CN113667145B - Hydrogel, preparation method and application thereof, and water plugging profile control agent - Google Patents

Hydrogel, preparation method and application thereof, and water plugging profile control agent Download PDF

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CN113667145B
CN113667145B CN202110963188.XA CN202110963188A CN113667145B CN 113667145 B CN113667145 B CN 113667145B CN 202110963188 A CN202110963188 A CN 202110963188A CN 113667145 B CN113667145 B CN 113667145B
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polyethylene glycol
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glycidyl ether
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王俊
王玲
刘向斌
王力
张娜
裴钰
翟岩亮
陈丽铎
谭金岩
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Northeast Petroleum University
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Abstract

The invention relates to a hydrogel, a preparation method and application thereof, and a water plugging profile control agent. The hydrogel comprises a polymer represented by the following structural formula:
Figure DDA0003222845510000011
wherein, the R and the n are defined in the specification. The hydrogel has better rheological property, temperature-sensitive property, pH value response property, swelling-deswelling reversibility and shear resistance.

Description

Hydrogel, preparation method and application thereof, and water plugging profile control agent
Technical Field
The invention relates to the technical field of oil exploitation, in particular to hydrogel, a preparation method and application thereof, and a water plugging profile control agent.
Background
The water shutoff profile control agent widely used in the oil field at present is difficult to meet the requirements of partial high-temperature and high-salinity oil reservoirs and alkaline environment, and the main reason is that one of the components in the water shutoff profile control agent in the related technology, namely the rheological property, the temperature-sensitive property, the pH value response property, the swelling-deswelling reversibility, the shear resistance and the like of hydrogel are poor.
Therefore, in view of the above disadvantages, it is desirable to provide a hydrogel having excellent rheological properties, temperature-sensitive properties, pH-responsive properties, swelling-deswelling reversibility or shear resistance.
Disclosure of Invention
The invention aims to solve the technical problem of providing hydrogel with better rheological property, temperature-sensitive property, pH value response property, swelling-deswelling reversibility or shearing resistance.
In order to solve the above technical problems, the present invention provides a hydrogel. The hydrogel comprises a polymer represented by the following structural formula:
Figure BDA0003222845490000011
wherein at least part of R is
Figure BDA0003222845490000021
The n is 6-24 or 38-47, and the viscosity of the polymer is not less than 10000mPa & s and not more than 250000mPa & s. The hydrogel has better rheological property, temperature-sensitive property, pH value response property, swelling-deswelling reversibility and shear resistance.
In embodiments of the invention, the number average molecular weight of the polymer is from 800g/mol to 2000g/mol or from 2200g/mol to 3000 g/mol.
In the embodiment of the present invention, in one molecule of the polymer, 3 to 7 of the Rs are the same as those of the polymer
Figure BDA0003222845490000022
In the embodiment of the invention, n is 15-24.
The present invention also provides a method for preparing the aforementioned hydrogel. The method comprises the following steps: mixing reaction raw materials for preparing the polymer to obtain a first mixture, wherein the reaction raw materials comprise polyethyleneimine and polyethylene glycol glycidyl ether; subjecting the first mixture to a first reaction at a temperature of 40 ℃ to 50 ℃ to obtain the polymer. The method is simple and convenient to operate, easy to realize, easy for industrial production, and capable of effectively preparing the hydrogel.
In some embodiments of the invention, the polyethyleneimine has a number average molecular weight of 400g/mol to 800 g/mol.
In some embodiments of the invention, the polyethylene glycol glycidyl ether has a number average molecular weight of 600g/mol to 2000 g/mol.
In some embodiments of the invention, the molar ratio of the polyethyleneimine to the polyethylene glycol glycidyl ether is 1: (3-8).
In some embodiments of the invention, the molar ratio of the polyethyleneimine to the polyethylene glycol glycidyl ether is 1: (5-7).
In some embodiments of the invention, the molar ratio of the polyethyleneimine to the polyethylene glycol glycidyl ether is 1: 5.
in some embodiments of the invention, the sum of the mass percentages of polyethyleneimine and polyethylene glycol glycidyl ether is 5% to 15% based on the total mass of the first mixture.
In some embodiments of the invention, the sum of the mass percentages of polyethyleneimine and polyethylene glycol glycidyl ether is 10% to 15% based on the total mass of the first mixture.
In some embodiments of the invention, the sum of the mass percentages of polyethyleneimine and polyethylene glycol glycidyl ether is 13% to 15% based on the total mass of the first mixture.
In some embodiments of the present invention, the polyethylene glycol glycidyl ether is prepared by: mixing polyethylene glycol and epichlorohydrin to obtain a second mixture; and (3) carrying out a second reaction on the second mixture under the conditions of preset temperature, alkalinity and existence of a catalyst, thereby obtaining the polyethylene glycol glycidyl ether.
In some embodiments of the invention, the predetermined temperature is 45 ℃ to 65 ℃.
In some embodiments of the invention, the predetermined temperature is 50 ℃ to 60 ℃.
In some embodiments of the invention, the predetermined temperature is 55 ℃.
In some embodiments of the invention, the reaction time of the second reaction is 4h to 11.5 h.
In some embodiments of the invention, the reaction time of the second reaction is 4h to 6 h.
In some embodiments of the invention, the reaction time of the second reaction is 4 h.
In some embodiments of the invention, in the second mixture, the ratio of the amounts of substance of the polyethylene glycol to the epichlorohydrin is 1: (2-6).
In some embodiments of the invention, in the second mixture, the ratio of the amounts of substance of the polyethylene glycol to the epichlorohydrin is 1: (3-5).
In some embodiments of the invention, in the second mixture, the ratio of the amounts of substance of the polyethylene glycol to the epichlorohydrin is 1: 4.
in some embodiments of the invention, the alkalinity in the second mixture is provided by hydroxide ions, and the amount of the hydroxide ion species is from 0.1mol to 0.4 mol.
In some embodiments of the invention, the amount of the hydroxide ion species is 0.2mol to 0.3 mol.
In some embodiments of the invention, the amount of the species of hydroxide ions is 0.2 mol.
The invention also provides the use of the aforementioned hydrogel in oil recovery. The hydrogel can be used as one of the components of a water plugging profile control agent used in oil exploitation, can better meet the requirements of high-temperature and high-salinity oil reservoirs and alkaline environments, and has better application prospect.
