阅读说明：本技术 化合物及其制备方法、聚合物及其制备方法和应用 (Compound and preparation method thereof, polymer and preparation method and application thereof ) 是由 方昭 杨金彪 伊卓 刘希 祝纶宇 胡晓娜 李雅婧 于 2020-06-28 设计创作，主要内容包括：本发明涉及聚合物驱油领域,具体地,涉及一种化合物及其制备方法、聚合物及其制备方法和应用。所述化合物具有式(1)所示的结构：其中,1≤n≤8,且为整数；M为H、Li、Na、K和NH-(4)中的一种。该化合物同时具有聚氧乙烯醚长链和磺酸基团,能够显著提高由其聚合得到的聚合物分子的溶解性、增粘性,同时兼具较为优异的表面活性,特别适用于作为驱油剂用于海上油藏。(The invention relates to the field of polymer flooding, in particular to a compound and a preparation method thereof, a polymer and a preparation method and application thereof. The compound has a structure represented by formula (1): wherein n is more than or equal to 1 and less than or equal to8, and is an integer; m is H, Li, Na, K and NH 4 One kind of (1). The compound has both a polyoxyethylene ether long chain and a sulfonic acid group, can obviously improve the solubility and the tackifying property of polymer molecules obtained by polymerization of the compound, has excellent surface activity, and is particularly suitable for being used as an oil displacement agent for offshore oil reservoirs.)

1. A compound having a structure according to formula (1):

wherein n is more than or equal to 1 and less than or equal to 8 and is an integer; m is H, Li, Na, K and NH₄One kind of (1).

2. The compound according to claim 1, wherein in formula (1), 1. ltoreq. n.ltoreq.5; m is Li, Na, K and NH₄One of (1);

preferably, n is 2. ltoreq. n.ltoreq.5 and M is Na.

3. The compound of claim 1, wherein the compound has a structure represented by one of formula (2) -formula (6):

4. a method for preparing a compound, comprising the steps of:

(1) under the condition of amidation reaction, the ethanolamine compound with the structure shown as the formula (7) reacts with the acrylic compound with the structure shown as the formula (8);

m is H, Li, Na, K and NH₄One of (1), R₁Is OH, Cl and CH₂-one of CH-CHO-;

(2) under the condition of etherification, contacting the product obtained in the step (1) with halogenated polyoxyethylene ether; the general formula of the halogenated polyoxyethylene ether is HO- (CH)₂CH₂O)_n-CH₂-CH₂-R₂N is an integer of 1 to 8, R₂Is halogen.

5. The production method according to claim 4, wherein the acrylic compound is used in an amount of 0.5 to 1.5mol, preferably 0.8 to 1.2mol, relative to 1mol of the ethanolamine-based compound; the dosage of the halogenated polyoxyethylene ether is 0.5-2mol, preferably 1.1-1.5 mol;

preferably, the acrylic compound is selected from at least one of acrylic acid, acryloyl chloride, and acrylic anhydride;

preferably, R₂Is Cl or Br.

6. The production process according to claim 4, wherein, in the step (1), the amidation reaction conditions include: the pH value is 8.5-11.5, preferably 9-10; the reaction temperature is 5-75 ℃, preferably 10-65 ℃; the reaction time is 6 to 15 hours, preferably 8 to 10 hours;

in the step (2), the etherification reaction conditions include: the pH value is 8.5-11.5, preferably 9-10; the reaction temperature is 60-90 ℃, preferably 75-85 ℃; the reaction time is 8 to 10 hours, preferably 3 to 4 hours.

7. A compound produced by the production method according to any one of claims 4 to 6.

8. A polymer characterized by comprising a structural unit A represented by formula (9) and a structural unit B represented by formula (10); based on the total weight of the polymer, the content of the structural unit A in the polymer is 2.5-15 wt%, and the content of the structural unit B is 85-97.5 wt%;

in the formula (9), n is an integer of 1 to 8, and M is H, Li, Na, K, or NH₄One kind of (1).

9. The polymer according to claim 8, wherein in formula (9), 1. ltoreq. n.ltoreq.5; m is Li, Na, K and NH₄One of (1);

preferably, 1. ltoreq. n.ltoreq.3; m is Na.

10. The polymer of claim 8 or 9, wherein the polymer has a viscosity average molecular weight of from 1000 to 2100 million, preferably from 1500 to 1800 million;

preferably, the polymer is a random copolymer or a block copolymer, preferably a random copolymer.

11. A method of making a polymer, the method comprising: polymerizing a monomer mixture in water under free radical aqueous solution polymerization conditions in the presence of an initiator, the monomer mixture comprising a monomer represented by formula (11) and a monomer represented by formula (1);

in the formula (1), n is more than or equal to 1 and less than or equal to 8 and is an integer; m is H, Li, Na, K and NH₄One kind of (1).

12. The method according to claim 11, wherein the monomer represented by formula (11) is used in an amount of 2.5 to 15% by weight and the monomer represented by formula (1) is used in an amount of 85 to 97.5% by weight, based on the total weight of the monomer mixture.

13. The process of claim 11 or 12, wherein the free radical aqueous solution polymerization reaction conditions comprise: the reaction temperature is-10 ℃ to 80 ℃; the reaction time is 2-30 hours; the pH value is 5-10;

preferably, the reaction temperature is 5 ℃ to 60 ℃; the reaction time is 8-20 hours; the pH value is 6-10.

14. The method of any one of claims 11-13, wherein the method further comprises, the polymerization reaction is carried out in the presence of a complexing agent and urea;

preferably, the complexing agent is selected from at least one of disodium ethylenediaminetetraacetate, sodium aminotriacetate and diethylenetriaminepentacarboxylate;

preferably, the complexing agent is used in an amount of 0.01 to 0.1 wt%, based on the total weight of the monomer mixture; the urea is used in an amount of 0.01 to 0.1 wt%.

15. The process of any one of claims 11-14, wherein the free radical aqueous solution polymerization reaction is carried out in an inert atmosphere;

preferably, the inert atmosphere is provided by nitrogen and/or a group zero element gas.

