 4 ' are each independently H or-CH 3, and X ' is Br or F.
In a third aspect the invention provides a terpolymer obtainable by the above process.
In a fourth aspect, the invention provides the use of the terpolymer as described above in an oilfield as a profile control agent.
Through the technical scheme, the terpolymer provided by the invention and the preparation method and application thereof have the following beneficial effects:
the macromolecular chain of the terpolymer provided by the invention comprises the structural unit B from the functional monomer X and the structural unit C from the functional monomer Y, so that the temperature resistance, salt resistance and surface interface activity of the copolymer can be greatly improved, the terpolymer can effectively enter the deep part of a high-temperature high-salt oil reservoir, and the purpose of deep profile control is achieved. Therefore, the terpolymer has higher viscosity under the conditions of high temperature (100 ℃) and high mineralization degree (48000 mg/L), can enter the deep part of an oil reservoir, can reduce the interfacial tension of an oil-water surface, and has better emulsifying property.
Further, in the preparation process of the terpolymer, the functional monomer Y containing a strong hydrophilic group and a lipophilic group, the functional monomer X and (methyl) acrylamide are subjected to polymerization reaction, and particularly, the functional monomer Y has a good emulsifying effect, plays a role in self-emulsifying in a polymerization system, and meanwhile, under the action of an accelerator and urea, the polymerization activity of the monomer is obviously improved, and structural units of three comonomers can be randomly distributed in a high molecular chain, so that the polymer has excellent tackifying property and oil washing emulsifying capability. In addition, the introduction of the functional monomer X can further improve the association of the polymer chains of the copolymer, so that the copolymer aqueous solution still maintains very high viscosity under the conditions of high temperature and high salt, and further the purposes of deep profile control and displacement and plugging control under an oil reservoir are realized.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The first aspect of the present invention provides a terpolymer characterized in that the terpolymer contains a structural unit a, a structural unit B and a structural unit C;
The structural unit A has a structure shown in a formula (1), the structural unit B has a structure shown in a formula (2), and the structural unit C has a structure shown in a formula (3); the content of the structural unit A is 90-97 wt%, the content of the structural unit B is 2-8 wt% and the content of the structural unit C is 1-4 wt% based on the total weight of the terpolymer;
Wherein R 1、R2、R3 and R 4 are each independently H or-CH 3, and X is Br or F.
The inventor of the invention discovers in the research that by simultaneously introducing the structural unit B and the structural unit C into the macromolecular structure of the acrylamide and controlling the content of each structural unit within the range, the obtained terpolymer has higher viscosity under the conditions of high temperature (100 ℃) and high mineralization degree (48000 mg/L), can reduce the interfacial tension of an oil-water surface, has better emulsifying property, can adapt to the environment with serious flooding of an oil well and complex oil-water relationship, and realizes the purpose of deep profile control.
Further, the content of the structural unit A is 90 to 92% by weight, the content of the structural unit B is 5 to 8% by weight, and the content of the structural unit C is 3 to 4% by weight, based on the total weight of the terpolymer.
In the present invention, the total content of the structural unit A, the structural unit B and the structural unit C is 100% by weight.
In the invention, the content of each structural unit in the copolymer can be tested by adopting a conventional method in the prior art, such as infrared spectrum, nuclear magnetism, the feeding amount of monomers in the polymerization process and the like.
In the invention, the monomer feeding amount is adopted to determine the content of each structural unit in the polymer, specifically, the feeding ratio of each monomer actually participating in polymerization is determined by testing the content of unreacted monomers, and then the content of each structural unit in the polymer is determined.
Further, in the present invention, when the content of each unreacted monomer in the tested polymer was 0.02% by weight or less, it was revealed that substantially all the monomer was involved in the polymerization reaction. Specifically, the content of the residual monomer is determined by liquid chromatography.
In a preferred embodiment of the invention, R 1、R2 and R 3 are H, R 4 is H or-CH 3, and X is Br.
