CN112126018A - 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 and a preparation method and application thereof. The copolymer of the 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 a formula (1), the structural unit B is a structural unit shown in a formula (2), the structural unit C is a structural unit shown in a 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, along with the continuous increase of water content of the oil field, the water plugging technology of the oil field enters a new development stage, the variety of plugging agents is rapidly increased, the number of treatment wells is increased, and the economic effect is also obviously improved. The water injection development mode is generally adopted in oil fields in China, the stratum heterogeneity is severe, the oil reservoir geology is complex, the water content rising speed is accelerated in the middle and later development periods, and the heterogeneity of a water injection section is further increased along with the increase of water injection quantity, so that a large amount of water is discharged from an oil well.
At present, the average water content of an oil well reaches more than 80 percent, and the water content of some old oil fields in eastern areas reaches more than 95 percent. Therefore, the workload of water shutoff and profile control is increased year by year, the work difficulty is continuously increased, the oil increasing potential is reduced, the situation promotes the continuous development of the profile control and water shutoff technology, a new hot point of the deep profile control technology research is formed, the important function is played in the aspects of oil and water stabilization and control, and novel chemical agents such as strong gel, weak gel, particle gel and the like are correspondingly developed. However, in the case of the extremely high water content stage, the chemical agents cannot achieve the purpose of deep profile control and flooding due to serious flooding of an oil well, complex oil-water relationship and the like, and can only act in a near-distance zone of the implemented well, so that the field implementation period is short and the effect is poor.
The aqueous solution copolymerization of the 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, etc. The polyacrylamide and its derivative are both homopolymer or copolymer with polyacrylamide as main chain. The polymerization process can be divided into the following according to the dispersion state of the monomers in the medium: aqueous solution polymerization, micelle polymerization, and emulsion polymerization.
Acrylamide copolymer refers to a new type of polymer with both hydrophilic group and lipophilic group in its polymer structure, so that its aqueous solution has good surface activity and characteristics of emulsified washing oil, etc. it generally adopts aqueous solution copolymerization or micelle copolymerization process, i.e. after initiating the polymerization of comonomer under the action of initiator and under a certain temperature, the acrylamide copolymer can be obtained by colloid post-treatment.
Acrylamide copolymers are very different from conventional polymeric surfactants. The properties of high molecular surfactants are more favorable than those of small molecular surfactants, and the active polymers are more favorable than those of high molecular weight polymers. The high molecular surfactant has low relative molecular weight (less than 200 ten thousand, low viscosity increasing effect, high viscoelasticity, certain oil and water surface interface tension reducing effect, and wide application foreground in middle and middle aged oil field, especially high water content oil deposit.
The acrylamide copolymer is a high-viscosity polymer with better water solubility, and has quite different properties with the traditional profile control agent and profile control agent. On one hand, the acrylamide copolymer has water-soluble high-molecular polymer tackifying property, can enter the deep part of an oil reservoir under certain pressure to perform deep profile control, effectively reduces the water phase permeability of a large pore passage, and can realize the characteristics of getting, blocking, transporting and the like; on the other hand, the introduction of the active functional monomer enables the novel acrylamide copolymer to have the characteristics of good surface activity, emulsification, compatibilization 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 a deep part. In general, the novel acrylamide copolymer oil displacement agent can achieve the function of multiple effects, so that the recovery rate of crude oil is improved. Therefore, the development of the acrylamide copolymer is an important way for realizing deep profile control and flooding and plugging control of the oil field, and meanwhile, measures are provided for creating and increasing the low-efficiency well of the low oil field, and technical support is provided for improving the productivity of the oil well in the ultra-high water-cut period.
Disclosure of Invention
The invention aims to solve the problem that the traditional profile control agent and profile control plugging agent in the prior art cannot meet the requirements of profile control, flooding and plugging control in an oil field with high water content and high well depth, and provides an acrylamide copolymer and a preparation method thereof.