16. A polymer made by the method of any one of claims 11-15.

17. Use of a polymer according to any one of claims 8 to 10 and claim 16 as an oil displacing agent.

Technical Field

The invention relates to the field of polymer flooding, in particular to a compound and a preparation method thereof, a polymer and a preparation method and application thereof.

Background

Currently, polyacrylamide (HPAM) solutions are used primarily in tertiary oil recovery in oil fields to increase viscosity, to control fluidity, and to extend swept volume for enhanced oil recovery. In oil fields such as Daqing, Shengli, Henan and Jianghanhan, the technology is widely applied and obtains good oil increasing effect. However, with the increasing production degree of the conventional oil reservoir, the recoverable reserves are reduced sharply, so that the comprehensive high-level mining of the offshore oil reservoir is urgent, and the requirements on the dissolution speed and the oil washing capacity of the polymer are gradually improved. The dissolving and curing time of the ordinary partially hydrolyzed polyacrylamide HPAM in mineralization water is about 120 minutes generally, and a mother liquor tank and a curing tank with huge volumes are needed to ensure that a uniform solution is formed to meet the injection requirement (the content of insoluble substances)<0.1%, filter factor (filterability ratio)<1.5). For an offshore oil reservoir exploitation operation platform, the limited operation space cannot meet the use requirement of a common HPAM. On the other hand, carboxyl group on HPAM polymer chain is Ca²⁺、Mg²⁺Sensitive to ions, insufficient viscosity in high-salinity oil reservoirs, and high viscosity of crude oil andcomplex rock wetting conditions underground make it difficult to efficiently establish the drag coefficient expansion swept volume. Generally, the current polymer flooding technology cannot completely meet the practical application requirements of oil field polymer flooding, especially offshore oil reservoirs. Therefore, it is desired to improve the solubility and salt resistance of the multipolymer from the viewpoint of structure-activity relationship by designing and developing new functional monomers, and attempt to impart other functions to the molecule by introducing new functional structures.

Disclosure of Invention

The invention aims to overcome the defects of limited dissolution and salt resistance of a polymer for oil displacement and insufficient injection tackifying effect in the prior art, and provides a compound and a preparation method thereof, a polymer and a preparation method and application thereof. The compound has both a polyoxyethylene ether long chain and a sulfonic acid group, can obviously improve the solubility and the tackifying property of polymer molecules obtained by polymerization of the compound, and has excellent surface activity.

In order to achieve the above object, a first aspect of the present invention provides a compound characterized in that the compound has a structure represented by formula (1):

wherein n is more than or equal to 1 and less than or equal to 8 and is an integer; m is H, Li, Na, K and NH₄One kind of (1).

In a second aspect, the present invention provides a process for the preparation of a compound, characterised in that the process comprises the steps of:

(1) under the condition of amidation reaction, the ethanolamine compound with the structure shown as the formula (7) reacts with the acrylic compound with the structure shown as the formula (8);

m is H, Li, Na, K and NH₄R1 is OH, Cl or CH₂-one of CH-CHO-;

(2) under the condition of etherification, contacting the product obtained in the step (1) with halogenated polyoxyethylene ether; the general formula of the chlorinated polyoxyethylene ether is HO- (CH)₂CH₂O)_n-CH₂-CH₂-R₂N is an integer of 1 to 8, R₂Is halogen.

In a third aspect, the present invention provides a compound obtainable by the above-described preparation method.

The fourth aspect of the present invention provides a polymer comprising a structural unit a represented by formula (9) and a structural unit B represented by formula (10); based on the total weight of the polymer, the content of the structural unit A in the polymer is 2.5-15 wt%, and the content of the structural unit B is 85-97.5 wt%;

in the formula (9), n is an integer of 1 to 8, and M is H, Li, Na, K, or NH₄One kind of (1).

In a fifth aspect, the present invention provides a method of preparing a polymer, the method comprising: polymerizing a monomer mixture in water under free radical aqueous solution polymerization conditions in the presence of an initiator, the monomer mixture comprising a monomer represented by formula (11) and a monomer represented by formula (1);

in the formula (1), n is more than or equal to 1 and less than or equal to 8 and is an integer; m is one of H, Li, Na, K and NH 4.

In a sixth aspect, the present invention provides a polymer obtainable by the above process.

The seventh aspect of the present invention provides the use of the above-mentioned polymer as an oil-displacing agent.

Through the technical scheme, the compound, the preparation method thereof, the polymer, the preparation method and the application thereof provided by the invention have the following beneficial effects:

the compound provided by the invention has a long polyoxyethylene ether chain and a sulfonic acid group, can obviously improve the solubility and the thickening property of polymer molecules obtained by polymerizing the compound, and has excellent surface activity.

Furthermore, the polymer provided by the invention has high apparent viscosity, obviously shortens the dissolving time, has certain activity, and can be used as an oil displacement agent for high-salinity offshore oil reservoirs.

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.

In a first aspect, the present invention provides a compound having a structure represented by formula (1):

wherein n is more than or equal to 1 and less than or equal to 8 and is an integer; m is H, Li, Na, K and NH₄One kind of (1).

In the invention, the inventor researches and discovers that when the compound simultaneously has a polyoxyethylene ether long chain and a sulfonic acid group, the compound shows good solubility and surface activity, and particularly, the compound can show good solubility due to the polar sulfonic acid group, and simultaneously the strong hydration performance and the electrostatic repulsion greatly increase the hydrodynamic volume of the molecular chain and show better tackifying effect; the long chain of the polyoxyethylene ether has good water solubility, and in addition, water molecules are promoted to enter and wrap the carbon chain structure, so that the process from swelling to dissolving is accelerated; and the molecular arrangement is influenced through interaction, so that excellent surface activity is brought to the monomer, and the monomer and the polymer prepared from the monomer have functional activity.

Although the instant active functional compound provided by the invention only needs to have the structure shown in the formula (1), in order to enable a polymer obtained by copolymerizing the instant active functional compound with other monomers to have better performance, the monomer is preferably 1-5; m is Li, Na, K and NH₄One kind of (1).

More preferably, 2. ltoreq. n.ltoreq.5 and M is Na from the viewpoint of availability of raw materials and economy.

