CN112126018B - Acrylamide copolymer, and preparation method and application thereof - Google Patents
Acrylamide copolymer, and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the field of acrylamide copolymers, and discloses an acrylamide copolymer, a preparation method and application thereof. The copolymer of the present invention comprises a structural unit A, a structural unit B and a structural unit C, wherein the structural unit A is a structural unit shown in the following formula (1), the structural unit B is a structural unit shown in the following formula (2), the structural unit C is a structural unit shown in the following formula (3),
Description
Technical Field
The invention relates to the field of acrylamide copolymers, in particular to an acrylamide copolymer, and a preparation method and application thereof.
Background
In the 90 s, as the water content of the oil field is continuously increased, the oil field water shutoff technology enters a new development stage, the variety of the plugging agent is rapidly increased, the treatment well times are increased, and the economic effect is also obviously improved. In China, water injection development mode is generally adopted in oil fields, formation heterogeneity is serious, oil reservoir geology is complex, water content rising speed in the middle and later stages of development is accelerated, and as water injection quantity is increased, water injection profile heterogeneity is further increased, so that a large amount of water is discharged from the oil wells.
The average water content of the current oil well is up to more than 80%, and the water content of some old oil fields in eastern areas is up to more than 95%. Therefore, the workload of water shutoff and profile control is increased year by year, the working difficulty is continuously increased, the oil increasing potential is reduced, the situation promotes the continuous development of the profile control and water shutoff technology, thereby forming a new hot spot for deep profile control technology research, playing an important role in the aspects of oil stabilization and water control, and correspondingly developing novel chemical agents such as strong gel, weak gel, particle gel and the like. However, the chemical agents can not achieve the purpose of deep profile control and flooding due to the problems of serious flooding of an oil well, complex oil-water relationship and the like in the ultra-high water-containing stage, and can only act in a short-distance zone of an implementation well, so that the field implementation period is short and the effect is poor.
The aqueous solution copolymerization of acrylamide monomer adopts free radical initiation polymerization, and the initiation mode mainly adopts initiator initiation and radiation initiation. The initiator is mainly peroxide, azo compound and the like. The polyacrylamide for oil displacement and profile control of the oil field and the derivative thereof are homopolymers or copolymers taking polyacrylamide as a main chain. The polymerization method can be classified into: aqueous solution polymerization, micelle polymerization, and emulsion polymerization.
The acrylamide copolymer is a novel polymer with hydrophilic groups and lipophilic groups in the macromolecular structure, so that the aqueous solution of the novel polymer has good surface interface activity and emulsifying oil-washing characteristics, and the acrylamide copolymer can be obtained by adopting an aqueous solution copolymerization or micelle copolymerization process, namely, initiating the polymerization of a comonomer under the action of a certain temperature and an initiator and then performing colloid post-treatment.
Acrylamide copolymers are quite different from conventional polymeric surfactants. The properties of high molecular surfactants are more favourable for small molecular surfactants, whereas the living polymers are more favourable for the properties of high molecular weight polymers. The relative molecular weight of the high molecular surfactant is not high, generally less than 200 ten thousand, the tackifying property is not strong, the relative molecular weight of the active polymer is higher than 800 ten thousand, even more than 2000 ten thousand, the high viscosity and the strong tackifying property and the viscoelasticity are realized, meanwhile, the interfacial tension of an oil-water surface can be effectively reduced, and certain oil washing capacity is realized, and the effect of one agent for multiple purposes can be achieved, so that the acrylamide copolymer is used as a novel deep profile control agent and a profile control agent for oil fields, and has wider application prospect in middle and old oil fields in China, especially in the field of ultra-high water oil reservoirs.
The acrylamide copolymer is a high-viscosity polymer with better water solubility, and has quite different properties from the traditional profile control agent and the traditional plugging agent. On one hand, the acrylamide copolymer has the viscosity enhancement property of a water-soluble high-molecular polymer, can enter the deep part of an oil reservoir under certain pressure, and can perform deep profile control, so that the water phase permeability of a large pore canal is effectively reduced, and the characteristics of getting in and out, blocking and movable and the like can be realized; on the other hand, the introduction of the active functional monomer ensures that the novel acrylamide copolymer has the characteristics of good surface activity, emulsification capacity increase and the like, and reduces the interfacial tension of the oil water meter, thereby increasing the oil washing capacity of the active functional polymer at the deep part. In sum, the novel acrylamide copolymer oil displacement agent can obtain a multi-effect function, so that the recovery ratio of crude oil is improved. Therefore, the development of the acrylamide copolymer is an important way for realizing the deep profile control and the plugging control of the oil field, and simultaneously provides a measure for the creation and the enhancement of low-efficiency wells of low oil fields and a technical support for improving the productivity of the oil wells in the ultra-high water-cut period.