The invention also provides a water shutoff profile control agent. The water shutoff profile control agent comprises the hydrogel or the hydrogel prepared by the method. The water shutoff profile control agent can better meet the requirements of high-temperature and high-salinity oil reservoirs and alkaline environments, and has better application prospect.
Compared with the prior art, the invention has the following beneficial effects:
the hydrogel has good rheological property, temperature-sensitive property, pH value response property, swelling-deswelling reversibility and anti-shearing capability, the preparation process is simple and convenient, easy to realize and easy for industrial production, can be used as one of the components of the water plugging profile control agent used in oil exploitation, and the water plugging profile control agent containing the hydrogel can better meet the requirements of high-temperature and high-salinity oil reservoirs and alkaline environments, and has good application prospect.
Drawings
FIG. 1 shows the reaction sequence of a first reaction between polyethyleneimine and polyethylene glycol glycidyl ether according to one embodiment of the present invention;
fig. 2 shows the reaction process of a second reaction occurring between polyethylene glycol and epichlorohydrin according to one embodiment of the present invention;
FIG. 3 shows the effect of different reaction temperatures on the reaction yield and the epoxy value of the product of the second reaction;
FIG. 4 shows the effect of different reaction times on the reaction yield and the epoxy value of the product of the second reaction;
FIG. 5 shows the effect of different amounts of polyethylene glycol and epichlorohydrin on the reaction yield for the second reaction and the epoxy value of the product;
FIG. 6 shows the effect of varying amounts of species of hydroxide ion on the reaction yield and epoxy value of the product of a second reaction;
FIG. 7 shows the results of IR spectroscopy of polyethyleneimine (line a), polyethylene glycol glycidyl ether (line b), and the hydrogel prepared in example 57 (line c);
FIG. 8 shows the results of the rheological property test of the hydrogel prepared in example 59;
FIG. 9 shows the results of a test for the temperature response property of the hydrogel prepared in example 57;
FIG. 10 shows the results of a test for pH-responsive properties of the hydrogel prepared in example 57;
FIG. 11 shows the results of the test for the mineralization resistance of the hydrogel prepared in example 57;
FIG. 12 shows the results of the measurement of swelling-swelling properties at different temperatures of the hydrogel prepared in example 57;
fig. 13 shows the results of the measurement of swelling-swelling properties at different phs of the hydrogel prepared in example 57.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
In a first aspect of the invention, the invention provides a hydrogel. The hydrogel comprises a polymer represented by the following structural formula:
Figure BDA0003222845490000061
wherein at least part of R is
Figure BDA0003222845490000062
The n is 6-24 or 38-47, and the viscosity of the polymer is not less than 10000mPa & s and not more than 250000mPa & s. The hydrogel has better rheological property, temperature-sensitive property, pH value response property, swelling-deswelling reversibility and shear resistance.
In the polymer, provided thatSatisfies that at least a part of the R is
Figure BDA0003222845490000063
That is, it is not required that all R's therein are
Figure BDA0003222845490000064
That is, if R also includes other kinds of groups, it is also within the scope of the present invention that it can achieve better rheological properties, temperature-sensitive properties, pH-responsive properties, swelling-deswelling reversibility, and shear resistance. However, in the above-mentioned polymer of the present invention, all of the R may not be hydrogen.
It will be understood by those skilled in the art that, in the hydrogel, as long as the polymer having the above structural formula is present, the above-mentioned preferable rheological properties, temperature-sensitive properties, pH-responsive properties, swelling-and-swelling reversibility and shear resistance can be achieved, and it is not excluded that a small amount of other structural compounds may also be present, and will not be described herein in detail.
N is in the polymer
Figure BDA0003222845490000071
The degree of polymerization of this structure. The value of n can be specifically 6-15, 15-24 or 38-47, more specifically 6, 7, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24 or 38, 39, 40, 41, 42, 43, 44, 45, 46, 17, etc., and further the polymer has a relatively proper polymerization degree, so that the polymer further has better rheological property, temperature-sensitive property, pH value response property, swelling-swelling reversibility and shear resistance.
In some embodiments of the present invention, specifically, the viscosity of the polymer may be 10000mPa · s, 50000mPa · s, 100000mPa · s, 150000mPa · s, 200000mPa · s, 250000mPa · s, and the like, and the polymer has a more suitable viscosity, and further the polymer has a better rheological property.
In some embodiments of the invention, the number average molecular weight of the polymer may be from 800g/mol to 2000g/mol or from 2200g/mol to 3000 g/mol. Specifically, the number average molecular weight may be 800g/mol, 900g/mol, 1000g/mol, 1200g/mol, 1300g/mol, 1400g/mol, 1500g/mol, 600g/mol, 1700g/mol, 1800g/mol, 1900g/mol, 2000g/mol or 2200g/mol, 2300g/mol, 2400g/mol, 2500g/mol, 2600g/mol, 2700g/mol, 2800g/mol, 2900g/mol, 3000g/mol, etc., and the polymer has a more suitable number average molecular weight, so that the polymer further has better rheological property, temperature-sensitive property, pH value response property, swelling-swelling reversibility and shear resistance.
As previously mentioned, in this polymer, all of R may be as previously described
Figure BDA0003222845490000081
And part of the polymer can also be hydrogen, and the polymer can realize better rheological property, temperature-sensitive property, pH value response property, swelling-deswelling reversibility and shearing resistance.
In some embodiments of the invention, in a molecule of said polymer, the foregoing are
Figure BDA0003222845490000082
The specific number of (A) is not particularly limited, and further, in one molecule of the polymer, there may be 3 to 7 of the R's as the above
Figure BDA0003222845490000083
Specifically, in one molecule of the polymer, 3, 4, 5, 6 or 7 of the Rs are the
Figure BDA0003222845490000084
Through the arrangement mode, the air conditioner is provided with the air inlet,
Figure BDA0003222845490000085
the amount of (A) is more suitable, and the hydrogel as described above can be formed more favorably. When in use
Figure BDA0003222845490000086
When the amount of the polymer is too low, the polymer is difficult to form a three-dimensional network structure and is difficult to generate phase change; when in
Figure BDA0003222845490000087
When the amount of the monomer is too high, the side reaction of the polymer in the preparation process is more, and industrialization is not easy to realize.