In the present invention, the apparent viscosity of the aqueous terpolymer solution is greater than 55 mPas, preferably greater than 60 mPas, under high-temperature (greater than 100 ℃) and high-salt (mineralization degree of 48,000 mg/L) conditions.
In the present invention, the apparent viscosity of the aqueous terpolymer solution was measured using a Brookfield viscometer, specifically, the apparent viscosity of the aqueous terpolymer solution (mass concentration: 0.15% by weight) was measured at a specified test temperature (100 ℃ C.) and mineralization degree (mineralization degree: 48,000 mg/L).
In a second aspect, the present invention provides a process for preparing a terpolymer, the process comprising:
1) Under the condition of solution polymerization and in the presence of an initiator, carrying out polymerization reaction on the monomer mixture in water to obtain copolymer colloid; wherein the monomer mixture comprises (meth) acrylamide, a monomer X and a monomer Y, wherein the monomer X has a structure shown in a formula (4), and the monomer Y has a structure shown in a formula (5);
The amount of (meth) acrylamide is 90 to 97% by weight, the amount of monomer X is 2 to 8% by weight, and the amount of monomer Y is 1 to 4% by weight, based on the total amount of the monomer mixture;
2) Carrying out hydrolysis reaction on the copolymer colloid to obtain a terpolymer;
wherein R 2'、R3 ' and R 4 ' are each independently H or-CH 3, and X ' is Br or F.
In the present invention, (meth) acrylamide, the monomer X and the monomer Y are all commercially available.
In the present invention, the monomer mixture is used in an amount of 20 to 40 parts by weight relative to 100 parts by weight of water.
In the invention, the (methyl) acrylamide, the monomer X with the structure shown in the formula (4) and the monomer Y with the structure shown in the formula (5) are copolymerized to obtain the terpolymer, and the terpolymer can have higher viscosity under the conditions of high temperature (100 ℃) and high mineralization degree (48000 mg/L), can enter the deep part of an oil reservoir, can reduce the interfacial tension of an oil-water surface, and has better emulsifying property.
Further, the (meth) acrylamide is used in an amount of 90 to 92% by weight and the monomer X is used in an amount of 5 to 8% by weight, based on the total weight of the monomer mixture; the monomers Y are used in an amount of 3 to 4% by weight.
In one embodiment of the invention, R 2'、R3 ' and R 4 ' are each independently H or-CH 3, and X ' is Br.
According to the present invention, the conditions for the solution polymerization reaction include: the initiator is an oxidation-reduction system initiator; the reaction temperature is 10-20 ℃, the reaction time is 8-10h, and the pH value is 6-8.
In the present invention, the adjustment of the pH value of the polymerization reaction system can be carried out by means commonly used in the prior art, for example, by adding an alkaline substance such as sodium hydroxide.
According to the present invention, the conditions of the solution polymerization reaction further include: under an inert atmosphere.
In the present invention, an atmosphere capable of providing an inert atmosphere, such as nitrogen, which is conventional in the art, may be employed.
According to the invention, the initiator is used in an amount of 0.015 to 0.15 parts by weight relative to 100 parts by weight of the monomer mixture.
In the present invention, the redox system initiator may be a conventional redox system initiator in the art, preferably a persulfate oxidizer and a sulfite reducer.
Specifically, the persulfate oxidizer may be, for example, potassium persulfate, ammonium persulfate, or the like. The sulfite may be, for example, potassium hydrogen sulfite, sodium hydrogen sulfite, or the like. Preferably, the persulfate oxidizer is 0.01 to 0.1 parts by weight relative to 100 parts by weight of the monomer mixture; the sulfite reducing agent is 0.005-0.05 weight parts.
According to the present invention, the conditions of the solution polymerization reaction further include: in the presence of complexing agents, urea and promoters.