Disclosure of Invention
The invention aims to solve the problems that the traditional profile control agent and the profile control agent in the prior art cannot meet the profile control and profile control in the oil field with high water content and high well depth, and provides an acrylamide copolymer and a preparation method thereof, wherein the acrylamide copolymer has excellent surface-to-surface activity and high-temperature high-salt resistance.
In order to achieve the above object, the present invention provides an acrylamide copolymer, wherein the copolymer comprises a structural unit A, a structural unit B and a structural unit C, the structural unit A is a structural unit having the following formula (1), the structural unit B is a structural unit having the following formula (2), the structural unit C is a structural unit having the following formula (3),
wherein n=an integer of 40 to 55, and m is an integer of 0 to 6.
Preferably, the content of the structural unit A is 87 to 98% by weight, the content of the structural unit B is 0.3 to 6% by weight, and the content of the structural unit C is 1 to 7% by weight, based on the total weight of the copolymer.
More preferably, the content of the structural unit A is 90 to 95% by weight, the content of the structural unit B is 0.5 to 4% by weight, and the content of the structural unit C is 1.5 to 5.5% by weight, based on the total weight of the copolymer.
In a second aspect, the present invention provides a process for preparing an acrylamide copolymer, comprising the steps of:
(1) Preparing acrylamide into an aqueous solution, and adjusting the pH value of the aqueous solution by using alkali;
(2) Mixing and stirring the functional monomer X, the functional monomer Y, the emulsifying agent, the complexing agent, the urea and the accelerating agent with the product obtained in the step (1) to obtain a stable micelle solution;
(3) Uniformly mixing the micelle solution and a composite initiator at a first temperature in a nitrogen atmosphere, and performing seal polymerization to obtain polymer colloid;
(4) Granulating the polymer colloid, mixing with granulesten, and hydrolyzing at a second temperature to obtain polymer colloidal particles;
(5) Re-granulating, drying, crushing and screening the polymer colloidal particles to obtain the acrylamide copolymer;
the functional monomer X has a structure shown in a formula (4),
the functional monomer Y has a structure shown in a formula (5),
wherein n=an integer of 40 to 55, and m is an integer of 0 to 6.
Preferably, in step (1), the pH is adjusted such that the pH of the product obtained in step (1) is between 6 and 10, preferably between 6 and 8.
Preferably, in step (1), the base comprises sodium hydroxide and/or sodium carbonate.
Preferably, in the step (2), the emulsifier is sodium dodecyl sulfate, the complexing agent is EDTA-2Na aqueous solution, and the accelerator is 1, 5-diamino biuret.
Preferably, the emulsifier is used in an amount of 0.05 to 1% by weight, the complexing agent is used in an amount of 0.01 to 0.1% by weight, the urea is used in an amount of 0.5 to 5% by weight, and the accelerator is used in an amount of 0.2 to 1% by weight, based on the total weight of acrylamide, functional monomer X and functional monomer Y.
Preferably, the mass concentration of EDTA-2Na in the EDTA-2Na aqueous solution is 0.5-3%.
Preferably, in step (3), the composite initiator comprises an oxidizing agent and a reducing agent.
Preferably, the oxidizing agent is used in an amount of 0.01 to 0.1% by weight and the reducing agent is used in an amount of 0.005 to 0.05% by weight, based on the total weight of acrylamide, functional monomer X and functional monomer Y.
Preferably, the oxidant is persulfate and the reducing agent is sulfite.
Preferably, the total concentration of acrylamide, functional monomer X and functional monomer Y in the aqueous solution is 20-40%, preferably 25-35%.
Preferably, the content of the functional monomer X is 0.3 to 6 wt%, the content of the functional monomer Y is 1 to 7 wt%, and the content of the acrylamide is 87 to 98 wt%, based on the total weight of the acrylamide, the functional monomer X and the functional monomer Y.
More preferably, the content of the functional monomer X is 0.5 to 4% by weight, the amount of the functional monomer used is 1.5 to 5.5% by weight, and the content of the acrylamide is 90 to 95% by weight, based on the total weight of the acrylamide, the functional monomer X and the functional monomer Y.
Preferably, in the step (3), the first temperature is 20-40 ℃, and the sealing polymerization time is 8-10h.
Preferably, in the step (4), the second temperature is 80-90 ℃ and the hydrolysis time is 2-3h.