In some more preferred embodiments of the present invention, when n is 15 to 24; and in one molecule of said polymer, 5 of said Rs are said
Figure BDA0003222845490000088
When the polymer is used, the polymer further has better rheological property, better temperature-sensitive property, better pH value response property, better swelling-deswelling reversibility and better shear resistance; and the preparation is easy, and the industrialization is easy to realize.
In a second aspect of the invention, there is also provided a method of preparing a hydrogel as hereinbefore described. The method may comprise the steps of: mixing reaction raw materials for preparing the polymer to obtain a first mixture, wherein the reaction raw materials at least comprise Polyethyleneimine (PEI) and polyethylene glycol glycidyl ether (PEGO); subjecting the first mixture to a first reaction at a temperature of 40 ℃ to 50 ℃ to obtain the polymer. The method is simple and convenient to operate, easy to realize, easy for industrial production, and capable of effectively preparing the hydrogel.
Further preferably, after mixing the polyethyleneimine with polyethylene glycol glycidyl ether to obtain a first mixture, the molar ratio of the polyethyleneimine to the polyethylene glycol glycidyl ether in the first mixture may be 1: (3-8), specifically, the molar ratio of the polyethyleneimine to the polyethylene glycol glycidyl ether may be 1: 3. 1: 4. 1: 5. 1: 6. 1: 7 or 1: 8, etc., wherein, when the molar ratio is 1: (5-7), the molar ratio of the two is more suitable, and the hydrogel can be formed better; when the consumption of the polyethyleneimine is too high, the molecular weight of the polyethyleneimine grafted with the polyethylene glycol glycidyl ether is too low, so that a three-dimensional network structure is difficult to form and phase change is difficult to occur; when the amount of the polyethylene glycol glycidyl ether is too high, the first mixture may contain a large amount of the polyethylene glycol glycidyl ether, which may hinder the polyethylene imine from undergoing the first reaction therewith; even more preferably, when the molar ratio is 1: and 5, the hydrogel forming effect of the two materials is better, the cost is lower, the material can be saved, and the industrialization is easier to realize.
In the present invention, the polymerization degree, number average molecular weight, etc. of the foregoing polyethyleneimine and the polyethylene glycol glycidyl ether are not particularly limited, and those skilled in the art can flexibly select them according to actual needs as long as the requirements are satisfied. For example, in some embodiments of the present invention, the polyethyleneimine may have a number average molecular weight of 400g/mol to 800g/mol g/mol, more specifically, the polyethyleneimine may have a number average molecular weight of 600 g/mol; the number average molecular weight of the polyethylene glycol glycidyl ether can be 600g/mol to 2000g/mol, more specifically, the number average molecular weight of the polyethylene glycol glycidyl ether can be 600g/mol, 1000g/mol, 2000g/mol, and the like, wherein when the number average molecular weight of the polyethylene glycol glycidyl ether is 1000g/mol, the performance of the hydrogel prepared is better.
In the present invention, the specific manner of mixing the polyethyleneimine and the polyethylene glycol glycidyl ether is not particularly limited, and those skilled in the art can flexibly select the mixture according to actual needs as long as the requirement is met, and redundant description is omitted here.
In some preferred embodiments, the sum of the mass percentages of the polyethyleneimine and the polyethylene glycol glycidyl ether may be 5% to 15%, based on the total mass of the first mixture. Specifically, the sum of the mass percentages of the polyethyleneimine and the polyethylene glycol glycidyl ether may be 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, or the like. More preferably, when the sum of the mass percent of the two is 10-15%, the hydrogel forming effect is better; more preferably, when the sum of the mass percentage of the hydrogel and the mass percentage of the hydrogel is 13-15%, the hydrogel forming effect is better, the required reaction time is shorter, the industrialization is easy to realize, and the production efficiency is high; when the sum of the above-mentioned mass percentages is too low, the amount of the solvent contained in the first mixture is too large, resulting in a low yield and poor stability of the hydrogel formed therefrom.
In the present invention, the reaction type of the first reaction between polyethyleneimine and polyethylene glycol glycidyl ether as described above may include a grafting reaction. For example, in some embodiments of the present invention, the reaction process of the first reaction may be as shown in FIG. 1, the epoxy group of the polyethylene glycol glycidyl ether and the amino group (-NH) of the polyethyleneimine2) Or the imino (-NH-) reacts to form an alcoholic hydroxyl group by a nucleophilic substitution reaction (SN2) to form the polymer described above (it should be noted that fig. 1 shows only the specific linkage between two R's on one N, and those skilled in the art will understand that the R's are linked to N in the same manner on the other N's of the polymer).
In some preferred embodiments, the reaction temperature of the first reaction is from 40 ℃ to 50 ℃. Specifically, the reaction temperature of the first reaction may be 40 ℃, 42 ℃, 44 ℃, 45 ℃, 46 ℃, 48 ℃, or 50 ℃ or the like. When the reaction temperature of the first reaction is the above temperature or in the above temperature range, the polymer as described above can be produced more efficiently.
In the present invention, the heating manner of the first reaction is not particularly limited. For example, in some embodiments of the present invention, the heating means for the first reaction may be water bath heating. The operation mode is simple and convenient to operate and easy to realize, so that the industrial production is easier.
In the present invention, the specific reaction time is not limited to the first reaction, as long as a stable polymer can be formed between the reactant polyethyleneimine and the polyethylene glycol glycidyl ether, that is, the reaction time of the first reaction may be based on the time required for forming a hydrogel after mixing the reactant polyethyleneimine and the polyethylene glycol glycidyl ether.
In addition, for the first reaction, the operation modes, steps, conditions and the like which are not mentioned above can be performed according to the conventional organic chemical reaction, and those skilled in the art can flexibly select according to the actual needs, and thus redundant description is not repeated herein.
In some preferred embodiments, the polyethylene glycol glycidyl ether described above can be prepared by: mixing polyethylene glycol and epichlorohydrin to obtain a second mixture, and carrying out a second reaction on the second mixture at a preset temperature under the conditions of alkalinity and the presence of a catalyst to obtain the polyethylene glycol glycidyl ether. The operation mode is simple and convenient to operate and easy to realize, so that the industrial production is easier.