According to the present invention, the compound has a structure represented by one of formula (2) to formula (6):

in a second aspect, the present invention provides a process for the preparation of a compound, characterised in that the process comprises the steps of:

(1) under the condition of amidation reaction, the ethanolamine compound with the structure shown as the formula (7) reacts with the acrylic compound with the structure shown as the formula (8);

m is H, Li, Na, K and NH₄R1 is OH, Cl or CH₂-one of CH-CHO-;

(2) under the condition of etherification, contacting the product obtained in the step (1) with halogenated polyoxyethylene ether; the general formula of the halogenated polyoxyethylene ether is HO- (CH)₂CH₂O)_n-CH₂-CH₂-R₂N is an integer of 1 to 8, R₂Is halogen.

In the present invention, the amount of each raw material used in the production of the compound is not particularly limited, and for example, the amount of the acrylic compound used is 0.5 to 1.5mol, preferably 0.8 to 1.2mol, relative to 1mol of the ethanolamine-based compound; the dosage of the halogenated polyoxyethylene ether is 0.5-2.0mol, preferably 1.1-1.5 mol.

According to the present invention, the acrylic compound is at least one selected from the group consisting of acrylic acid, acryloyl chloride, and acrylic anhydride; r₂Is Cl or Br.

In the present invention, in the amidation reaction and the etherification reaction in steps (1) and (2), the pH may be 8.5 to 11.5, preferably 9 to 10, independently of each other. The method of adjusting the pH of the reaction system to the above range is well known to those skilled in the art, and for example, a weakly basic compound may be generally added to the reaction system. The basic compound may be an organic basic compound and/or an inorganic basic compound, and is particularly preferably at least one of triethylamine, potassium carbonate, and sodium carbonate, from the viewpoint of availability of raw materials.

In the present invention, in step (1), the amidation reaction conditions generally include: the reaction temperature is 5-75 ℃, and the reaction time is 6-15 hours; preferably, the amidation reaction conditions include: the reaction temperature is 10-65 ℃ and the reaction time is 8-10 hours.

In the invention, in the step (2), the etherification reaction conditions generally include a reaction temperature of 60-90 ℃ and a reaction time of 2-5 hours; preferably, the etherification reaction conditions include a reaction temperature of 75 to 85 ℃ and a reaction time of 3 to 4 hours.

According to a preferred embodiment of the invention, the compound is prepared by:

(1) dissolving ethanolamine compounds in a solvent under an alkaline condition, slowly dropwise adding acryloyl chloride under a low temperature condition of (-5 ℃ to 0 ℃), continuously stirring at room temperature for a period of time (0.5 to 3 hours) after dropwise adding is finished, and then purifying reaction products;

(2) and (2) heating and refluxing the purified product obtained in the step (1) and the halogenated polyoxyethylene ether at the temperature of 60-90 ℃ for 8-10 hours under an alkaline condition, and then purifying.

The purification methods of the present invention are not particularly limited, and for example, purification can be performed by extraction spin-drying, recrystallization, column chromatography, or the like, independently of each other. According to a particular embodiment of the invention, the purification is carried out as follows: and adding water to the reaction product for quenching, extracting by using ethyl acetate, drying an organic phase obtained by extraction by using sodium sulfate, spin-drying a dried product, and then recrystallizing by using n-hexane and/or dichloromethane.

In the present invention, in step (1), it is preferable to provide the low temperature condition by using an ice water bath or an ice salt (sodium chloride) bath.

In a third aspect, the present invention provides a compound obtained by the above-mentioned production method.

The fourth aspect of the present invention provides a polymer comprising a structural unit a represented by formula (9) and a structural unit B represented by formula (10); based on the total weight of the polymer, the content of the structural unit A in the polymer is 2.5-15 wt%, and the content of the structural unit B is 85-97.5 wt%;

in the formula (9), n is an integer of 1 to 8, and M is H, Li, Na, K, or NH₄One kind of (1).

Although the invention provides the polymer as long as the polymer has the structural unit A shown in the formula (9), in order to enable the polymer to have better instant dissolution performance and functional activity, preferably, the structural unit A shown in the formula (9) has 1 ≦ n ≦ 5; m is Li, Na, K and NH₄One kind of (1).

More preferably, 2. ltoreq. n.ltoreq.5 and M is Na from the viewpoint of availability of raw materials and economy.

Further, in order to obtain a polymer having more excellent instant property and functional activity, the content of the structural unit a in the polymer is preferably 2.5 to 7.5% by weight, and the content of the structural unit B is preferably 97.5 to 92.5% by weight, based on the total weight of the polymer.

In the invention, the monomer feeding amount is adopted to determine the contents of the structural unit A and the structural unit B in the polymer, specifically, the feeding ratio of each monomer actually participating in polymerization is determined by testing the content of unreacted monomers, and then the content of each structural unit in the polymer is determined.

Further, in the present invention, when the content of each unreacted monomer in the tested polymer is 0.1% by weight or less, it is indicated that substantially all the monomer participates in the polymerization reaction. Specifically, the content of the residual monomer is measured by liquid chromatography.

According to the invention, the viscosity average molecular weight of the polymer may be between 1000 and 2100 million, preferably between 1500 and 1800 million. Further, the polymer may be a random copolymer or a block copolymer, preferably a random copolymer.

In the present invention, the viscosity average molecular weight of the polymer is determined by a one-point method using an Ubbelohde viscometer according to the formula M ([ eta ])]/K)^1/αTo calculate the viscosity average molecular weight of the polymer, where K is 4.75X 10^-3，α＝0.80，[η]Is the intrinsic viscosity.

In the present invention, the apparent viscosity of the polymer is more than 55 mPas, preferably 65 mPas or more.

In the present invention, the apparent viscosity of the polymer is measured with a Brookfield viscometer at 65 ℃ and a mineralization degree of 8100mg/L of the simulated seawater.

In the present invention, the oil-dispersing ability of the polymer is not less than 70%, preferably not less than 75%.

In the present invention, the oil-dispersing ability of the polymer is measured by mixing a solution of the polymer in a predetermined preparation water at a predetermined concentration, then mixing and shaking the crude oil and the solution in a predetermined ratio, standing the mixture at a predetermined temperature, and separating oil from water after 24 hours. The stronger the oil dispersing ability, the less easily the oil and water are separated. The determination was carried out according to the Q/SH 10201957-2008 standard. For oil displacement agents, it is required to improve the oil dispersing ability while ensuring the apparent viscosity.