The third aspect of the invention provides an application of the acrylamide copolymer, wherein the acrylamide copolymer is the acrylamide copolymer disclosed by the invention or the acrylamide copolymer prepared by the method disclosed by any one of the invention.
Preferably, the application is at least one of an oilfield flooding agent, a plugging agent and an oil displacement agent.
By the technical scheme of the invention, the acrylamide copolymer provided by the invention can obtain the following
The beneficial effects are that:
according to the invention, the functional monomer X and the functional monomer Y are introduced into the macromolecular structure of the polyacrylamide, and meanwhile, the emulsifier and the accelerator are added into a polymerization system, so that stable micelles can be formed, and the polymerization activity of the two functional monomers can be obviously improved, and further, the molecular weight of a polymer product and the surface-interface activity of a copolymer aqueous solution are improved, so that the polymer has excellent tackifying and emulsified oil washing capabilities. In addition, the functional monomer X structural unit in the active functional copolymer molecular chain is introduced to enable a slight cross-linking structure to occur among the copolymer high molecular chains, so that the hydraulic volume among the copolymer molecular chains is enhanced, the copolymer aqueous solution still maintains high viscosity under the conditions of high temperature and high salt, and the purposes of deep profile control, flooding control and plugging control under an oil reservoir are further realized.
More importantly, the invention can also adjust the distribution of the copolymer structural units and the sequence structure thereof according to the geological conditions of the oil reservoirs and the properties of crude oil so as to meet the requirements of different oil reservoir conditions on deep profile control agents or profile control agents.
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 an acrylamide copolymer, wherein the copolymer comprises a structural unit A, a structural unit B and a structural unit C, wherein the structural unit A is a structural unit having the following formula (1), the structural unit B is a structural unit having the following formula (2), the structural unit C is a structural unit having the following formula (3),
wherein n=an integer of 40 to 55, and m is an integer of 0 to 6.
In the invention, the acrylamide and the specific functional monomer are copolymerized in a copolymerization mode, so that the copolymer not only has the tackifying property of a common water-soluble polymer, but also has excellent temperature resistance, salt resistance and surface interface activity.
In the invention, the acrylamide copolymer comprises a structural unit A, a structural unit B and a structural unit C, wherein the introduction of the structural unit B enables a slight cross-linking structure to occur among polymer high molecular chains, enhances the hydrodynamic volume among the polymer molecular chains, ensures that the polymer aqueous solution still maintains high viscosity under the conditions of high temperature and high salt, and further realizes the purposes of deep profile control, displacement control and profile control under an oil reservoir.
The introduction of the structural unit C enables a certain association between the molecular chains of the copolymer to increase the hydrodynamic volume of the copolymer, thereby increasing the viscosity of the polymer under high temperature and high salt.
In order to enable the acrylamide copolymer to have proper viscosity and low surface interfacial tension, the inventor researches the content of each structural unit in the polymer, and discovers that when the content of the structural unit A is 87-98 wt% and the content of the structural unit B is 0.3-6 wt% and the content of the structural unit C is 1-7 wt% based on the total weight of the copolymer, the copolymer still maintains higher viscosity under the conditions of high temperature and high salt, and the copolymer has low surface interfacial tension, so that the purposes of deep profile control and plugging under an oil reservoir are realized.
Preferably, the content of the structural unit A is 90 to 95% by weight, the content of the structural unit B is 0.5 to 4% by weight, and the content of the structural unit C is 1.5 to 5.5% by weight, based on the total weight of the copolymer.
In a second aspect, the present invention provides a process for preparing an acrylamide copolymer, comprising the steps of:
(1) Preparing acrylamide into an aqueous solution, and adjusting the pH value of the aqueous solution by using alkali;
(2) Mixing and stirring the functional monomer X, the functional monomer Y, the emulsifying agent, the complexing agent, the urea and the accelerating agent with the product obtained in the step (1) to obtain a stable micelle solution;
(3) Uniformly mixing the micelle solution and a composite initiator at a first temperature in a nitrogen atmosphere, and performing seal polymerization to obtain polymer colloid;
(4) Granulating the polymer colloid, mixing with granulesten, and hydrolyzing at a second temperature to obtain polymer colloidal particles;
(5) Re-granulating, drying, crushing and screening the polymer colloidal particles to obtain the acrylamide copolymer;
the functional monomer X has a structure shown in a formula (4),
the functional monomer Y has a structure shown in a formula (5),
wherein n=an integer of 40 to 55, and m is an integer of 0 to 6.