In other preferred embodiments, the predetermined temperature may be 45 ℃ to 65 ℃. Specifically, the predetermined temperature may be 45 ℃, 50 ℃, 55 ℃, 60 ℃, or 65 ℃ or the like. Still more preferably, the yield of the above second reaction and the epoxy value of the formed polyethylene glycol glycidyl ether are higher when the predetermined temperature is 50 ℃ to 60 ℃; still further preferably, when the predetermined temperature is 55 ℃, the yield of the above-mentioned second reaction and the epoxy value of the formed polyethylene glycol glycidyl ether can be further improved. Specifically, when the predetermined temperature is too low, the molecular thermal motion of the reactant is slow, and the probability of effective thermal motion of the polyethylene glycol and the epichlorohydrin is low; as the predetermined temperature is increased, the probability of collision between molecules is increased, so that the yield and the epoxy value are increased, but when the temperature is too high, epichlorohydrin is polymerized because of being more active, and byproducts are increased, so that the yield of the polyethylene glycol glycidyl ether is reduced.
In other preferred embodiments, the heating manner of the second reaction is not particularly limited, and specifically, in some embodiments of the present invention, the heating manner of the second reaction may be water bath heating. The operation mode is simple and convenient to operate and easy to realize, so that the industrial production is easier.
In other preferred embodiments, the reaction time of the second reaction may be 4h to 11.5h, and specifically, the reaction time of the second reaction may be 4h, 6h, 8h, 9.5h, 11.5h, or the like. Still more preferably, when the reaction time is 4 to 6 hours, the yield of the above second reaction and the epoxy value of the formed polyethylene glycol glycidyl ether are high; still more preferably, when the reaction time is 4 hours, the yield of the second reaction and the epoxy value of the formed glycidyl ether of polyethylene glycol can be further improved, and the production cycle is short, and the production efficiency is high, specifically, because the molecular weight of polyethylene glycol is large, and when the reaction time is short (for example, less than 4 hours), the reaction is incomplete, and as the reaction time increases, the reaction approaches equilibrium, and both the yield and the epoxy value approach the maximum value, but as the reaction time continues to extend, the probability of side reaction increases greatly, and the yield and the epoxy value tend to decrease again.
In other preferred embodiments, the mass ratio of the polyethylene glycol to the epichlorohydrin may be 1: (2 to 6), specifically, the ratio of the amounts of the polyethylene glycol and the epichlorohydrin may be 1: 2. 1: 3. 1: 4. 1: 5 or 1: 6, and the like. Still further preferably, when the mass ratio of the polyethylene glycol to the epichlorohydrin is 1: (3-5), the yield of the second reaction and the epoxy value of the formed polyethylene glycol glycidyl ether are high; still further preferably, when the ratio of the amounts of the substance of the polyethylene glycol and the epichlorohydrin is 1: when 4, the yield of the second reaction and the epoxy value of the formed polyethylene glycol glycidyl ether can be further improved, specifically, because the molecular weight of polyethylene glycol is large and the reactivity is low, and the yield of the product can be improved by increasing the amount of epichlorohydrin to promote the forward progress of the second reaction, but the ratio of the amounts of the materials of the raw materials is 1: 4, the reaction reaches the maximum limit, and the yield can not be increased by increasing the molar ratio of the raw materials; further, as the ratio of the amounts of the raw materials increases, the reaction becomes more sufficient, and the epoxy value increases, but when the amount of epichlorohydrin is too high, a side reaction occurs, and the epoxy value decreases.
In other preferred embodiments, the specific manner of mixing the polyethylene glycol and the epichlorohydrin is not particularly limited, and as long as the requirements are met, those skilled in the art can flexibly select the mixture according to actual needs, and redundant description is omitted here.
In other preferred embodiments, the polymerization degree, the number average molecular weight, and the like of the polyethylene glycol are not particularly limited, and those skilled in the art can flexibly select the polyethylene glycol according to actual needs as long as the requirements are met, and redundant description is omitted.
In other preferred embodiments, the alkalinity in the second mixture is provided by hydroxide ions in an amount of 0.1 to 0.4 moles, and specifically, the molar fraction of the hydroxide ions may be 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, or 0.4 moles, etc., based on the total amount of the second mixture. More preferably, when the amount of the hydroxyl ion is 0.2mol to 0.3mol, the yield of the second reaction and the epoxy value of the formed polyethylene glycol glycidyl ether are higher, and more preferably, when the amount of the hydroxyl ion is 0.2mol, the yield of the second reaction and the epoxy value of the formed polyethylene glycol glycidyl ether are higher, specifically, the hydroxyl ion can make the whole reaction system alkaline, and the alkaline is a key reagent for the ring closure of dehydrochloride in the second reaction to form the polyethylene glycol glycidyl ether, and the amount of the hydroxyl ion influences the degree of the second reaction; when the amount of hydroxide ions is too small, the second reaction is not completely performed, and the yield and epoxy value of the product polyethylene glycol glycidyl ether are low; when the amount of hydroxide ions is too much, epichlorohydrin can undergo ring-opening polymerization under the action of strong alkali, so that by-products are increased, and the epoxy value is reduced.
In the present invention, the specific addition form of the hydroxide ions in the second mixture is not particularly limited, and the hydroxide ions may be introduced by adding sodium hydroxide, potassium hydroxide, or the like, for example. Among them, sodium hydroxide is more preferable because it is low in cost and the introduction of sodium ions does not affect the progress of the whole reaction.
In the present invention, the types of reactions of the second reaction between polyethylene glycol and epichlorohydrin described above are ring-opening and ring-closing reactions of epichlorohydrin. In some embodiments of the present invention, referring to fig. 2, the reaction process of the second reaction is that epichlorohydrin is subjected to a ring-opening reaction under the action of a catalyst (for example, TBAB, tetrabutylammonium bromide), and then subjected to a ring-closing reaction under an alkaline condition (for example, the alkalinity is provided by hydroxide ions, and the substance providing the hydroxide ions is sodium hydroxide), so as to remove hydrogen chloride, so as to form polyethylene glycol glycidyl ether.
For the second reaction, the operation modes, steps, conditions and the like which are not mentioned above can be performed according to conventional organic chemical reactions, and those skilled in the art can flexibly select according to actual needs, and thus redundant description is omitted.