A fifth aspect of the present invention provides a method of preparing a polymer, characterized in that the method comprises: polymerizing a monomer mixture in water under free radical aqueous solution polymerization conditions in the presence of an initiator, the monomer mixture comprising a monomer represented by formula (11) and a monomer represented by formula (1);

in the formula (1), n is more than or equal to 1 and less than or equal to 8 and is an integer; m is H, Li, Na, K and NH₄One kind of (1).

In the present invention, the weight ratio between the monomers in the monomer mixture at the start of the solution polymerization reaction may vary within a certain range, and preferably, the monomer represented by formula (11) is used in an amount of 2.5 to 15% by weight and the monomer represented by formula (1) is used in an amount of 85 to 97.5% by weight, based on the total weight of the monomer mixture.

Further, the monomer represented by the formula (11) is used in an amount of 92.5 to 97.5% by weight and the monomer represented by the formula (1) is used in an amount of 2.5 to 7.5% by weight, based on the total weight of the monomer mixture.

In the present invention, the initiator may be any initiator commonly used in the art, and may be selected from, for example, azo-based initiators and/or redox-based initiators, preferably redox-based initiators. Wherein the redox initiator contains both an oxidizing agent and a reducing agent. Specifically, the redox initiator is selected from one or more of sulfate-sulfite, persulfate-thiourea, persulfate-organic salt, persulfate-sulfite and ammonium persulfate-fatty amine. Wherein, the sulfate-sulfite can be selected from one or more of sodium sulfate-sodium sulfite, potassium sulfate-potassium sulfite and ammonium sulfate-ammonium sulfite; the persulfate-thiourea can be one or more selected from sodium persulfate-thiourea, potassium persulfate-thiourea and ammonium persulfate-thiourea; the persulfate-organic salt can be selected from one or more of sodium persulfate-potassium acetate, potassium persulfate-potassium acetate and ammonium persulfate-ammonium acetate; the persulfate-sulfite can be ammonium persulfate-sodium bisulfite; the ammonium persulfate-fatty amine may be selected from one or more of ammonium persulfate-N, N-tetramethylethylenediamine and ammonium persulfate-diethylamine. In addition, the amount of the initiator can be selected conventionally in the art, and is known to those skilled in the art, and will not be described herein.

According to the present invention, the conditions of the polymerization reaction may be conventionally selected in the art. For example, the conditions of the polymerization reaction may include: the temperature is-10 ℃ to 80 ℃, preferably 5 ℃ to 60 ℃; the time is 2 to 30 hours, preferably 8 to 20 hours; the pH value is 5-10, preferably 6-10.

According to a preferred embodiment of the invention, the polymerization is carried out in the presence of a complexing agent and urea, and the manner and conditions of the polymerization are as follows: dissolving the monomer mixture in water, adjusting the pH value of the obtained water solution of the monomer mixture to 6-10, then adding a complexing agent and urea, introducing nitrogen into the reaction system at the temperature of 5-15 ℃ for 10-30 minutes, then adding an initiator, introducing the nitrogen for 5-30 minutes until the reaction solution becomes viscous, and then stopping introducing the nitrogen and carrying out adiabatic polymerization for 4-10 hours. The inventors of the present invention have unexpectedly found that the polymer obtained by using the above polymerization manner and polymerization conditions has more excellent solubility and functional activity.

In the invention, the urea is used for increasing the solubility and stability of polyacrylamide, and the complexing agent is used for complexing metal ions, improving the conversion rate of polymerized monomers and playing a role in solubilization. The complexing agent may be selected from at least one of disodium ethylenediaminetetraacetate (EDTA-2Na), sodium aminotriacetate (NTA) and Diethylenetriaminepentacarboxylate (DTPA), preferably disodium ethylenediaminetetraacetate (EDTA-2 Na). The amount of the complexing agent is 0.01-0.1 wt% of the total weight of the monomer mixture; the urea is used in an amount of 0.01 to 0.1% by weight based on the total weight of the monomer mixture. In addition, the complexing agent and urea are generally used in the form of their aqueous solutions, wherein the aqueous solution of the complexing agent is preferably an aqueous solution of EDTA-2Na having a concentration of 1 wt%, and the aqueous solution of urea is preferably an aqueous solution of urea having a concentration of 1 wt%.

In addition, in order to overcome oxygen inhibition, a polymer having a larger molecular weight is obtained, and preferably, the polymerization reaction is carried out in an inert atmosphere. The inert gas used for maintaining the inert atmosphere may be any of various gases or gas mixtures which do not react with the raw materials and products, and may be at least one of nitrogen gas and group zero element gas in the periodic table of elements.

In a sixth aspect, the present invention provides a polymer obtainable by the above process.

The seventh aspect of the present invention provides the use of the above-mentioned polymer as an oil-displacing agent.

The present invention will be described in detail below by way of examples.

In the following preparation examples, nuclear magnetic data of the compounds were measured by a nuclear magnetic resonance spectrometer (available from Bruker, switzerland, 300MHz in resolution), and the samples were dissolved with a deuterated reagent and tested at room temperature.

In the following examples, the performance test of the product was carried out using the following method:

1) according to the method prescribed in GB12005.10-92, using Ubbelohde viscometer and adopting one-point method, according to formula M ([ eta η ═ M)]/K)^1/αTo calculate the viscosity average molecular weight of the polymer (M is the viscosity average molecular weight), where K is 4.75X 10^-3，α＝0.80，[η]Is the intrinsic viscosity;

2) the apparent viscosity of the polymer was determined with a Brookfield viscometer using a simulated seawater at a temperature of 65 ℃ and a degree of mineralization of 8100 mg/L.

3) The oil dispersing ability was measured according to the Q/SH 10201957-2008 standard.

4) The content of each structural unit in the polymer is calculated according to the feeding amount and the balance of raw materials.

The raw materials used in the preparation examples, examples and comparative examples of the present invention are commercially available.

Preparation example 1

Preparation example 1 is intended to illustrate Compound M1 provided by the present invention and a method for preparing the same.