In the invention, the acrylamide and the specific functional monomer are copolymerized in a copolymerization mode, so that the copolymer not only has the tackifying property of a common water-soluble polymer, but also has excellent temperature resistance, salt resistance and surface interface activity.
In the invention, the acrylamide copolymer is prepared by copolymerizing an acrylamide monomer with functional monomers X and Y. Specifically, the introduction of the functional monomer X leads to a slight cross-linking structure among polymer high molecular chains, enhances the hydrodynamic volume among polymer molecular chains, ensures that the polymer aqueous solution still maintains very high viscosity under the conditions of high temperature and high salt, and further realizes the purposes of deep profile control, flooding and plugging control under an oil reservoir. The introduction of the functional monomer Y enables a certain association between polymer molecular chains, increases the hydrodynamic volume of the polymer molecular chains, and further increases the viscosity of the polymer under high temperature and high salt.
According to the invention, in step (1), the pH is adjusted so that the pH of the product obtained in step (1) is 6-10, preferably 6-8.
According to the invention, in step (1), the base comprises sodium hydroxide and/or sodium carbonate.
According to the invention, in the step (2), the emulsifier is sodium dodecyl sulfate, the complexing agent is EDTA-2Na aqueous solution, and the accelerator is 1, 5-diamino biuret.
According to the invention, the emulsifier is used in an amount of 0.05 to 1% by weight, the complexing agent is used in an amount of 0.01 to 0.1% by weight, the urea is used in an amount of 0.5 to 5% by weight, and the accelerator is used in an amount of 0.2 to 1% by weight, based on the total weight of acrylamide, functional monomer X and functional monomer Y.
According to the invention, the mass concentration of EDTA-2Na in the EDTA-2Na aqueous solution is 0.5-3%.
According to the invention, in step (3), the complex initiator comprises an oxidizing agent and a reducing agent.
Preferably, the oxidant is persulfate and the reducing agent is sulfite.
In the present invention, preferably, the persulfate and sulfite are present in the form of an aqueous solution, and further preferably, the persulfate is an aqueous potassium persulfate solution and/or an aqueous ammonium persulfate solution having a mass concentration of 0.1 to 0.5%; the sulfite is potassium hydrogen sulfite aqueous solution and/or sodium hydrogen sulfite aqueous solution with mass concentration of 0.05-0.3%.
In the invention, the promoter 1, 5-diamino biuret and auxiliary agents such as a composite initiator are matched with each other, so that the reactivity between the functional monomer and the acrylamide monomer is obviously improved, the functional monomer can be effectively introduced into the molecular chain of the acrylamide polymer, and the prepared acrylamide copolymer has excellent surface interface activity and high-temperature and high-salt resistance.
In the invention, the inventor finds through a great deal of experimental research that the active polymer with excellent cohesiveness, temperature resistance, salt resistance and surface interface activity can be prepared by adopting the amount of the emulsifier, the complexing agent, the urea, the accelerator, the oxidant and the reducing agent.
In the step (4), the granulin is sodium hydroxide granulin.
According to the invention, the total concentration of acrylamide, functional monomer X and functional monomer Y in the aqueous solution is 20-40%, preferably 25-35%.
Furthermore, the inventor researches the respective dosage of the acrylamide, the functional monomer X and the functional monomer Y, and researches that when the content of the functional monomer X is 0.3 to 6 weight percent, the content of the functional monomer Y is 1 to 7 weight percent and the content of the acrylamide is 87 to 98 weight percent based on the total weight of the acrylamide, the functional monomer X and the functional monomer Y, the prepared active polymer has excellent cohesiveness, temperature resistance, salt resistance and surface interface activity, and can meet the requirements of deep profile control agents and/or plugging agents under different oil reservoir conditions.
Still more preferably, the content of the functional monomer X is 0.5 to 4% by weight, the content of the functional monomer is 1.5 to 5.5% by weight, and the content of the acrylamide is 90 to 95% by weight, based on the total weight of the acrylamide, the functional monomer X and the functional monomer Y.
According to the invention, in the step (3), the first temperature is 20-40 ℃, and the sealing polymerization time is 8-10h.
According to the invention, in the step (4), the second temperature is 80-90 ℃ and the hydrolysis time is 2-3h.
The third aspect of the invention provides an application of the acrylamide copolymer, wherein the acrylamide copolymer is the acrylamide copolymer disclosed by the invention or the acrylamide copolymer prepared by the method disclosed by any one of the invention.
According to the invention, the application is at least one of an oil field oil displacement agent, a plugging agent and an oil displacement agent.