In a third aspect of the invention, the invention also provides the use of a hydrogel as hereinbefore described in oil recovery. For example, the hydrogel can be used as one of components of a water shutoff profile control agent used in oil exploitation, can better meet the requirements of high-temperature and high-salinity oil reservoirs and alkaline environment, and has better application prospects.
In a fourth aspect of the invention, the invention also provides a water shutoff profile control agent. The water shutoff profile control agent comprises the hydrogel or the hydrogel prepared by the method, can better meet the requirements of high-temperature and high-salinity oil reservoirs and alkaline environments, and has better application prospect.
It is understood that the water shutoff profile control agent of the present invention may further include other components and auxiliaries used in conventional water shutoff profile control agents of the related art. For example, in some embodiments of the present invention, the water shutoff profile control agent may further include a stabilizer, a solvent, and the like, which are not described in detail herein.
The following describes embodiments of the present invention in detail. In the examples of the present invention, reagents and instruments as described below were used:
polyethylene glycol-600, polyethylene glycol-1000, polyethylene glycol-2000: the chemical reagent factory of Daozhi, Tianjin is analyzed and purified; polyethyleneimine: Sigma-Aldrich, analytical grade, MnAbout 600 g/mol; tetrabutylammonium bromide: the analytical purity of the Guangfu fine chemical research institute in Tianjin; epoxy chloropropane: the analytical purity of the product is more than 98.0 percent in Daozhi chemical reagent factory in Tianjin; absolute ethanol, sodium hydroxide: the analytical reagent is pure by Damao chemical reagent factory in Tianjin; nitrogen gas: 99.99%, daqing xuelong petrochemical technology development limited; the secondary distilled water is prepared by self, and other reagents except special instructions are analytical pure.
Analytical balance, BS124S, sartorius instruments ltd; digital display heat collection type magnetic stirrer: DF-II, Ronghua instruments, Inc.; super constant temperature water bath: model DF-101S, Wen Water medical facilities.
It should be noted that, in addition to the reagents and apparatuses described above, no specific techniques or conditions are noted in the examples of the present invention, and the procedures and conditions are described in the literature in the art or the product specification. The other reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Example 1 method for preparing the hydrogel described previously:
(1) synthesis of polyethylene glycol glycidyl ether: respectively mixing 50g of the mixture and the number average molecular weight MnAdding 600g/mol, 1000g/mol and 2000g/mol of polyethylene glycol into a three-neck flask with a stirring and refluxing condenser pipe and a constant pressure dropping funnel, and stirring at 45 ℃ until the polyethylene glycol is dissolved; 0.6447g of tetrabutylammonium bromide were added with stirring; after 5min, 15.8mL of epichlorohydrin is dripped into the reaction liquid by using a constant pressure dropping funnel; stirring for 5min, and heating to 55 deg.C; 4g of solid hydrogen hydroxide was addedSodium reaction for 4 hours; filtering twice (filtering with Buchner funnel) while hot, and reserving liquid in the filter flask; finally transferring the liquid in the suction filtration bottle to a single-mouth bottle, distilling under reduced pressure for 2 times (the reduced pressure distillation temperature is set to 55 ℃, the negative pressure of a circulating water vacuum pump is set to be-1 MPa, 30mL of absolute ethyl alcohol is added during the second distillation), obtaining a light yellow product, wherein the yield is about 90%, and the M of the prepared polyethylene glycol glycidyl ether is determined to be M of the polyethylene glycol glycidyl ethernRespectively 600g/mol, 1000g/mol and 2000 g/mol. The specific reaction equation is shown in FIG. 2.
(2) Synthesis of hydrogel: weighing 20g of polyethylene glycol glycidyl ether prepared in the step (1) and polyethyleneimine (M)n600g/mol) is put into a three-mouth bottle, water is used as a solvent, the mixture is stirred to be viscous at the temperature of 45 ℃, and heating is stopped, so that the target product is obtained, wherein in the step, the molar ratio and the mass percentage content of the polyethylene glycol glycidyl ether to the polyethyleneimine can be shown in table 2.
Examples 2 to 20
Examples 2 to 20 differ from example 1 only in the synthesis of polyethylene glycol glycidyl ether in step (1), the reaction conditions or the molar ratio of each reactant are different, and specifically, see table 1, where n (peg) represents the amount of polyethylene glycol and n (C) represents the amount of polyethylene glycol3H5ClO) represents the amount of epichlorohydrin and n (C)16H36BrN) represents the amount of tetrabutylammonium bromide species, n (naoh) represents the amount of sodium hydroxide species:
table 1 reaction conditions or molar ratio of reactants in the synthesis of polyethylene glycol glycidyl ether in the method for producing hydrogel according to example 1 to example 20
Figure BDA0003222845490000161
Examples 21 to 71
The step (1) in examples 21 to 71 was carried out in the same manner and under the same conditions as those described in example 1, and the only difference between examples 21 to 71 was that the molar ratio of each reactant and the mass percentage of each reactant in the synthesis of hydrogel in step (2) were different, and specifically, refer to table 2:
TABLE 2 reaction conditions and molar ratios of reactants in the synthesis of hydrogel in the methods for preparing hydrogel in examples 21 to 71
Figure BDA0003222845490000171
Figure BDA0003222845490000181
Figure BDA0003222845490000191
The test method comprises the following steps:
(1) infrared spectrum test: the infrared spectrum of the series of hydrogels was measured on a PERKIN-ELMERL700 type FT-IR spectrometer (Perkin elmer, USA) using KBr salt sheet as a coating film and a scanning range of 400-4000 cm-1Wherein the preparation method of the coating comprises the following steps: grinding 1 mg-2 mg of sample and 200mg of pure KBr, uniformly mixing, placing in a mould, and using 5X 107Pa～7×107Pressing Pa into transparent sheet on oil press.
(2) And (3) rheological property testing: the strain is 0.05% and the scanning frequency is 1 Hz. And performing rheological property characterization by using a dynamic test method. And (4) putting the newly prepared sample into a conical plate test fixture, and sealing with silicone oil to prevent volatilization, so that the sample can be used for measurement.
(3) And (3) testing temperature response performance: the hydrogel synthesized in example 57 was cut into small pieces and dried, a temperature gradient was set at intervals of 5 ℃ between 40 ℃ and 60 ℃, the dried small pieces of hydrogel were put at different temperatures to absorb water and swell, and the swelling ratio was measured.