In order to achieve the above object, a first aspect of the present invention provides an acrylamide copolymer comprising a structural unit a represented by the following formula (1), a structural unit B represented by the following formula (2), and a structural unit C represented by the following formula (3),
wherein n is an integer of 40-55, and m is an integer of 0-6.
Preferably, 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.
More preferably, the content of the structural unit A is 90 to 95 wt%, the content of the structural unit B is 0.5 to 4 wt%, and the content of the structural unit C is 1.5 to 5.5 wt%, based on the total weight of the copolymer.
The second aspect of the present invention provides a method 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 a functional monomer X, a functional monomer Y, an emulsifier, a complexing agent, urea, an accelerant and 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 carrying out sealing polymerization to obtain a polymer colloid;
(4) granulating the polymer colloid, mixing the polymer colloid with granular alkali, 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 is an integer of 40-55, and m is an integer of 0-6.
Preferably, in step (1), the pH is adjusted so that the product obtained in step (1) has a pH of 6 to 10, preferably 6 to 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 an aqueous EDTA-2Na solution, and the accelerator is 1, 5-diaminobiuret.
Preferably, 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%, based on the total weight of the acrylamide, the functional monomer X, and the 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 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.
Preferably, the oxidizing agent is a persulfate and the reducing agent is a sulfite.
Preferably, the total weight concentration of the acrylamide, the functional monomer X and the functional monomer Y in the aqueous solution is 20 to 40%, preferably 25 to 35%.
Preferably, the content of the functional monomer X is 0.3 to 6% by weight, the content of the functional monomer Y is 1 to 7% by weight, and the content of acrylamide is 87 to 98% by weight, based on the total weight of acrylamide, functional monomer X and functional monomer Y.
More preferably, the content of the functional monomer X is 0.5 to 4% by weight, the functional monomer is used in an amount of 1.5 to 5.5% by weight, and the content of acrylamide is 90 to 95% by weight, based on the total weight of acrylamide, functional monomer X and functional monomer Y.
Preferably, in the step (3), the first temperature is 20-40 ℃ and the sealing polymerization time is 8-10 h.
Preferably, in the step (4), the second temperature is 80-90 ℃, and the hydrolysis time is 2-3 h.
The third aspect of the present invention provides a use of an acrylamide copolymer, wherein the acrylamide copolymer is the acrylamide copolymer according to the present invention or the acrylamide copolymer obtained by the method according to any one of the present invention.
Preferably, the application is at least one of a profile control agent, a plugging agent and an oil displacement agent for oil fields.
By the technical scheme of the invention, the acrylamide copolymer provided by the invention has the following advantages
Has the advantages that:
the functional monomer X and the functional monomer Y are introduced into the macromolecular structure of polyacrylamide, and the emulsifier and the accelerant are added into a polymerization system, so that on one hand, a stable micelle can be formed, on the other hand, the polymerization activity of the two functional monomers can be obviously improved, and further, the molecular weight of a polymer product and the surface activity of a copolymer aqueous solution are improved, and the polymer product has excellent tackifying and emulsifying oil washing capabilities. In addition, due to the introduction of a functional monomer X structural unit in an active functional copolymer molecular chain, a slight cross-linking structure is generated among copolymer high molecular chains, so that the hydraulic volume among the copolymer molecular chains is enhanced, the copolymer aqueous solution still keeps high viscosity under the conditions of high temperature and high salt, and the purposes of deep profile control and plugging control under an oil reservoir are further realized.
More importantly, the invention can also adjust the distribution and the sequence structure of the copolymer structural unit according to the geological conditions of the oil reservoir and the properties of crude oil so as to meet the requirements of different oil reservoir conditions on a deep profile control agent or a profile plugging agent.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The first aspect of the present invention provides an acrylamide copolymer comprising a structural unit a represented by the following formula (1), a structural unit B represented by the following formula (2), and a structural unit C represented by the following formula (3),
wherein n is an integer of 40-55, and m is an integer of 0-6.