Sodium 1-hydroxy-2-aminoethanesulfonate (16.2989g, 100mmol) was added to a dry three-necked flask, followed by addition of 250mL of anhydrous THF for dissolutionAfter decomposition, triethylamine (11.1301g, 110mmol) was added, the mixture was dissolved with stirring at room temperature and 25 ℃ and the whole system was cooled to 0 ℃ in a brine bath and acryloyl chloride (9.0521g, 110mmol) was added slowly dropwise while maintaining the temperature constant. Stirring for 30min after the dropwise addition, naturally returning to room temperature of 25 ℃ after the reaction is finished, dropwise adding water (100mL) to quench the reaction system, extracting the reaction product with diethyl ether (75mL multiplied by 3), and adding Na₂SO₄The organic phase was dried, and after spin-drying, recrystallization (recrystallization solvent was a mixture of n-hexane and dichloromethane at a volume ratio of 4: 1) gave sodium 2-acrylamido-1-hydroxyethanesulfonate (12.5966g, 58mmol) as a white solid.

2-acrylamido-1-hydroxyethanesulfonic acid sodium salt (12.5966g, 58mmol) was dissolved in tetrahydrofuran (200mL), potassium carbonate (8.8050g, 64mmol) was added thereto, the mixture was stirred well, heated to 75 ℃ under reflux, 2-chloroethoxyethanol (7.5980g, 61mmol) was added thereto, and the reaction was carried out under reflux for 4 hours. Naturally cooling to room temperature after the reaction is finished, then quenching the reaction system by water, then adjusting the pH value of the mixed phase to 9 by using a dilute sodium hydroxide solution, extracting the reaction product by using ether (75mL multiplied by 3), repeatedly using saturated sodium chloride washing liquor and Na₂SO₄The organic phase was dried, spun-dried and recrystallized (the recrystallization solvent was a mixture of dichloromethane and water at a volume ratio of 4: 1) to obtain compound M1(7.3269g, 24 mmol).

The reaction process is as follows:

m1 has a structure represented by formula (1), wherein n is 1 and M is Na.

The structure of the white waxy solid M1 was identified as follows:

¹H NMR(300MHz,CDCl₃)δ:8.15(s,1H),6.37(m,1H),5.98(d,1H),5.41(d,1H),4.89(t,1H),3.83(d,1H),3.77-3.25(m,9H)；¹³C NMR(75MHz,CDCl₃)δ:168.9,134.1,126.8,105.4,70.4,70.1,66.7,61.4,40.8。

preparation example 2

Preparation example 2 is intended to illustrate Compound M2 provided by the present invention and a method for preparing the same.

Sodium 1-hydroxy-2-aminoethanesulfonate (16.2989g, 100mmol) was added to a dry three-necked flask, followed by addition of 250mL of anhydrous THF for dissolution, triethylamine (11.1301g, 110mmol) was added thereto, and after stirring and dissolution at room temperature of 25 ℃, the whole was cooled to 0 ℃ in a saline bath, and acryloyl chloride (9.0521g, 110mmol) was slowly added dropwise while maintaining the temperature constant. Stirring for 30min after the dropwise addition, naturally returning to room temperature of 25 ℃ after the reaction is finished, dropwise adding water (100mL) to quench the reaction system, extracting the reaction product with diethyl ether (75mL multiplied by 3), and adding Na₂SO₄The organic phase was dried, and after spin-drying, recrystallization (recrystallization solvent was a mixture of n-hexane and dichloromethane at a volume ratio of 4: 1) gave sodium 2-acrylamido-1-hydroxyethanesulfonate (12.5966g, 58mmol) as a white solid.

2-acrylamido-1-hydroxyethanesulfonic acid sodium salt (12.5966g, 58mmol) was dissolved in tetrahydrofuran (200mL), potassium carbonate (8.8050g, 64mmol) was added thereto, the mixture was stirred well, heated to 75 ℃ under reflux, 2-chloroethoxyethanol (7.5980g, 61mmol) was added thereto, and the reaction was carried out under reflux for 4 hours. Naturally cooling to room temperature after the reaction is finished, then quenching the reaction system by water, then adjusting the pH value of a mixed phase to 4 by using a dilute hydrochloric acid solution, extracting a reaction product by using ether (75mL multiplied by 3), repeatedly using saturated sodium chloride washing liquor and Na₂SO₄The organic phase was dried, and after spin-drying, recrystallization (recrystallization solvent was a mixture of n-hexane and dichloromethane at a volume ratio of 2: 1) was carried out to obtain compound M2(5.6661g, 20 mmol).

The reaction process is as follows:

m2 has a structure represented by formula (1), wherein n is 1 and M is H.

The structure of the yellow waxy solid M2 was identified as follows:

¹H NMR(300MHz,CDCl₃)δ:8.13(s,1H),6.40(m,1H),5.99(d,1H),5.41(d,1H),4.85(t,1H),3.82(d,1H),3.76-3.25(m,9H),1.57(bs,1H)；¹³C NMR(75MHz,CDCl₃)δ:168.7,134.2,136.0,105.6,70.5,70.2,66.7,61.5,41.2。

preparation example 3

Preparation example 3 is intended to illustrate Compound M3 provided by the present invention and a method for preparing the same.

Sodium 1-hydroxy-2-aminoethanesulfonate (16.2989g, 100mmol) was added to a dry three-necked flask, followed by addition of 250mL of anhydrous THF for dissolution, triethylamine (11.1301g, 110mmol) was added thereto, and after stirring and dissolution at room temperature of 25 ℃, the whole was cooled to 0 ℃ in a saline bath, and acryloyl chloride (9.0521g, 110mmol) was slowly added dropwise while maintaining the temperature constant. Stirring for 30min after the dropwise addition, naturally returning to room temperature of 25 ℃ after the reaction is finished, dropwise adding water (100mL) to quench the reaction system, extracting the reaction product with diethyl ether (75mL multiplied by 3), and adding Na₂SO₄The organic phase was dried, and after spin-drying, recrystallization (recrystallization solvent was a mixture of n-hexane and dichloromethane at a volume ratio of 4: 1) gave sodium 2-acrylamido-1-hydroxyethanesulfonate (12.5966g, 58mmol) as a white solid.