The present invention will be described in detail by examples. In the following examples, apparent viscosity of the polymer was measured using a Brookfield viscometer, specifically, at a specified test temperature (85 ℃ C.), apparent viscosity of a polymer solution (mass concentration: 1500 mg/L) at a mineralization degree of 33000mg/L was measured, and the higher the apparent viscosity, the more excellent the temperature resistance and salt resistance were shown;
the surface tension of the aqueous solution of the polymer is measured by a DCAT-21 surface tension meter, specifically, the surface tension of the aqueous solution of the polymer under pure water is measured at a specified test temperature (25 ℃), and the smaller the surface tension is, the more excellent the surface activity is;
the interfacial tension of the polymer solution was measured using a TX500C interfacial tension meter from keno, usa, specifically, the interfacial tension of the polymer solution at a specified test temperature (80 ℃) was measured, and the experimental solution was kerosene, the smaller the interfacial tension, the more excellent the interfacial activity.
The following examples and comparative examples were prepared from the following raw materials:
acrylamide was purchased from Shandong Bao Mohs Biochemical Co., ltd;
functional monomer X was purchased from belvedere chemical company, inc, where n=42;
the structure of the functional monomer Y1 is shown in formula 5, wherein m=0, purchased from the company of the chemical reagent of carbofuran;
the structure of functional monomer Y2 is shown in formula 5, wherein m=1, purchased from the company of the chemical reagent of carbofuran;
the structure of functional monomer Y3 is shown in formula 5, wherein m=6, purchased from the company of belvedere chemical reagent;
the other raw materials are all commercially available.
Example 1
1. Adding 34.8g of acrylamide (the mass content is 87%) into a thermal insulation polymerization reaction bottle (namely a polymerization bottle), adding 120.0g of deionized water to dissolve and prepare an aqueous solution, and adding sodium hydroxide to regulate the pH to 7.2;
2. 2.4g of functional monomer X (mass content 6%), 2.8g of functional monomer Y1 (mass content 7%), 0.35g of emulsifier, 3.0g of 1% EDTA-2Na aqueous solution, 2.0g of urea and 350.0mg of 1, 5-diamino biuret are added in sequence and fully stirred into stable micelle;
3. controlling the temperature of the aqueous solution at 20 ℃, introducing nitrogen to drive oxygen for 30 minutes, then adding 2.0g of 0.2% potassium persulfate aqueous solution and 2.0g of 0.1% sodium bisulfate aqueous solution, initiating reaction, continuing introducing nitrogen for five minutes, stopping, sealing, and performing polymerization reaction for 9 hours;
4. taking out the gel block, granulating, adding 0.85g of granular alkali, uniformly mixing, and hydrolyzing at 85 ℃ for 2.5 hours;
5. taking out the colloidal particles, granulating, drying at 60 ℃ to constant weight, crushing and sieving to obtain a white granular acrylamide copolymer sample.
The apparent viscosity was 70.5 mPas, the surface tension was 29.8mN/m, and the interfacial tension was 8.4X10 -2 mN/m, exhibits excellent surface-interfacial activity and high-temperature and high-salt resistance.
Example 2
1. Adding 39.2g of acrylamide (the mass content is 98%) into a thermal insulation polymerization reaction bottle (namely a polymerization bottle), adding 120.0g of deionized water to dissolve and prepare an aqueous solution, and adding sodium hydroxide to adjust the pH to 6.0;
2. sequentially adding 0.12g of functional monomer X (mass content is 0.3%), 0.68g of functional monomer Y2 (mass content is 1.7%), 0.4g of emulsifier, 0.4g of 1% EDTA-2Na aqueous solution, 0.2g of urea and 250.0mg of 1, 5-diamino biuret, and fully stirring to form stable micelle;
3. controlling the temperature of the aqueous solution at 30 ℃, introducing nitrogen to drive oxygen for 30 minutes, then adding 8.0g of 0.2% potassium persulfate aqueous solution and 8.0g of 0.1% sodium bisulfate aqueous solution, initiating reaction, continuing introducing nitrogen for five minutes, stopping, sealing, and performing polymerization reaction for 10 hours;
4. taking out the gel block, granulating, adding 0.88g of granular alkali, uniformly mixing, and hydrolyzing at 90 ℃ for 2 hours;
5. taking out the colloidal particles, granulating, drying at 60 ℃ to constant weight, crushing and sieving to obtain a white granular acrylamide copolymer sample.
The apparent viscosity was 75.5 mPas, the surface tension was 28.2mN/m, and the interfacial tension was 7.8X10 -2 mN/m, exhibits excellent surface-interfacial activity and high-temperature and high-salt resistance.