According to the invention, the influence of impurities on polymerization activity can be obviously reduced through complexation of the complexing agent, the water solubility of the copolymer is obviously increased through the introduction of urea, and the viscosity increasing property and the emulsifying property of the prepared terpolymer can be further improved through the introduction of the accelerator.
According to the invention, the complexing agent is 0.01-0.1 parts by weight, the urea is 0.5-5 parts by weight, and the accelerator is 0.05-0.5 parts by weight, relative to 100 parts by weight of the monomer mixture.
According to the invention, the complexing agent is disodium ethylenediamine tetraacetate (EDTA-2 Na) and the accelerator is 1, 3-bis (4-methoxyphenyl) thiourea.
In the present invention, the hydrolysis reaction may be performed under alkaline conditions, which may be achieved by adding sodium hydroxide, and the like, and the amount of the alkaline substance to be added is not particularly limited, and may be adjusted according to the reaction requirements by those skilled in the art. Preferably, the conditions of the hydrolysis reaction include: the temperature is 80-90 ℃ and the time is 2-3h.
Preferably, after the hydrolysis reaction, the reaction product is granulated, dried, pulverized, and sieved to obtain a terpolymer.
In a preferred embodiment of the present invention, the process for preparing a terpolymer comprises:
1) Adding (methyl) acrylamide into a reactor to prepare an aqueous solution, then adding a monomer X, a monomer Y, a complex aqueous solution, urea and an accelerator, regulating the pH value, and fully stirring to form a stable solution;
2) Adding an oxidation-reduction system initiator, blowing inert gas to uniformly mix the initiator and the inert gas, and polymerizing the initiator after sealing to obtain polymer colloid;
3) Taking out colloid, granulating, adding alkaline substances, uniformly mixing, and performing hydrolysis reaction;
4) Granulating, drying, crushing and sieving the hydrolysis reaction product to obtain the terpolymer.
In a third aspect the invention provides a terpolymer obtainable by the above process.
The terpolymer provided by the invention has higher viscosity under the conditions of high temperature (100 ℃) and high mineralization degree (48000 mg/L), can enter into the deep part of an oil reservoir, can reduce the interfacial tension of an oil-water surface, has better emulsifying property, and can be applied to a profile control agent to realize deep profile control.
In a fourth aspect, the invention provides the use of the terpolymer as described above in an oilfield as a profile control agent.
The present invention will be described in detail by examples. In the following examples of the present invention,
All materials are commercially available, except for the specific descriptions. Wherein, the monomer X shown in the formula (4) (R 2 ' is H in X1; R 2 ' is CH 3 in X2) is purchased from Beijing Inocover technology Co., ltd, the monomer Y shown in the formula (5) (Y1; R 3 ' is H, R 4 ' is CH 3, X ' is Br; R 3 ' is H, R 4 ' is H, X ' is Br in Y2; R 3 ' is CH 3,R4 ' is H, X ' is F) is purchased from Williams technology Co., ltd.
Example 1
1) Adding 291g of acrylamide into a thermal insulation polymerization reaction bottle, adding 900g of deionized water, dissolving to prepare an aqueous solution, sequentially adding 16g of monomer X, 1g of monomer Y, 0.03g of EDTA-2Na, 2g of urea, 0.15g of 1, 3-bis (4-methoxyphenyl) thiourea, adding sodium hydroxide to adjust the pH to 7.15, and fully stirring to obtain a stable solution;
2) Introducing nitrogen into the solution at 10 ℃ to expel oxygen for 30 minutes, then adding 3g of 1 wt% potassium persulfate aqueous solution and 1.5g of 1 wt% sodium bisulfate aqueous solution, initiating reaction, continuing introducing nitrogen for five minutes, stopping, sealing, and performing polymerization reaction for 10 hours to obtain polymer colloid;
3) Taking out the colloid, granulating, adding 30.4g of sodium hydroxide, uniformly mixing, and carrying out hydrolysis reaction for 2.5 hours at 80 ℃;
4) Taking out the colloidal particles, granulating, drying at 60 ℃ to constant weight, crushing and sieving to obtain the white granular terpolymer J1.