In the invention, acrylamide and a specific functional monomer are copolymerized in a copolymerization mode, so that the copolymer not only has the tackifying property of common water-soluble polymers, but also has excellent temperature resistance, salt resistance and surface activity.
According to 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, the hydraulic volume among the polymer molecular chains is enhanced, and the polymer aqueous solution still keeps high viscosity under the conditions of high temperature and high salt, so that the purposes of deep profile control and plugging control under an oil reservoir are realized.
The introduction of the structural unit C enables the molecular chains of the copolymer to have a certain association effect, increases the hydraulic volume of the copolymer, and further increases the viscosity of the polymer at 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 through the research, when 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 copolymer still maintains higher viscosity under high-temperature and high-salt conditions, and the copolymer has low surface interfacial tension, so that the purposes of deep profile control and blockage control under oil reservoirs are achieved.
Preferably, the content of the structural unit A is 90 to 95 wt%, the content of the structural unit B is 0.5 to 4 wt%, and the content of the structural unit C is 1.5 to 5.5 wt%, based on the total weight of the copolymer.
The second aspect of the present invention provides a method 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 a functional monomer X, a functional monomer Y, an emulsifier, a complexing agent, urea, an accelerant and 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 carrying out sealing polymerization to obtain a polymer colloid;
(4) granulating the polymer colloid, mixing the polymer colloid with granular alkali, 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 is an integer of 40-55, and m is an integer of 0-6.
In the invention, acrylamide and a specific functional monomer are copolymerized in a copolymerization mode, so that the copolymer not only has the tackifying property of common water-soluble polymers, but also has excellent temperature resistance, salt resistance and surface activity.
In the invention, the acrylamide copolymer is prepared by copolymerizing an acrylamide monomer and functional monomers X and Y. Specifically, the introduction of the functional monomer X enables polymer high molecular chains to generate a slight cross-linking structure, the hydraulic volume among the polymer molecular chains is enhanced, the polymer aqueous solution still keeps high viscosity under the conditions of high temperature and high salt, and the purposes of deep profile control and plugging control under an oil reservoir are further achieved. The introduction of the functional monomer Y enables polymer molecular chains to have a certain association effect, increases the hydraulic volume of the polymer, and further increases the viscosity of the polymer at high temperature and high salt.
According to the invention, in step (1), the pH is adjusted so that the product obtained in step (1) has a pH of 6 to 10, preferably 6 to 8.
According to the invention, in step (1), the base comprises sodium hydroxide and/or sodium carbonate.
According to the invention, in step (2), the emulsifier is sodium dodecyl sulfate, the complexing agent is an aqueous EDTA-2Na solution, and the accelerator is 1, 5-diaminobiuret.
According to the invention, the emulsifier is used in an amount of 0.05 to 1 wt.%, the complexing agent in an amount of 0.01 to 0.1 wt.%, the urea in an amount of 0.5 to 5 wt.%, and the accelerator in an amount of 0.2 to 1 wt.%, 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 present invention, in the step (3), the composite initiator comprises an oxidizing agent and a reducing agent.
Preferably, the oxidizing agent is a persulfate and the reducing agent is a sulfite.
In the invention, preferably, the persulfate and the sulfite exist in the form of an aqueous solution, and further preferably, the persulfate is a potassium persulfate aqueous solution and/or an ammonium persulfate aqueous solution with a mass concentration of 0.1-0.5%; the sulfite is a potassium bisulfite aqueous solution and/or a sodium bisulfite aqueous solution with the mass concentration of 0.05-0.3%.
In the invention, the accelerator 1, 5-diamino biuret is matched with auxiliary agents such as a composite initiator and the like, so that the reaction activity between a functional monomer and an acrylamide monomer is obviously improved, the functional monomer can be effectively introduced into a molecular chain of an acrylamide polymer, and the prepared acrylamide copolymer has excellent surface activity and high temperature and high salt resistance.