2-acrylamide-1-hydroxyethanesulfonic acid sodium salt (12.5966g, 58mmol) is dissolved in tetrahydrofuran (200mL), potassium carbonate (8.8050g, 64mmol) is added, the mixture is stirred uniformly, heated to 75 ℃ and refluxed, chlorinated polyoxyethylene ether (10.2859g, 61mmol) is added, and the reflux reaction is carried out for 4 hours. Naturally cooling to room temperature after the reaction is finished, then quenching the reaction system by water, then adjusting the pH value of a mixed phase to 9 by using a sodium hydroxide solution, extracting a reaction product by using ether (75mL multiplied by 3), repeatedly using saturated sodium chloride washing liquor and Na₂SO₄The organic phase was dried, and after spin-drying, recrystallization (recrystallization solvent was a mixture of n-hexane and dichloromethane at a volume ratio of 2: 1) was carried out to obtain compound M3(7.2018g, 22 mmol).

The reaction process is as follows:

m3 has a structure represented by formula (1), wherein n is 2 and M is Na.

The structure of the yellow waxy solid M3 was identified as follows:

¹H NMR(300MHz,CDCl₃)δ:8.14(s,1H),6.42(m,1H),5.98(d,1H),5.41(d,1H),4.86(t,1H),3.81(d,1H),3.79-3.22(m,11H),1.64(bs,1H)；¹³C NMR(75MHz,CDCl₃)δ:168.9,134.1,126.7,104.9,70.5,70.3,70.2,66.2,61.5,41.3。

preparation example 4

Preparation example 4 is intended to illustrate Compound M4 provided by the present invention and a method for preparing the same.

Sodium 1-hydroxy-2-aminoethanesulfonate (16.2989g, 100mmol) was added to a dry three-necked flask, followed by addition of 250mL of anhydrous THF for dissolution, triethylamine (11.1301g, 110mmol) was added thereto, and after stirring and dissolution at room temperature of 25 ℃, the whole was cooled to 0 ℃ in a saline bath, and acryloyl chloride (9.0521g, 110mmol) was slowly added dropwise while maintaining the temperature constant. Stirring for 30min after the dropwise addition, naturally returning to room temperature of 25 ℃ after the reaction is finished, dropwise adding ammonia water (100mL, 15% concentration) to quench the reaction system, extracting the reaction product with diethyl ether (75mL multiplied by 3), and adding Na₂SO₄The organic phase was dried, and after spin-drying, recrystallization (recrystallization solvent was a mixture of n-hexane and dichloromethane at a volume ratio of 4: 1) gave ammonium 2-acrylamido-1-hydroxyethanesulfonate (7.8517g, 37mmol) as a white solid.

2-acrylamide-1-hydroxyethanesulfonic acid sodium salt (7.8517g, 37mmol) is dissolved in tetrahydrofuran (200mL), potassium carbonate (5.6577g, 41mmol) is added, the mixture is stirred uniformly, heated to 75 ℃ and refluxed, chlorinated polyoxyethylene ether (16.8849g, 39mmol) is added, and the reflux reaction is carried out for 4 hours. Naturally cooling to room temperature after the reaction is finished, then quenching the reaction system by water, then adjusting the pH value of a mixed phase to 9 by using a sodium hydroxide solution, extracting a reaction product by using ether (75mL multiplied by 3), repeatedly using saturated sodium chloride washing liquor and Na₂SO₄The organic phase was dried, and after spin-drying, recrystallization (recrystallization solvent was a mixture of n-hexane and dichloromethane at a volume ratio of 2: 1) was carried out to obtain compound M4(10.9486g, 18 mmol).

The reaction process is as follows:

m4 has a structure represented by formula (1), wherein n is 8 and M is NH₄。

The structure of the white waxy solid M4 was identified as follows:

¹H NMR(300MHz,CDCl₃)δ:8.37(s,1H),7.37(s,4H),6.48(m,1H),6.10(d,1H),5.77(d,1H),5.42(t,1H),4.41(bs,1H),3.77-3.24(m,38H)；¹³C NMR(75MHz,CDCl₃)δ:167.9,133.1,126.8,107.2,70.4,70.3,66.1,61.3,41.4。

preparation example 5

Preparation example 5 is intended to illustrate Compound M5 provided by the present invention and a method for preparing the same.

Sodium 1-hydroxy-2-aminoethanesulfonate (16.2989g, 100mmol) was added to a dry three-necked flask, followed by addition of 250mL of anhydrous THF for dissolution, triethylamine (11.1301g, 110mmol) was added thereto, and after stirring and dissolution at room temperature of 25 ℃, the whole was cooled to 0 ℃ in a saline bath, and acryloyl chloride (9.0521g, 110mmol) was slowly added dropwise while maintaining the temperature constant. Stirring for 30min after the dropwise addition, naturally returning to room temperature of 25 ℃ after the reaction is finished, dropwise adding water (100mL) to quench the reaction system, extracting the reaction product with diethyl ether (75mL multiplied by 3), and adding Na₂SO₄The organic phase was dried, and after spin-drying, recrystallization (recrystallization solvent was a mixture of n-hexane and dichloromethane at a volume ratio of 4: 1) gave sodium 2-acrylamido-1-hydroxyethanesulfonate (12.5966g, 58mmol) as a white solid.

2-acrylamide-1-hydroxyethanesulfonic acid sodium salt (12.5966g, 58mmol) is dissolved in tetrahydrofuran (200mL), potassium carbonate (8.8050g, 64mmol) is added, the mixture is stirred uniformly, heated to 75 ℃ and refluxed, chlorinated polyoxyethylene ether (18.3459g, 61mmol) is added, and the reflux reaction is carried out for 4 hours. Naturally cooling to room temperature after the reaction is finished, then quenching the reaction system by water, then adjusting the pH value of the mixed phase to 9 by using sodium hydroxide solution, extracting the reaction product by using ether (75mL multiplied by 3), and repeatedly using saturated solutionAnd sodium chloride lotion, Na₂SO₄The organic phase was dried, and after spin-drying, recrystallization (recrystallization solvent was a mixture of n-hexane and dichloromethane at a volume ratio of 8: 1) was carried out to obtain compound M5(11.5555g, 24 mmol).

The reaction process is as follows:

m5 has a structure represented by formula (1), wherein n is 5 and M is Na.