The content of the structural unit A was 97% by weight, the content of the structural unit B was 2% by weight and the content of the structural unit C was 1% by weight based on the total weight of the terpolymer J1, as determined by calculation of the charge amount.
Example 2
1) Adding 270g of acrylamide into a thermal insulation polymerization reaction bottle, adding 900g of deionized water, dissolving to prepare an aqueous solution, sequentially adding 118g of monomer X, 112g of monomer Y, 0.25g of EDTA-2Na, 15g of urea, 1.0g of 1, 3-bis (4-methoxyphenyl) thiourea, adding sodium hydroxide to adjust the pH to 6.0, and fully stirring to obtain a stable solution;
2) Introducing nitrogen into the solution at 17.5 ℃ to expel oxygen for 30 minutes, then adding 12g of 1 weight percent potassium persulfate aqueous solution and 6g of 1 weight percent sodium bisulfate aqueous solution, initiating reaction, continuing introducing nitrogen for five minutes, stopping, sealing, and carrying out polymerization reaction for 8 hours to obtain polymer colloid; hydrolysis reaction is carried out for 2 hours at 90 ℃;
3) Taking out the colloid, granulating, adding 32.9g of sodium hydroxide, uniformly mixing, and carrying out hydrolysis reaction for 2 hours at 90 ℃;
4) Taking out the colloidal particles, granulating, drying at 60 ℃ to constant weight, crushing and sieving to obtain the white granular terpolymer J2.
The content of the structural unit A was 90% by weight, the content of the structural unit B was 6% by weight and the content of the structural unit C was 4% by weight based on the total weight of the terpolymer J2, which was determined by calculation of the charge amount.
Example 3
1) Adding 270g of acrylamide into a thermal insulation polymerization reaction bottle, adding 900g of deionized water, dissolving to prepare an aqueous solution, sequentially adding 124g of monomer X, 6g of monomer Y, 0.1g of EDTA-2Na, 10g of urea and 1.5g of 1, 3-bis (4-methoxyphenyl) thiourea, adding sodium hydroxide to adjust the pH to 8.0, and fully stirring to obtain a stable solution;
2) Introducing nitrogen into the solution at 20 ℃ to expel oxygen for 30 minutes, then adding 30g of 1 wt% potassium persulfate aqueous solution and 15g of 1 wt% sodium bisulfate aqueous solution, initiating reaction, continuing introducing nitrogen for five minutes, stopping, sealing, and performing polymerization reaction for 9 hours to obtain polymer colloid;
3) Taking out the colloid, granulating, adding 37.2g of sodium hydroxide, uniformly mixing, and carrying out hydrolysis reaction for 3 hours at 85 ℃;
4) Taking out the colloidal particles, granulating, drying at 60 ℃ to constant weight, crushing and sieving to obtain the white granular terpolymer J3.
The content of the structural unit A was 90% by weight, the content of the structural unit B was 8% by weight and the content of the structural unit C was 2% by weight based on the total weight of the terpolymer J4, which was determined by calculation of the charge amount.
Example 4
1) Adding 279g of acrylamide into a thermal insulation polymerization reaction bottle, adding 900g of deionized water to dissolve and prepare an aqueous solution, sequentially adding 115g of monomer X, 26g of monomer Y, 0.3g of EDTA-2Na, 7g of urea and 0.8g of 1, 3-bis (4-methoxyphenyl) thiourea, adding sodium hydroxide to adjust the pH to 7.5, and fully stirring to obtain a stable solution;
2) Introducing nitrogen into the solution at 15 ℃ to expel oxygen for 30 minutes, then adding 18g of 1 wt% potassium persulfate aqueous solution and 9g of 1 wt% sodium bisulfate aqueous solution, initiating reaction, continuing introducing nitrogen for five minutes, stopping, sealing, and performing polymerization reaction for 98 hours to obtain polymer colloid;
3) Taking out the colloid, granulating, adding 35.1g of sodium hydroxide, uniformly mixing, and carrying out hydrolysis reaction for 2 hours at 90 ℃;
4) Taking out the colloidal particles, granulating, drying at 60 ℃ to constant weight, crushing and sieving to obtain the white granular terpolymer J4.