In the invention, through a large number of experimental researches, the inventor discovers that the active polymer with excellent cohesiveness, temperature resistance, salt resistance and surface activity can be prepared by using the emulsifier, the complexing agent, the urea, the accelerator, the oxidant and the reducing agent in the amount of the invention.
In the invention, in the step (4), the granular alkali is sodium hydroxide granular alkali.
According to the invention, the total concentration by weight of acrylamide, functional monomer X and functional monomer Y in the aqueous solution is between 20 and 40%, preferably between 25 and 35%.
Furthermore, the inventor researches the respective amounts of acrylamide, functional monomer X and functional monomer Y, and finds that when the total weight of acrylamide, functional monomer X and functional monomer Y is taken as a reference, the content of functional monomer X is 0.3-6 wt%, the content of functional monomer Y is 1-7 wt%, and the content of acrylamide is 87-98 wt%, the prepared active polymer has excellent cohesiveness, temperature resistance, salt resistance and surface activity, and can meet the requirements of deep profile control agents and/or profile control agents under different oil reservoir conditions.
Still more preferably, the content of the functional monomer X is 0.5 to 4% by weight, the functional monomer is used in an amount of 1.5 to 5.5% by weight, and the content of acrylamide is 90 to 95% by weight, based on the total weight of acrylamide, functional monomer X and functional monomer Y.
According to the invention, in the step (3), the first temperature is 20-40 ℃, and the sealing polymerization time is 8-10 h.
According to the invention, in the step (4), the second temperature is 80-90 ℃, and the hydrolysis time is 2-3 h.
The third aspect of the present invention provides a use of an acrylamide copolymer, wherein the acrylamide copolymer is the acrylamide copolymer according to the present invention or the acrylamide copolymer obtained by the method according to any one of the present invention.
According to the invention, the application is at least one of oil field profile control and flooding agent, profile control and plugging agent and oil displacement agent.
The present invention will be described in detail below by way of examples. In the following examples, the apparent viscosity of the polymer was measured with a Brookfield viscometer, specifically, at a specified test temperature (85 ℃), the apparent viscosity of a polymer solution (with a mass concentration of 1500mg/L) at a mineralization degree of 33000mg/L was measured, and the greater the apparent viscosity, the more excellent the heat and salt resistance;
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 in 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 is measured by an interfacial tension meter TX500C, namely, the interfacial tension of the polymer solution is measured at a specified test temperature (80 ℃), and the lower the interfacial tension is, the better the interfacial activity is.
The following examples and comparative examples used the starting materials:
acrylamide was purchased from bio-chemical industries, ltd, Shandong Baomo;
functional monomer X is available from carbofuran chemicals, ltd, where n is 42;
the structure of the functional monomer Y1 is shown in formula 5, wherein m is 0 and is purchased from Bailingwei chemical reagent company Limited;
the structure of the functional monomer Y2 is shown in formula 5, wherein m is 1 and is purchased from carbofuran chemical reagent company Limited;
the structure of the functional monomer Y3 is shown in formula 5, wherein m is 6, and the functional monomer is purchased from carbofuran chemical reagent company Limited;
all other raw materials are commercially available.
Example 1
1. Adding 34.8g of acrylamide (mass content is 87%) into a heat-preservation polymerization reaction bottle (namely a polymerization bottle), adding 120.0g of deionized water, dissolving to prepare an aqueous solution, and adding sodium hydroxide to adjust the pH value to 7.2;
2. sequentially adding 2.4g of functional monomer X (mass content is 6%), 2.8g of functional monomer Y1 (mass content is 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, and fully stirring to obtain stable micelles;
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 bisulfite aqueous solution to initiate reaction, continuing introducing nitrogen for five minutes, stopping, and carrying out polymerization reaction for 9 hours after sealing;
4. taking out the rubber block, adding 0.85g of granular alkali after granulation, 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 white granular acrylamide copolymer samples.
The apparent viscosity was 70.5 mPas, the surface tension was 29.8mN/m, and the interfacial tension was 8.4X 10-2mN/m, and the nano-composite material shows excellent surface activity and high temperature and high salt resistance.