Example 3
1. Adding 38.0g of acrylamide (the mass content is 95%) into a thermal insulation polymerization reaction bottle (namely a polymerization bottle), adding 120.0g of deionized water to dissolve and prepare an aqueous solution, and adding sodium hydroxide to regulate the pH to 10.0;
2. sequentially adding 1.6g of functional monomer X (mass content is 4%), 0.4g of functional monomer Y3 (mass content is 1%), 0.4g of emulsifier, 2.0g of 1% EDTA-2Na aqueous solution, 2.0g of urea and 400.0mg of 1, 5-diamino biuret, and fully stirring to form stable micelle;
3. controlling the temperature of the aqueous solution at 27 ℃, introducing nitrogen to drive oxygen for 30 minutes, then adding 13.0g of 0.2% potassium persulfate aqueous solution and 13.0g of 0.1% sodium bisulfate aqueous solution, initiating the reaction, continuing introducing nitrogen for five minutes, stopping the reaction, sealing, and performing polymerization reaction for 10 hours;
4. taking out the gel block, granulating, adding 0.88g of granular alkali, uniformly mixing, and hydrolyzing at 80 ℃ for 3 hours;
5. taking out the colloidal particles, granulating, drying at 60 ℃ to constant weight, crushing and sieving to obtain a white granular acrylamide copolymer sample.
The apparent viscosity was 76.8 mPas, the surface tension was 29.4mN/m, and the interfacial tension was 7.1X10 -2 mN/m, exhibits excellent surface-interfacial activity and high-temperature and high-salt resistance.
Example 4
1. Adding 36.8g of acrylamide (the mass content is 92%) into a thermal insulation polymerization reaction bottle (namely a polymerization bottle), adding 120.0g of deionized water to dissolve and prepare an aqueous solution, and adding sodium hydroxide to regulate the pH to 7.5;
2. 1.4g of functional monomer X (mass content is 3.5%), 1.8g of functional monomer Y2 (mass content is 4.5%), 0.3g of emulsifier, 3.5g of 1% EDTA-2Na aqueous solution, 1.5g of urea and 80.0mg of 1, 5-diamino biuret are added in sequence and fully stirred into stable micelle;
3. controlling the temperature of the aqueous solution at 30 ℃, introducing nitrogen to drive oxygen for 30 minutes, then adding 20.0g of 0.2% potassium persulfate aqueous solution and 20.0g of 0.1% sodium bisulfate aqueous solution, initiating reaction, continuing introducing nitrogen for five minutes, stopping, sealing, and performing polymerization reaction for 8 hours;
4. taking out the gel block, granulating, adding 0.92g of granular alkali, uniformly mixing, and hydrolyzing at 85 ℃ for 2.0 hours;
5. taking out the colloidal particles, granulating, drying at 60 ℃ to constant weight, crushing and sieving to obtain a white granular acrylamide copolymer sample.
The apparent viscosity was 82.3 mPas, the surface tension was 27.8mN/m and the interfacial tension was 6.2X10 -2 mN/m, exhibits excellent surface-interfacial activity and high-temperature and high-salt resistance.
Comparative example 1
An acrylamide copolymer was prepared according to the method of example 1, except that: the functional monomer X is N, N-methylene bisacrylamide, and the functional monomer Y is maleimide. The apparent viscosity was 34.6 mPas, the surface tension was 51.8mN/m and the interfacial tension was 13.1mN/m. The apparent viscosity of the polymer is obviously reduced, which indicates that the high temperature resistance and the salt resistance of the acrylamide functional polymer are poor, and the surface tension and the interfacial tension are both increased, which indicates that the surface-interfacial activity of the acrylamide functional polymer is poor.
Comparative example 2
An acrylamide copolymer was prepared according to the method of example 2, except that: the amount of the functional monomer X was 3.2g (mass content: 8%), and the amount of the functional monomer Y was 0.2g (mass content: 0.5%).
The apparent viscosity was 36.7 mPas, the surface tension was 36.8mN/m and the interfacial tension was 4.5X10 -1 mN/m. The apparent viscosity of the polymer is obviously reduced, which indicates that the high temperature resistance and the salt resistance of the acrylamide functional polymer are poor, and the surface tension and the interfacial tension are both increased, which indicates that the surface-interfacial activity of the acrylamide functional polymer is poor.