The content of the structural unit A was 93% by weight, the content of the structural unit B was 5% by weight and the content of the structural unit C was 2% by weight based on the total weight of the terpolymer J3, which was determined by calculation of the charge amount.
Example 5
A terpolymer was prepared as in example 1, except that: methacrylamide was used instead of acrylamide. The terpolymer J5 was obtained.
The content of the structural unit A was 97% by weight, the content of the structural unit B was 2% by weight and the content of the structural unit C was 1% by weight based on the total weight of the terpolymer J5, as determined by calculation of the charge amount.
Example 6
A terpolymer was prepared as in example 1, except that: monomer X2 was used instead of monomer X1. The terpolymer J6 was obtained.
The content of the structural unit A was 97% by weight, the content of the structural unit B was 2% by weight and the content of the structural unit C was 1% by weight based on the total weight of the terpolymer J6, which was determined by calculation of the charge amount.
Example 7
A terpolymer was prepared as in example 1, except that: monomer Y3 was used instead of monomer Y1. The terpolymer J7 was obtained.
The content of the structural unit A was 97% by weight, the content of the structural unit B was 2% by weight and the content of the structural unit C was 1% by weight based on the total weight of the terpolymer J7, as determined by calculation of the charge amount.
Comparative example 1
A terpolymer was prepared as in example 1, except that: the monomer Y is replaced by the monomer X with equal mass. To obtain a terpolymer D1.
The content of the structural unit A was 97% by weight, the content of the structural unit B was 3% by weight and the content of the structural unit C was 0% by weight based on the total weight of the terpolymer D1, which was determined by calculation of the charge amount.
Comparative example 2
A terpolymer was prepared as in example 1, except that: the monomer X is replaced by the monomer Y with equal mass. To obtain a terpolymer D2.
The content of the structural unit A was 97% by weight, the content of the structural unit B was 0% by weight and the content of the structural unit C was 3% by weight based on the total weight of the terpolymer D2, which was determined by calculation of the charge amount.
Comparative example 3
A terpolymer was prepared as in example 1, except that: the amount of acrylamide was 294g, the amount of monomer X1 was 4.5g, and the amount of monomer Y1 was 1.5g. To obtain a terpolymer D3.
Based on the total weight of the terpolymer D3, the content of the structural unit A was 98% by weight, the content of the structural unit B was 1.5% by weight and the content of the structural unit C was 0.5% by weight, as determined by calculation of the charge amount.
Test case
The terpolymers obtained in examples and comparative examples were prepared as 0.15 wt% aqueous solutions, respectively, and the apparent viscosity, surface tension and interfacial tension of each aqueous solution were measured, and the test results are shown in table 1.
Wherein, the apparent viscosity of the terpolymer aqueous solution is measured by a Brookfield viscometer, the test temperature is 100 ℃, and the mineralization degree is 48000mg/L;
The surface tension of the terpolymer aqueous solution under pure water is measured by a DCAT-21 surface tensiometer, and the test temperature is 25 ℃;
the interfacial tension of the terpolymer aqueous solution was measured by a TX500C interfacial tensiometer from keno, usa at 100 ℃ and the experimental oil was the victory oilfield crude oil.