(4) Testing pH response performance: the hydrogel synthesized in example 57 was cut into small pieces and dried, and the dried small pieces of hydrogel were put into different pH's for swelling by water absorption under a temperature gradient of 6 with pH set to 8 to 13, and the swelling ratio was measured.
(5) And (3) testing the mineralization resistance: the hydrogel synthesized in example 57 was cut into small pieces and dried, and 0.1% NaCl solution and 0.1% CaCl were prepared2And (3) solution, namely respectively putting the small hydrogel blocks into the two solutions, and measuring the swelling ratio of the small hydrogel blocks.
(6) Swelling-detumescence test:
a. and (3) testing swelling and deswelling performances at different temperatures: the hydrogel synthesized in example 57 was cut into small pieces and dried, and then placed at 20 ℃ for 24 hours, and then the swelling ratio was measured, and then transferred to 60 ℃ for 24 hours, and then the swelling ratio was measured, and the above-mentioned operations were repeated.
b. Swelling and deswelling performance tests at different pH values: the hydrogel synthesized in example 57 was cut into small pieces and dried, and then placed at pH 8, and the swelling ratio was measured after 24 hours, and then transferred to pH 13, and the swelling ratio was measured after 24 hours, and the above-described operations were repeated.
Results of experiments and tests of examples 1 to 20:
from examples 2 to 5 and 12, and FIG. 3, it can be seen that the predetermined temperature in the second reaction described above may be from 45 ℃ to 65 ℃; it is still further preferred that the yield of the above second reaction and the epoxy value of the formed polyethylene glycol glycidyl ether are higher when the predetermined temperature is 50 ℃ to 60 ℃; it is still further preferred that the yield of the above-mentioned second reaction and the epoxy value of the formed polyethylene glycol glycidyl ether can be further improved when the predetermined temperature is 55 deg.c, and in fig. 3, the yield is 83.2% when the predetermined temperature is 45 deg.c; the epoxy value of the product was 0.145 mmol/g; the yield was 86.1% at a predetermined temperature of 50 ℃; the epoxy value of the product was 0.156 mmol/g; when the preset temperature is 55 ℃, the yield is 88.6 percent; the epoxy value of the product was 0.161 mmol/g; the yield is 85.7% when the preset temperature is 60 ℃; the epoxy value of the product was 0.157 mmol/g; the yield was 82.9% at a predetermined temperature of 65 ℃; the epoxy value of the product was 0.149 mmol/g.
As is clear from example 3 and examples 6 to 9, and fig. 4, the reaction time of the second reaction described above may be 4 to 11.5 hours; it is still further preferred that the yield of the above second reaction and the epoxy value of the formed polyethylene glycol glycidyl ether are higher when the reaction time is 4 to 6 hours; still more preferably, the yield of the above second reaction and the epoxy value of the formed polyethylene glycol glycidyl ether can be further improved when the reaction time is 4 hours, and in fig. 4, the yield is 88% when the reaction time is 4 hours; the epoxy value of the product was 0.1629 mmol/g; when the reaction time is 6 hours, the yield is 87.9 percent; the epoxy value of the product is 0.1630 mmol/g; when the reaction time is 8 hours, the yield is 85.9 percent; the epoxy value of the product was 0.1590 mmol/g; when the reaction time is 10 hours, the yield is 84.7 percent; the epoxy value of the product was 0.1545 mmol/g; when the reaction time is 11.5h, the yield is 82.6 percent; the epoxy value of the product was 0.1532 mmol/g.
As is clear from examples 1, 10, 11, 13, 14 and fig. 5, the ratio of the amounts of the polyethylene glycol to the epichlorohydrin may be 1: (2-6); it is still further preferred when the mass ratio of polyethylene glycol to epichlorohydrin is 1: (3-5), the yield of the second reaction and the epoxy value of the formed polyethylene glycol glycidyl ether are higher; still further preferably, when the ratio of the amounts of the substance of the polyethylene glycol and the epichlorohydrin is 1: 4, the yield of the above second reaction and the epoxy value of the formed polyethylene glycol glycidyl ether can be further improved, and in fig. 5, the mass ratio of polyethylene glycol to epichlorohydrin is 1: 2, the yield is 87.1 percent; the epoxy value of the product was 0.1251 mmol/g; the ratio of the amounts of the substances is 1: at 3, the yield is 89.2%; the epoxy value of the product was 0.1690 mmol/g; the ratio of the amounts of the substances is 1: 4 hours, the yield is 90.5%; the epoxy value of the product was 0.1763 mmol/g; the ratio of the amounts of the substances is 1: at 5, the yield is 90.3%; the epoxy value of the product was 0.1650 mmol/g; the ratio of the amounts of the substances is 1: at 6h, the yield is 90.2%; the epoxy value of the product was 0.1629 mmol/g.
As is clear from example 1, examples 15 to 20, and FIG. 6, the amounts of the species of hydroxide ion were 0.1mol, 0.15mol, 0.2mol, 0.25mol, 0.3mol, 0.35mol, and 0.4 mol; it is further preferred that the yield of the above second reaction and the epoxy value of the formed polyethylene glycol glycidyl ether are high when the amount of the substance of hydroxide ion is 0.2 to 0.3 mol; still more preferably, when the amount of the hydroxyl ion substance is 0.2mol, the yield of the second reaction and the epoxy value of the formed polyethylene glycol glycidyl ether are higher and more than 90%, and the epoxy value is relatively close to the theoretical epoxy value, and in FIG. 6, when the amount of the hydroxyl ion substance is 0.1mol, the yield is 81.7%; the epoxy value of the product was 0.1250; when the amount of the above substance was 0.15mol, the yield was 87.5%; the epoxy value of the product was 0.1561; when the amount of the above substance was 0.2mol, the yield was 90.6%; the epoxy value of the product was 0.1762; when the amount of the above substance was 0.25mol, the yield was 89.5%; the epoxy value of the product was 0.1732; when the amount of the above substance was 0.3mol, the yield was 88.0%; the epoxy value of the product was 0.1662; when the amount of the above substance was 0.35mol, the yield was 87.5%; the epoxy value of the product was 0.1532 mmol/g; when the amount of the above substance was 0.4mol, the yield was 87%; the epoxy value of the product was 0.1425 mmol/g.