The structure of the white waxy solid M5 was identified as follows:

¹H NMR(300MHz,CDCl₃)δ:8.77(s,1H),6.57(m,1H),6.11(d,1H),5.89(d,1H),5.14(bs,1H),5.05(t,1H),3.97(d,2H),3.50-3.70(m,24H)；¹³C NMR(75MHz,CDCl₃)δ:170.1,134.8,127.1,108.9,70.6,70.5,66.3,62.0,41.4。

example 1

This example serves to illustrate the polymers provided by the present invention and their preparation.

45g of acrylamide and 5g of compound M1 were dissolved in 300g of deionized water and the pH was adjusted to 7 with sodium hydroxide; then 0.8g of EDTA-2Na aqueous solution (1 wt%) and 0.8g of urea aqueous solution (1 wt%) were added and mixed well; the mixture was then cooled to 5 ℃ and then charged into a vessel with nitrogen gas for 30min, after which 0.8g of an aqueous ammonium persulfate solution (1 wt%) and 1.6g of an aqueous sodium bisulfite solution (1 wt%) were added, followed by nitrogen gas introduction for another 10 min until the reaction solution started to become viscous. The drum nitrogen was then stopped and the polymerization was carried out adiabatically for 8 h. Shearing the colloid into strips by using scissors after the polymerization reaction is finished, preparing the strip colloid into colloidal particles by using a granulator, hydrolyzing the colloidal particles by using 40 wt% of sodium hydroxide solution in a water bath at 90 ℃ for 2 hours, drying in an oven at 50 ℃, and drying by using

Pulverizing into polymer particles of 20-80 meshes. According to the test, the viscosity average molecular weight of the polymer is 1670 ten thousand, the content of the structural unit of the acrylamide in the polymer is 90 weight percent, and the content of the structural unit of the compound M1 is 10 weight percent; the polymer was completely dissolved and matured within 50 minutes, and had an apparent viscosity of 71.7 mPas and an oil-dispersing ability of 78%.

Example 2

This example serves to illustrate the polymers provided by the present invention and their preparation.

Dissolving 48g of acrylamide and 2g of compound M1 in 300g of deionized water, and adjusting the pH value to 7 with sodium hydroxide; then 0.8g of EDTA-2Na aqueous solution (1 wt%) and 0.8g of urea aqueous solution (1 wt%) were added and mixed well; the mixture was then cooled to 5 ℃ and then charged into a vessel with nitrogen gas for 30min, after which 1g of an aqueous ammonium persulfate solution (1 wt%) and 1.6g of an aqueous sodium bisulfite solution (1 wt%) were added, followed by nitrogen gas introduction for another 10 min until the reaction solution started to become viscous. The drum nitrogen was then stopped and the polymerization was carried out adiabatically for 8 h. After the polymerization reaction, cutting the colloid into strips by using scissors, preparing the strip colloid into colloidal particles by using a granulator, hydrolyzing the colloidal particles for 2 hours by using 40 wt% of sodium hydroxide solution in a water bath at 90 ℃, drying in an oven at about 50 ℃, and crushing into polymer particles with 20-80 meshes by using a pulverizer. According to the test, the viscosity average molecular weight of the polymer is 1610 ten thousand, the content of the structural unit of the acrylamide in the polymer is 96 weight percent, and the content of the structural unit of the compound M1 is 4 weight percent; the polymer was completely dissolved and matured within 55 minutes, and had an apparent viscosity of 75.1 mPas and an oil-dispersing ability of 73%.

Example 3

Dissolving 48g of acrylamide and 2g of compound M2 in 300g of deionized water, and adjusting the pH value to 7 with sodium hydroxide; then 0.8g of EDTA-2Na aqueous solution (1 wt%) and 0.8g of urea aqueous solution (1 wt%) were added and mixed well; the mixture was then cooled to 5 ℃ and then charged into a vessel with nitrogen gas for 30min, after which 1g of an aqueous ammonium persulfate solution (1 wt%) and 1.6g of an aqueous sodium bisulfite solution (1 wt%) were added, followed by nitrogen gas introduction for another 10 min until the reaction solution started to become viscous. The drum nitrogen was then stopped and the polymerization was carried out adiabatically for 8 h. After the polymerization reaction, cutting the colloid into strips by using scissors, preparing the strip colloid into colloidal particles by using a granulator, hydrolyzing the colloidal particles for 2 hours by using 40 wt% of sodium hydroxide solution in a water bath at 90 ℃, drying in an oven at about 50 ℃, and crushing into polymer particles with 20-80 meshes by using a pulverizer. In the polymer, the content of the structural unit of acrylamide was 96% by weight, and the content of the structural unit of compound M2 was 4% by weight; the viscosity average molecular weight of the polymer is 1540ten thousand through testing, the polymer is completely dissolved and cured within 60 minutes, the apparent viscosity is 69.8mPa & s, and the oil dispersing capacity is 74%.

Example 4

This example serves to illustrate the polymers provided by the present invention and their preparation.

Dissolving 48g of acrylamide and 2g of compound M3 in 300g of deionized water, and adjusting the pH value to 7 with sodium hydroxide; then 0.8g of EDTA-2Na aqueous solution (1 wt%) and 0.8g of urea aqueous solution (1 wt%) were added and mixed well; the mixture was then cooled to 5 ℃ and then charged into a vessel with nitrogen gas for 30min, after which 1g of an aqueous ammonium persulfate solution (1 wt%) and 1.6g of an aqueous sodium bisulfite solution (1 wt%) were added, followed by nitrogen gas introduction for another 10 min until the reaction solution started to become viscous. The drum nitrogen was then stopped and the polymerization was carried out adiabatically for 8 h. After the polymerization reaction, cutting the colloid into strips by using scissors, preparing the strip colloid into colloidal particles by using a granulator, hydrolyzing the colloidal particles for 2 hours by using 40 wt% of sodium hydroxide solution in a water bath at 90 ℃, drying in an oven at about 50 ℃, and crushing into polymer particles with 20-80 meshes by using a pulverizer. The content of acrylamide structural units in the polymer was 96% by weight, and the content of structural units of compound M3 was 4% by weight. The viscosity average molecular weight of the polymer is 1690 ten thousand by test, the polymer is completely dissolved and cured within 50 minutes, the apparent viscosity is 77.8 mPa.s, and the oil dispersing capacity is 72 percent.