TABLE 1
| Product numbering | Apparent viscosity (mPa. S) | Surface tension (mN/m) | Interfacial tension (mN/m) |
| J1 | 76.5 | 29.1 | 8.4×10-2 |
| J2 | 88.7 | 26.3 | 5.2×10-2 |
| J3 | 85.3 | 27.4 | 6.4×10-2 |
| J4 | 82.4 | 29.5 | 7.8×10-2 |
| J5 | 72.6 | 30.5 | 8.8×10-2 |
| J6 | 68.2 | 31.2 | 9.1×10-2 |
| J7 | 65.7 | 30.9 | 8.5×10-2 |
| D1 | 46.7 | 68.8 | 4.2 |
| D2 | 36.8 | 31.5 | 7.8×10-2 |
| D3 | 45.1 | 50.8 | 0.8 |
As can be seen from the results in Table 1, the terpolymer provided by the invention has higher apparent viscosity under the conditions of 100 ℃ and 48000mg/L mineralization degree, and shows excellent high-temperature and high-salt resistance; at the same time, the polymer has lower surface tension and interfacial tension and shows excellent surface activity.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (11)
1. A method of preparing a terpolymer, the method comprising:
1) Under the condition of solution polymerization and in the presence of an initiator, carrying out solution polymerization on the monomer mixture in water to obtain copolymer colloid; wherein the monomer mixture comprises (meth) acrylamide, a monomer X and a monomer Y, wherein the monomer X has a structure shown in a formula (4), and the monomer Y has a structure shown in a formula (5);
The amount of (meth) acrylamide is 90 to 97% by weight, the amount of monomer X is 2 to 8% by weight, and the amount of monomer Y is 1 to 4% by weight, based on the total amount of the monomer mixture;
2) Carrying out hydrolysis reaction on the copolymer colloid to obtain a terpolymer;
wherein R 2'、R3 ' and R 4 ' are each independently H or-CH 3, and X ' is Br or F.
2. The method of claim 1, wherein the conditions of the solution polymerization reaction comprise: the initiator is an oxidation-reduction system initiator; the reaction temperature is 10-20 ℃, the reaction time is 8-10h, and the pH value is 6-8.
3. The method of claim 1, wherein the conditions of the solution polymerization reaction further comprise: under an inert atmosphere.
4. The method according to claim 1, wherein the initiator is used in an amount of 0.015 to 0.15 parts by weight relative to 100 parts by weight of the monomer mixture.
5. The method of claim 2, wherein the oxidation-reduction system initiator is a persulfate oxidizer and a sulfite reducer.
6. The method according to claim 5, wherein the persulfate oxidizer is 0.01 to 0.1 parts by weight relative to 100 parts by weight of the monomer mixture; the sulfite reducing agent is 0.005-0.05 weight parts.
7. The method of any of claims 1-6, wherein the conditions of the solution polymerization reaction further comprise: in the presence of complexing agents, urea and promoters.
8. The method according to claim 7, wherein the complexing agent is 0.01 to 0.1 part by weight, the urea is 0.5 to 5 parts by weight, and the accelerator is 0.05 to 0.5 parts by weight, relative to 100 parts by weight of the monomer mixture.
9. The method of claim 7, wherein the complexing agent is disodium edetate and the accelerator is 1, 3-bis (4-methoxyphenyl) thiourea.
10. A terpolymer obtainable by the process of any one of claims 1 to 9.
11. Use of the terpolymer of claim 10 as a profile control agent in an oilfield.
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| JP2010270170A (en) * | 2009-05-19 | 2010-12-02 | Toagosei Co Ltd | Oil recovery chemical and method for producing the same, and injection liquid for recovering oil |
| CN106589232A (en) * | 2015-10-20 | 2017-04-26 | 中国石油化工股份有限公司 | Hydrophobic association acrylamide copolymer and preparing method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2010270170A (en) * | 2009-05-19 | 2010-12-02 | Toagosei Co Ltd | Oil recovery chemical and method for producing the same, and injection liquid for recovering oil |
| CN106589232A (en) * | 2015-10-20 | 2017-04-26 | 中国石油化工股份有限公司 | Hydrophobic association acrylamide copolymer and preparing method |
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