The hydrogel formation conditions of examples 21 to 71 are shown in Table 3
TABLE 3 hydrogel formation in examples 21 to 71
Figure BDA0003222845490000221
Figure BDA0003222845490000231
Figure BDA0003222845490000241
As can be seen from the experimental results of examples 21 to 35 in table 3, the gelling time is shorter on the premise that the hydrogel in example 25 is produced at a lower cost; as is clear from the experimental results of examples 36 to 71 in Table 3, when the sum of the mass percentages of polyethyleneimine and polyethylene glycol glycidyl ether is less than 8%, polyethylene glycol glycidyl ether having a number average molecular weight of 600g/mol does not react with polyethyleneimine; when the sum of the mass percentages of the polyethyleneimine and the polyethylene glycol glycidyl ether is less than 5%, the polyethylene glycol glycidyl ether with the number average molecular weight of 600g/mol and the polyethylene glycol glycidyl ether with the number average molecular weight of 1000g/mol do not react with the polyethyleneimine, and the polyethylene glycol glycidyl ether with the number average molecular weight of 2000g/mol can react with the polyethyleneimine to generate a colloid with better viscoelasticity. Therefore, under the reaction condition of lower concentration, polyethylene glycol glycidyl ether with larger molecular weight can be grafted to the skeleton of polyethyleneimine to generate hydrogel.
Infrared spectrum test: the hydrogel prepared in example 57 was subjected to infrared spectroscopic measurement in accordance with the method described above, and the measurement results are shown in FIG. 7.
The wavelength is 3350-3150 cm as shown by the spectral line (a)-1The broad peaks are less pronounced in shape and shifted to lower wavenumbers than normal primary amine peaks, indicating that there is not only associated-NH in the polymer2Structure, also present is-NH-structure, wavelength at 2941cm-1Is represented by-CH2Has a peak of stretching vibration of 1687cm-1And 1592cm-1The peak is the N-H bending vibration peak of primary amine and secondary amine, and the wavelength is 1446-1058 cm-1Is C-N stretching vibration peak of primary amine and secondary amine, and the wavelength is 1024cm-1The existence of an absorption peak indicates that the compound has a tertiary amine structure, and the compound is branched polyethyleneimine; the wavelength is 1126cm as can be seen from the spectral line of (b)-1A stretching vibration absorption peak of an ether bond C-O-C; wavelength is 2877cm-1In the form of methylene-CH2The stretching vibration peak of (1); wavelength of 1279cm-1、946cm-1、843cm-1The characteristic peak of the three-membered ring epoxy group is shown; the wavelength is 3200-3600 cm-1The weak absorption peak of (a) indicates that a small amount of-OH in the synthesized polyethylene glycol glycidyl ether remains incompletely epoxidized. As can be seen from the comparison of the curve (c) with the curves (a) and (b), the wavelength is 1048cm-1The tertiary amine C-N stretching vibration peak is enhanced, and the wavelength is 3410-3480 cm-1the-OH peak is shifted and enhanced, the characteristic peak of the epoxy group disappears,illustrating the epoxy groups of the polyethylene glycol glycidyl ether and-NH-or-NH-in PEI2A ring-opening addition reaction occurs to produce an alcoholic hydroxyl group.
And (3) rheological property testing:
the hydrogel prepared in example 59 was subjected to rheological measurements using a rheometer according to the test method described above, after standing for two days, at a shear rate of 7s-1The test interval is 40-60 ℃, and the test result is shown in figure 8.
As can be seen from fig. 8, the viscosity of the hydrogel increased with the increase in temperature, the lowest viscosity thereof was also greater than 10000mPa · s, and the viscosity of the gel sharply increased when the temperature was increased to 55 ℃ or higher. This is because as the temperature increases, the gaps between the molecular chains become smaller, the network structure becomes denser, and the long chain branches can increase entanglement with neighboring molecules, so that flow is hindered and the hydrogel viscosity increases; when the temperature is increased to 55 ℃, the viscosity is increased sharply, the temperature is the Lower Critical Solution Temperature (LCST) of the hydrogel, the hydrogel is a block polymer, has a plurality of temperature response arms and contains a certain proportion of hydrophilic and hydrophobic groups, when the hydrogel is heated to be higher than the LCST, the molecular self-assembly process is triggered, the hydrogel structure tends to be stable, the hydrophobicity of the whole hydrogel is increased, the water content in the hydrogel is reduced, and the viscosity of the hydrogel is increased.
And (3) testing temperature response performance:
the hydrogel prepared in example 57 was subjected to a temperature response property test according to the test method described previously, and the test results are shown in FIG. 9.
As can be seen from fig. 9, as the temperature increases, the swelling ratio of the hydrogel increases, and thermal expansibility is exhibited. The molecular chain movement is promoted by the temperature rise, so that the network structure of the hydrogel can be relaxed to accommodate more water molecules, meanwhile, the water molecules are easier to diffuse into a gel system, the polyethylene glycol glycidyl ether and the polyethyleneimine are combined in a covalent bond form, the temperature rise and the molecular thermal movement are violent, the covalent bond is broken, more hydrophilic groups in the hydrogel are exposed, more water molecules can be associated, and the swelling rate of the hydrogel is improved.
Testing pH response performance:
the hydrogel prepared in example 57 was subjected to the pH response property test according to the test method described above, and the test results are shown in fig. 10.
As can be seen from fig. 10, the swelling ratio of the hydrogel decreased with increasing pH. The amino groups can be protonated under acidic and neutral conditions to enable the hydrogel molecular chain belts to have the same charges and repel each other, the network structure is in an expanded state, and the protonation is more difficult as the pH value is larger under alkaline conditions, the network structure of the hydrogel tends to shrink, and the swelling rate is reduced.
And (3) testing mineralization resistance:
the hydrogel prepared in example 57 was subjected to the mineralization resistance test according to the test method described above, and the test results are shown in FIG. 11.