Comparative example 3
An acrylamide copolymer was prepared according to the method of example 4, except that: the apparent viscosity was 30.2 mPas, the surface tension was 41.5mN/m and the interfacial tension was 2.6mN/m as tested without adding the functional monomer Y. The apparent viscosity of the polymer is obviously reduced, which indicates that the high temperature resistance and the salt resistance of the acrylamide functional polymer are poor, and the surface tension and the interfacial tension are both increased, which indicates that the surface-interfacial activity of the acrylamide functional polymer is poor.
Comparative example 4
An acrylamide copolymer was prepared according to the method of example 3, except that: no accelerator was added. The apparent viscosity was tested to be 32.6 mPas, the surface tension was 43.1mN/m and the interfacial tension was 10.9mN/m. The apparent viscosity of the polymer is obviously reduced, which indicates that the high temperature resistance and the salt resistance of the acrylamide functional polymer are poor, and the surface tension and the interfacial tension are both increased, which indicates that the surface-interfacial activity of the acrylamide functional polymer is poor.
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 (23)
1. An acrylamide copolymer, wherein the copolymer comprises a structural unit A, a structural unit B and a structural unit C, wherein the structural unit A is a structural unit shown in the following formula (1), the structural unit B is a structural unit shown in the following formula (2), the structural unit C is a structural unit shown in the following formula (3),
Wherein n=an integer of 40 to 55, and m is an integer of 0 to 6;
the content of the structural unit A is 87-98 wt%, the content of the structural unit B is 0.3-6 wt% and the content of the structural unit C is 1-7 wt% based on the total weight of the copolymer;
the preparation method of the acrylamide copolymer comprises the following steps:
(1) Preparing acrylamide into an aqueous solution, and adjusting the pH value of the aqueous solution by using alkali;
(2) Mixing and stirring the functional monomer X, the functional monomer Y, the emulsifying agent, the complexing agent, the urea and the accelerating agent with the product obtained in the step (1) to obtain a stable micelle solution;
(3) Uniformly mixing the micelle solution and a composite initiator at a first temperature in a nitrogen atmosphere, and performing seal polymerization to obtain polymer colloid;
(4) Granulating the polymer colloid, mixing with granulesten, and hydrolyzing at a second temperature to obtain polymer colloidal particles;
(5) Re-granulating, drying, crushing and screening the polymer colloidal particles to obtain the acrylamide copolymer;
the functional monomer X has a structure shown in a formula (4),
The functional monomer Y has a structure shown in a formula (5),
Wherein n=an integer of 40 to 55, and m is an integer of 0 to 6.
2. The acrylamide copolymer according to claim 1, wherein the content of structural unit a is 90-95 wt%, the content of structural unit B is 0.5-4 wt% and the content of structural unit C is 1.5-5.5 wt%, based on the total weight of the copolymer.
3. A process for preparing the acrylamide copolymer of claim 1, comprising the steps of:
(1) Preparing acrylamide into an aqueous solution, and adjusting the pH value of the aqueous solution by using alkali;
(2) Mixing and stirring the functional monomer X, the functional monomer Y, the emulsifying agent, the complexing agent, the urea and the accelerating agent with the product obtained in the step (1) to obtain a stable micelle solution;
(3) Uniformly mixing the micelle solution and a composite initiator at a first temperature in a nitrogen atmosphere, and performing seal polymerization to obtain polymer colloid;
(4) Granulating the polymer colloid, mixing with granulesten, and hydrolyzing at a second temperature to obtain polymer colloidal particles;
(5) Re-granulating, drying, crushing and screening the polymer colloidal particles to obtain the acrylamide copolymer;
the functional monomer X has a structure shown in a formula (4),
The functional monomer Y has a structure shown in a formula (5),
Wherein n=an integer of 40 to 55, and m is an integer of 0 to 6.
4. A process according to claim 3, wherein in step (1) the pH is adjusted such that the pH of the product obtained in step (1) is between 6 and 10;
and/or, in step (1), the base comprises sodium hydroxide and/or sodium carbonate.
5. The method according to claim 4, wherein in the step (1), the pH value is adjusted so that the pH value of the product obtained in the step (1) is 6 to 8.
6. The method of any one of claims 3-5, wherein in step (2), the emulsifier is sodium dodecyl sulfate, the complexing agent is an aqueous EDTA-2Na solution, and the accelerator is 1, 5-diamino biuret;
and/or, based on the total weight of acrylamide, functional monomer X and functional monomer Y, the emulsifier is used in an amount of 0.05 to 1 wt%, the complexing agent is used in an amount of 0.01 to 0.1 wt%, the urea is used in an amount of 0.5 to 5 wt%, and the accelerator is used in an amount of 0.2 to 1 wt%.
7. The method according to claim 6, wherein the mass concentration of EDTA-2Na in the EDTA-2Na aqueous solution is 0.5-3%.