Example 5

Dissolving 48g of acrylamide and 2g of compound M4 in 300g of deionized water, and adjusting the pH value to 7 with sodium hydroxide; then 0.8g of EDTA-2Na aqueous solution (1 wt%) and 0.8g of urea aqueous solution (1 wt%) were added and mixed well; the mixture was then cooled to 5 ℃ and then charged into a vessel with nitrogen gas for 30min, after which 1g of an aqueous ammonium persulfate solution (1 wt%) and 1.6g of an aqueous sodium bisulfite solution (1 wt%) were added, followed by nitrogen gas introduction for another 10 min until the reaction solution started to become viscous. The drum nitrogen was then stopped and the polymerization was carried out adiabatically for 8 h. After the polymerization reaction, cutting the colloid into strips by using scissors, preparing the strip colloid into colloidal particles by using a granulator, hydrolyzing the colloidal particles for 2 hours by using 40 wt% of sodium hydroxide solution in a water bath at 90 ℃, drying in an oven at about 50 ℃, and crushing into polymer particles with 20-80 meshes by using a pulverizer. The content of acrylamide structural units in the polymer was 96% by weight, and the content of structural units of compound M1 was 4% by weight. The viscosity average molecular weight of the polymer is 1470 ten thousand through tests, the polymer is completely dissolved and cured within 55 minutes, the apparent viscosity is 72.1mPa & s, and the oil dispersing capacity is 82%.

Example 6

Dissolving 48g of acrylamide and 2g of compound M5 in 300g of deionized water, and adjusting the pH value to 7 with sodium hydroxide; then 0.8g of EDTA-2Na aqueous solution (1 wt%) and 0.8g of urea aqueous solution (1 wt%) were added and mixed well; the mixture was then cooled to 5 ℃ and then charged into a vessel with nitrogen gas for 30min, after which 1g of an aqueous ammonium persulfate solution (1 wt%) and 1.6g of an aqueous sodium bisulfite solution (1 wt%) were added, followed by nitrogen gas introduction for another 10 min until the reaction solution started to become viscous. The drum nitrogen was then stopped and the polymerization was carried out adiabatically for 8 h. After the polymerization reaction, cutting the colloid into strips by using scissors, preparing the strip colloid into colloidal particles by using a granulator, hydrolyzing the colloidal particles for 2 hours by using 40 wt% of sodium hydroxide solution in a water bath at 90 ℃, drying in an oven at about 50 ℃, and crushing into polymer particles with 20-80 meshes by using a pulverizer. The content of acrylamide structural units in the polymer was 96% by weight, and the content of structural units of compound M1 was 4% by weight. The viscosity average molecular weight of the polymer is 1730 ten thousand, the polymer is completely dissolved and cured within 45 minutes, the apparent viscosity is 80.4 mPa.s, and the oil dispersing capacity is 81 percent.

Comparative example 1

This comparative example serves to illustrate a reference conventional polymer and a method for its preparation.

A polymer was prepared according to the method described in example 1, except that compound M1 was not added, the resulting polymer had a viscosity average molecular weight of 2010 ten thousand, a uniform dissolution ripening time of 105 minutes, an apparent viscosity of 55.2 mPas, and no significant oil dispersing ability.

Comparative example 2

This comparative example serves to illustrate a reference functional polymer and a method for its preparation.

A functional polymer was prepared according to the procedure described in example 1, except that the same parts by weight of 2-acrylamido-2-methyl-propanesulfonic acid was used in place of the compound M1, and the resulting polymer had a viscosity average molecular weight of 1950 ten thousand, a uniform dissolution ripening time of 95 minutes, an apparent viscosity of 58.6 mPas and an oil dispersing ability of about 20%.

Example 7

This comparative example serves to illustrate a reference functional polymer and a method for its preparation.

30g of acrylamide and 20g of compound M1 were dissolved in 300g of deionized water and the pH was adjusted to 7 with sodium hydroxide; then 0.8g of EDTA-2Na aqueous solution (1 wt%) and 0.8g of urea aqueous solution (1 wt%) were added and mixed well; the mixture was then cooled to 5 ℃ and then charged into a vessel with nitrogen gas for 30min, after which 1g of an aqueous ammonium persulfate solution (1 wt%) and 1.6g of an aqueous sodium bisulfite solution (1 wt%) were added, followed by nitrogen gas introduction for another 10 min until the reaction solution started to become viscous. The drum nitrogen was then stopped and the polymerization was carried out adiabatically for 8 h. After the polymerization reaction, cutting the colloid into strips by using scissors, preparing the strip colloid into colloidal particles by using a granulator, hydrolyzing the colloidal particles for 2 hours by using 40 wt% of sodium hydroxide solution in a water bath at 90 ℃, drying in an oven at about 50 ℃, and crushing into polymer particles with 20-80 meshes by using a pulverizer. The polymer contained acrylamide as a constitutional unit in an amount of 60% by weight and M1 as a constitutional unit in an amount of 40% by weight. The viscosity-average molecular weight of the polymer is 810 ten thousand, the polymer is completely dissolved and cured within 35 minutes, the apparent viscosity is 45.4mPa & s, and the oil dispersing capacity is 87%.

From the results of the above examples, it can be seen that under otherwise identical conditions, the apparent viscosity of the functional polymer obtained in example 1 of the present invention can be 70 mPas or more under the test conditions (temperature 65 ℃ C., degree of mineralization 8100mg/L), whereas the apparent viscosity of the polymer obtained in comparative example 1 under such conditions is only 55.2 mPas, and the apparent viscosity of the polymer obtained in comparative example 2 under such conditions is only 58.6 mPas, and the dissolution aging time is also significantly shortened. Therefore, the apparent viscosity of the polymer obtained by copolymerizing the compound disclosed by the invention and other polymerizable monomers which can be used for preparing the oil-displacing agent composition under the condition is far higher than that of the polymer without the compound disclosed by the invention, the dissolving time is obviously shortened, and meanwhile, the compound has certain activity.

The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.

It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.

In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.