Example 2
1. Adding 39.2g of acrylamide (with the mass content of 98%) into a heat-preservation polymerization reaction bottle (namely a polymerization bottle), adding 120.0g of deionized water, dissolving to prepare an aqueous solution, and adding sodium hydroxide to adjust the pH value to 6.0;
2. 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 are added in sequence and fully stirred to form stable micelles;
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 bisulfite aqueous solution to initiate reaction, continuing introducing nitrogen for five minutes, stopping, and carrying out polymerization reaction for 10 hours after sealing;
4. taking out the rubber block, adding 0.88g of granular alkali after granulation, uniformly mixing, and hydrolyzing for 2 hours at 90 ℃;
5. taking out the colloidal particles, granulating, drying at 60 ℃ to constant weight, crushing and sieving to obtain white granular acrylamide copolymer samples.
The apparent viscosity was 75.5 mPas, the surface tension was 28.2mN/m, and the interfacial tension was 7.8X 10-2mN/m, and the nano-composite material shows excellent surface activity and high temperature and high salt resistance.
Example 3
1. Adding 38.0g of acrylamide (the mass content of the acrylamide is 95%) into a heat-preservation polymerization reaction bottle (namely a polymerization bottle), adding 120.0g of deionized water, dissolving to prepare an aqueous solution, and adding sodium hydroxide to adjust the pH value to 10.0;
2. sequentially adding 1.6g of functional monomer X (the mass content is 4%), 0.4g of functional monomer Y3 (the 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 micelles;
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 bisulfite aqueous solution to initiate reaction, continuing introducing nitrogen for five minutes, stopping, and carrying out polymerization reaction for 10 hours after sealing;
4. taking out the rubber block, adding 0.88g of granular alkali after granulation, uniformly mixing, and hydrolyzing for 3 hours at 80 ℃;
5. taking out the colloidal particles, granulating, drying at 60 ℃ to constant weight, crushing and sieving to obtain white granular acrylamide copolymer samples.
The apparent viscosity was found to be 76.8 mPas, the surface tension was found to be 29.4mN/m, and the interfacial tension was found to be 7.1X 10-2mN/m, and the nano-composite material shows excellent surface activity and high temperature and high salt resistance.
Example 4
1. Adding 36.8g of acrylamide (with the mass content of 92%) into a heat-preservation polymerization reaction bottle (namely a polymerization bottle), adding 120.0g of deionized water, dissolving to prepare an aqueous solution, and adding sodium hydroxide to adjust the pH value to 7.5;
2. sequentially adding 1.4g of functional monomer X (the mass content is 3.5%), 1.8g of functional monomer Y2 (the 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, and fully stirring to obtain stable micelles;
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 bisulfite aqueous solution to initiate reaction, continuously introducing nitrogen for five minutes, stopping, and carrying out polymerization reaction for 8 hours after sealing;
4. taking out the rubber block, adding 0.92g of granular alkali after granulation, 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 white granular acrylamide copolymer samples.
The apparent viscosity is 82.3 mPas and the surface tension is 278mN/m, interfacial tension 6.2X 10-2mN/m, and the nano-composite material shows excellent surface 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 found to be 34.6 mPas, the surface tension was found to be 51.8mN/m, and the interfacial tension was found to be 13.1 mN/m. The apparent viscosity is remarkably reduced, which shows that the high temperature resistance and salt tolerance of the acrylamide functional polymer are poor, and the surface tension and the interfacial tension are increased, which shows 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 used was 3.2g (mass content: 8%), and the amount of the functional monomer Y used 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 4.5X 10-1mN/m. The apparent viscosity is remarkably reduced, which shows that the high temperature resistance and salt tolerance of the acrylamide functional polymer are poor, and the surface tension and the interfacial tension are increased, which shows 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: without adding the functional monomer Y, the apparent viscosity was 30.2 mPas, the surface tension was 41.5mN/m, and the interfacial tension was 2.6mN/m, as measured. The apparent viscosity is remarkably reduced, which shows that the high temperature resistance and salt tolerance of the acrylamide functional polymer are poor, and the surface tension and the interfacial tension are increased, which shows 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 found to be 32.6 mPas, the surface tension to be 43.1mN/m, and the interfacial tension to be 10.9 mN/m. The apparent viscosity is remarkably reduced, which shows that the high temperature resistance and salt tolerance of the acrylamide functional polymer are poor, and the surface tension and the interfacial tension are increased, which shows that the surface interfacial activity of the acrylamide functional polymer is poor.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. An acrylamide copolymer comprising a structural unit A, a structural unit B and a structural unit C, wherein the structural unit A is a structural unit represented by the following formula (1), the structural unit B is a structural unit represented by the following formula (2), and the structural unit C is a structural unit represented by the following formula (3),
wherein n is an integer of 40-55, and m is an integer of 0-6.