As can be seen from FIG. 11, the hydrogel began to approach the equilibrium of swelling at 5 days of swelling, in NaCl, CaCl2The swelling ratio of the solution is obviously lower than that of distilled water, and the swelling ratio of the solution is in CaCl2The swelling ratio in solution is lowest. The addition of the salt solution obviously reduces the swelling rate of the hydrogel, because when the absorbed water contains salt, the ion concentration in the solution is increased, the concentration difference between the inner side and the outer side of the hydrogel is reduced, the osmotic pressure of water molecules permeating into the hydrogel is reduced, the hydrogel is a polymer electrolyte, a plurality of cationic groups capable of being ionized are arranged on molecular chains, the ionization balance of the hydrogel in the salt solution moves leftwards, the ionization degree is reduced, and the water absorption rate of the hydrogel is reduced; hydrogel in CaCl2The swelling ratio in solution is lowest because of Ca2+Ca of (2)2+The ionic charge of (2) is larger, so that the effect of reducing the water absorption of the hydrogel is stronger.
Swelling-relieving performance test:
the hydrogel prepared in example 57 was subjected to swelling-swelling property tests at different temperatures according to the test methods described above, and the test results are shown in FIG. 12; swelling-deswelling performance at different pH values was tested and the results are shown in FIG. 13.
As can be seen from fig. 12, the swelling ratio of the hydrogel showed a periodic variation trend as a whole, showing a distinct temperature sensitivity and good reversibility. The temperature rise promotes the movement of molecular chains, the molecular chains can expand to accommodate more water molecules, meanwhile, the polyethylene glycol glycidyl ether is combined with the polyethyleneimine in a covalent bond form, the thermal movement of the temperature rise macromolecules is more violent, more hydrophilic groups are exposed after the covalent bonds are broken, so that more water molecules can be associated, and the swelling rate of the hydrogel is increased; the bonding effect between the molecular chain and the water molecule can be reversibly rebuilt by the temperature reduction, so that the hydrophobicity of the hydrogel molecular chain is improved, and the hydrogel volume is shrunk.
As can be seen from fig. 13, the swelling ratio of the hydrogel showed a periodic change tendency as a whole, showing a remarkable pH sensitivity and good reversibility. Because the tertiary amine groups in hydrogel molecules are easy to protonate, the swelling rate of the hydrogel under acidic conditions is high due to electrostatic repulsion, the protonation of the amine groups is more difficult when the pH value is larger, the acidic amine groups can be protonated and converted into neutral amine groups under alkaline conditions, and the molecular chains curl, so that the swelling rate is reduced.
In conclusion, the hydrogel provided by the invention has better rheological property, temperature-sensitive property, pH value response property, swelling-deswelling reversibility and shearing resistance, simple and convenient preparation process, easy realization and easy industrial production, can be used as one of the components of the water plugging profile control agent used in oil exploitation, can better meet the requirements of high-temperature and high-salinity oil reservoirs and alkaline environment, and has better application prospect.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.

Claims (12)

1. A hydrogel comprising a polymer represented by the following structural formula:
Figure FDA0003596450640000011
wherein at least part of R is
Figure FDA0003596450640000012
The n is 6-24 or 38-47, and the viscosity of the polymer is not less than 10000mPa & s and not more than 250000mPa & s;
wherein the number average molecular weight of the polymer is 800 g/mol-2000 g/mol or 2200 g/mol-3000 g/mol;
wherein the hydrogel satisfies the following conditions: in one molecule of said polymer, 3 to 7 of said Rs are said
Figure FDA0003596450640000013
2. The hydrogel of claim 1, wherein n is 15 to 24.
3. A method of preparing the hydrogel of claim 1 or 2, comprising:
mixing reaction raw materials for preparing the polymer to obtain a first mixture, wherein the reaction raw materials comprise polyethyleneimine and polyethylene glycol glycidyl ether;
carrying out a first reaction on the first mixture at the temperature of 40-50 ℃ to obtain the polymer;
the method satisfies the following conditions:
(1) the number average molecular weight of the polyethyleneimine is 400 g/mol-800 g/mol;
(2) the number average molecular weight of the polyethylene glycol glycidyl ether is 600g/mol to 2000 g/mol;
(3) the molar ratio of the polyethyleneimine to the polyethylene glycol glycidyl ether is 1: (3-8);
(4) based on the total mass of the first mixture, the sum of the mass percentages of the polyethyleneimine and the polyethylene glycol glycidyl ether is 10-15%.
4. The method according to claim 3, wherein the molar ratio of the polyethyleneimine to the polyethylene glycol glycidyl ether is 1: (5-7).
5. The method according to claim 3, wherein the molar ratio of the polyethyleneimine to the polyethylene glycol glycidyl ether is 1: 5.
6. the method according to claim 3, wherein the sum of the mass percentages of the polyethyleneimine and the polyethylene glycol glycidyl ether is 13-15%.
7. The method according to claim 3, wherein the polyethylene glycol glycidyl ether is prepared by the following steps:
mixing polyethylene glycol and epichlorohydrin to obtain a second mixture;
and (3) carrying out a second reaction on the second mixture under the conditions of preset temperature, alkalinity and existence of a catalyst to obtain the polyethylene glycol glycidyl ether.
8. The method of claim 7, wherein at least one of the following conditions is satisfied:
(1) the preset temperature is 45-65 ℃;
(2) the reaction time of the second reaction is 4-11.5 h;
(3) in the second mixture, the mass ratio of polyethylene glycol to epichlorohydrin is 1: (2-6);
(4) the alkalinity in the second mixture is provided by hydroxide ions, and the amount of the hydroxide ion species is 0.1 to 0.4 mol.
9. The method of claim 8, wherein at least one of the following conditions is satisfied:
(1) the preset temperature is 50-60 ℃;
(2) the reaction time of the second reaction is 4-6 h;
(3) in the second mixture, the mass ratio of polyethylene glycol to epichlorohydrin is 1: (3-5);
(4) the alkalinity in the second mixture is provided by hydroxide ions, and the amount of the hydroxide ions is 0.2mol to 0.3 mol.
10. The method of claim 8, wherein at least one of the following conditions is satisfied:
(1) the predetermined temperature is 55 ℃;
(2) the reaction time of the second reaction is 4 h;
(3) in the second mixture, the mass ratio of polyethylene glycol to epichlorohydrin is 1: 4;
(4) the amount of the hydroxide ion species was 0.2 mol.
11. Use of the hydrogel of claim 1 or 2 in oil recovery.
12. A water shutoff profile control agent is characterized in that: comprising the hydrogel of claim 1 or 2 or the hydrogel produced by the method of any one of claims 3 to 10.
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