8. The method of any one of claims 3-5 or 7, wherein in step (3), the composite initiator comprises an oxidizing agent and a reducing agent.
9. The method according to claim 8, wherein the oxidizing agent is used in an amount of 0.01 to 0.1 wt% and the reducing agent is used in an amount of 0.005 to 0.05 wt% based on the total weight of acrylamide, functional monomer X and functional monomer Y;
and/or the oxidant is persulfate, and the reducing agent is sulfite.
10. The method of claim 6, wherein in step (3), the composite initiator comprises an oxidizing agent and a reducing agent.
11. The process according to claim 10, wherein the oxidizing agent is used in an amount of 0.01 to 0.1% by weight and the reducing agent is used in an amount of 0.005 to 0.05% by weight, based on the total weight of acrylamide, functional monomer X and functional monomer Y;
and/or the oxidant is persulfate, and the reducing agent is sulfite.
12. The method according to any one of claims 3-5, 7 or 9-11, wherein the total weight concentration of acrylamide, functional monomer X and functional monomer Y in the aqueous solution is 20-40%;
and/or, based on the total weight of the acrylamide, the functional monomer X and the functional monomer Y, the content of the functional monomer X is 0.3-6 wt%, the content of the functional monomer Y is 1-7 wt%, and the content of the acrylamide is 87-98 wt%.
13. The method of claim 12, wherein the total weight concentration of acrylamide, functional monomer X and functional monomer Y in the aqueous solution is 25-35%;
and/or, the content of the functional monomer X is 0.5-4 wt% based on the total weight of the acrylamide, the functional monomer X and the functional monomer Y, the content of the functional monomer Y is 1.5-5.5 wt%, and the content of the acrylamide is 90-95 wt%.
14. The method according to claim 6, wherein the total weight concentration of acrylamide, functional monomer X and functional monomer Y in the aqueous solution is 20-40%;
and/or, based on the total weight of the acrylamide, the functional monomer X and the functional monomer Y, the content of the functional monomer X is 0.3-6 wt%, the content of the functional monomer Y is 1-7 wt%, and the content of the acrylamide is 87-98 wt%.
15. The method of claim 14, wherein the total weight concentration of acrylamide, functional monomer X and functional monomer Y in the aqueous solution is 25-35%;
and/or, the content of the functional monomer X is 0.5-4 wt% based on the total weight of the acrylamide, the functional monomer X and the functional monomer Y, the content of the functional monomer Y is 1.5-5.5 wt%, and the content of the acrylamide is 90-95 wt%.
16. The method of claim 8, wherein the total weight concentration of acrylamide, functional monomer X and functional monomer Y in the aqueous solution is 20-40%;
and/or, based on the total weight of the acrylamide, the functional monomer X and the functional monomer Y, the content of the functional monomer X is 0.3-6 wt%, the content of the functional monomer Y is 1-7 wt%, and the content of the acrylamide is 87-98 wt%.
17. The method of claim 16, wherein the total weight concentration of acrylamide, functional monomer X and functional monomer Y in the aqueous solution is 25-35%;
and/or, the content of the functional monomer X is 0.5-4 wt% based on the total weight of the acrylamide, the functional monomer X and the functional monomer Y, the content of the functional monomer Y is 1.5-5.5 wt%, and the content of the acrylamide is 90-95 wt%.
18. The process of any one of claims 3-5, 7, 9-11, or 13-17, wherein in step (3), the first temperature is 20-40 ℃, and the seal polymerization time is 8-10 hours;
in the step (4), the second temperature is 80-90 ℃ and the hydrolysis time is 2-3h.
19. The method of claim 6, wherein in step (3), the first temperature is 20-40 ℃ and the seal polymerization time is 8-10 hours;
in the step (4), the second temperature is 80-90 ℃ and the hydrolysis time is 2-3h.
20. The method of claim 8, wherein in step (3), the first temperature is 20-40 ℃ and the seal polymerization time is 8-10 hours;
in the step (4), the second temperature is 80-90 ℃ and the hydrolysis time is 2-3h.
21. The method of claim 12, wherein in step (3), the first temperature is 20-40 ℃ and the seal polymerization time is 8-10 hours;
in the step (4), the second temperature is 80-90 ℃ and the hydrolysis time is 2-3h.
22. Use of an acrylamide copolymer according to claim 1 or 2 or obtainable by a process according to any one of claims 3 to 21.
23. The use of claim 22, wherein the use is at least one of an oilfield flooding agent, a plugging agent, and an oil displacement agent.
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