2. The acrylamide copolymer according to claim 1, wherein the content of the structural unit a is 87 to 98 wt%, the content of the structural unit B is 0.3 to 6 wt%, and the content of the structural unit C is 1 to 7 wt%, based on the total weight of the copolymer;
preferably, the content of the structural unit A is 90 to 95 wt%, the content of the structural unit B is 0.5 to 4 wt%, and the content of the structural unit C is 1.5 to 5.5 wt%, based on the total weight of the copolymer.
3. A process for preparing the acrylamide copolymer according to claim 1 or 2, 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 a functional monomer X, a functional monomer Y, an emulsifier, a complexing agent, urea, an accelerant and 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 carrying out sealing polymerization to obtain a polymer colloid;
(4) granulating the polymer colloid, mixing the polymer colloid with granular alkali, 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 is an integer of 40-55, and m is an integer of 0-6.
4. The process according to claim 3, wherein in step (1), the pH is adjusted so that the pH of the product obtained in step (1) is 6 to 10, preferably 6 to 8;
preferably, in step (1), the base comprises sodium hydroxide and/or sodium carbonate.
5. The method according to claim 3 or 4, wherein in step (2), the emulsifier is sodium lauryl sulfate, the complexing agent is an aqueous EDTA-2Na solution, and the accelerator is 1, 5-diaminobiuret;
preferably, 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%, based on the total weight of the acrylamide, the functional monomer X, and the functional monomer Y;
preferably, the mass concentration of EDTA-2Na in the EDTA-2Na aqueous solution is 0.5-3%.
6. The method according to any one of claims 3 to 5, wherein 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 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;
preferably, the oxidizing agent is a persulfate and the reducing agent is a sulfite.
7. The process according to any one of claims 3 to 6, wherein the total weight 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 0.3-6 wt%, the content of the functional monomer Y is 1-7 wt%, and the content of acrylamide is 87-98 wt%, based on the total weight of 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 functional monomer Y is used in an amount of 1.5 to 5.5% by weight, and the content of acrylamide is 90 to 95% by weight, based on the total weight of acrylamide, functional monomer X and functional monomer Y.
8. The method according to any one of claims 3 to 7, wherein in step (3), the first temperature is 20 to 40 ℃ and the seal polymerization time is 8 to 10 hours;
in the step (4), the second temperature is 80-90 ℃, and the hydrolysis time is 2-3 h.
9. Use of an acrylamide copolymer according to claim 1 or 2 or obtained by the method according to any one of claims 3 to 8.
10. The use of claim 9, wherein the use is at least one of an oil field profile control agent, a profile control agent, and an oil displacement agent.
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| CN116063621A (en) * | 2021-11-01 | 2023-05-05 | 中国石油化工股份有限公司 | Acrylamide deep profile control copolymer and preparation method and application thereof |
| CN116063619A (en) * | 2021-11-01 | 2023-05-05 | 中国石油化工股份有限公司 | Acrylamide copolymer containing hydroxyl-terminated long-chain structure, and preparation method and application thereof |
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