CN105504153A - Fluorine-containing hydrophobic-associating surface-active polyacrylamide and preparation method thereof - Google Patents

Abstract

A fluorine-containing hydrophobic association surface active polyacrylamide, the molecular structure is as follows: Wherein, x=100, y=10-20, z=0.05-1.5, n=4, 6, 8, R, R' are alkyl groups; the advantage is that the prepared polyacrylamide has excellent viscosity-increasing properties, It has temperature and salt resistance properties, can reduce the surface tension of water to 24-32mN/m, and has good application prospects in tertiary oil recovery, drilling fluid and coatings.

Description

A kind of fluorine-containing hydrophobic association surface-active polyacrylamide and its preparation method

technical field

The invention relates to the technical field of water-soluble polymers, in particular to a fluorine-containing hydrophobic association surface-active polyacrylamide and a preparation method thereof.

Background technique

Tertiary oil recovery is the main measure to enhance oil recovery, among which relying on polymer flooding plays an important role. At present, the polymer used in tertiary oil recovery is mainly PAM, but conventional PAM has poor heat resistance, salt resistance and shear resistance, which leads to unsatisfactory oil recovery. In order to increase the recovery factor more, many scholars have proposed the use of compound flooding, that is, binary and three-element compound flooding. For example: Chinese patent "Binary compound flooding composition and its preparation method" CN102220120A; Its preparation method" CN102277146A; Chinese patent "oil displacement composition for tertiary oil recovery and its preparation method" CN102220124A, etc. The recovery of binary and ASP flooding is more obvious than that of polymer flooding, but there are also some defects. Laboratory studies have shown that during polymer binary flooding and ASP flooding, due to the migration of different components Due to the poor speed, chromatographic separation will occur, resulting in the weakening of the synergy between different oil displacement agents and the deterioration of the oil displacement effect.

At the same time, when synthesizing fluorine-containing polyacrylamide, due to the poor water solubility of fluorine-containing hydrophobic monomers, micellar polymerization is generally used. However, there are many shortcomings in the preparation process. First, during the micellar polymerization process, due to the poor water solubility of fluorine-containing hydrophobic monomers, even if surfactants are added to form micelles, the synthesized polyacrylamide contains very little fluorine. ; Secondly, after the synthesis, it is necessary to remove the surfactant through a complex post-treatment process.

Contents of the invention

The purpose of the present invention is to provide a fluorine-containing hydrophobic association polyacrylamide with better viscosification and lower surface tension in view of the chromatographic separation effect of the above-mentioned composite flooding and the technical deficiencies in the polymer synthesis process and its preparation method.

In order to achieve the above purpose, a fluorine-containing hydrophobic association surface-active polyacrylamide has the following molecular structure:

Wherein, x=100, y=10-20, z=0.05-1.5, n=4, 6, 8, R, R' are alkyl groups.

A preparation method of fluorine-containing hydrophobic association surface-active polyacrylamide, specifically comprising the following steps:

Step 1: Synthesis of Surface Active Fluorinated Polymerizable Macromonomer HAPS

①. Synthesis of N-dialkyl perfluoroalkylsulfonamides

Stir and mix the organic amine, triethylamine and organic solvent evenly, then add perfluoroalkylsulfonyl fluoride, then raise the temperature to 30-60°C, and continue the reaction for 4-10 hours; the reaction mixture is washed, dried, and distilled under reduced pressure to obtain the product N-Dialkyl perfluorooctane sulfonamides.

Wherein, the mol ratio of raw materials used is as follows:

Perfluoroalkylsulfonyl fluoride: organic amine: triethylamine is 1:1~2:1.2~2;

Preferably, the washing is sequentially washed with water, washed with 0.5% hydrochloric acid aqueous solution, washed with saturated brine, and dried with anhydrous sodium sulfate;

Preferably, the organic amine is one or more of dimethylamine, diethylamine, dipropylamine, di-n-butylamine, and methylethylamine;

Preferably, the organic solvent is one or more of toluene, isopropanol, isopropyl ether, acetone or xylene;

Preferably, the perfluoroalkylsulfonyl fluoride is one or more of perfluorobutylsulfonyl fluoride, perfluorohexylsulfonyl fluoride and perfluorooctanesulfonyl fluoride.

②, Synthesis of hydroxypropyl chloroacrylate

Mix hydroxypropyl acrylate and organic solvent, add thionyl chloride at 20-35°C under nitrogen gas, react at 40°C-60°C for 4-10 hours; cool, wash, dry, and distill under reduced pressure Obtain hydroxypropyl chlorinated acrylate;

Wherein, the mol ratio of raw materials used is as follows:

Hydroxypropyl acrylate: thionyl chloride is 1:1.5~2;

The organic solvent is one or more of isopropanol, acetone, methylene chloride, pyridine or tetrahydrofuran;

When washing, use NaOH aqueous solution to wash to neutral; dry with anhydrous sodium sulfate.

③. Synthesis of macromonomer HAPS

Mix N-dialkyl perfluoroalkyl sulfonamide and organic solvent, add hydroxypropyl chloroacrylate under the condition of nitrogen gas, react at 30-50°C for 20-48 hours, cool, wash, dry, reduce Pressure distillation to obtain surface active fluorine-containing polymerizable macromonomer HAPS;

Wherein, the mol ratio of raw materials used is as follows:

Hydroxypropyl chloroacrylate: N-dialkyl perfluoroalkyl sulfonamide is 1.5～2:1;

The washing is sequentially washed with 0.05% HCl and saturated brine, and dried with anhydrous sodium sulfate;

Wherein, the organic solvent is one or more of toluene, isopropanol, isopropyl ether, acetone or xylene.

The second step: Synthesis of fluorine-containing hydrophobically associative polyacrylamide

Add HAPS monomer and AM to the AMPS aqueous solution with a pH of 7, and control the total mass fraction of AMPS, AM and HAPS monomer to be 5-25%, wherein the molar ratio of AM, AMPS and HAPS monomer is 100:10- 20: 0.05-1.5; stir after ultrasonication, feed nitrogen, add an initiator accounting for 0.2%-1% of the total mass of the monomer, and control the temperature at 30-50°C; after 4-10 hours of reaction, a colloidal product is obtained, washed, The white precipitate was obtained, dried and pulverized to obtain fluorine-containing hydrophobically associated polyacrylamide;

The initiator is ammonium persulfate and sodium sulfite with a mass ratio of 1:1, or potassium persulfate and sodium bisulfite with a mass ratio of 1:1.

A fluorine-containing hydrophobic association surface-active polyacrylamide and a preparation method thereof have the advantages of:

①. Introduce fluorine-containing surface-active monomers into the molecule. The fluorocarbon chain has strong thermal and chemical stability. Therefore, the synthesized polyacrylamide has strong temperature resistance and can reduce the surface tension of water. It has a good application prospect in tertiary oil recovery, drilling fluid and coating;

②. The fluorocarbon hydrophobic group has low cohesive energy and surface energy, so that the synthesized polymer has strong viscosity-increasing performance and low surface tension;

③. No other surfactants are added in the polymer preparation process, and the cost is low.

Description of drawings

Fig. 1 is the infrared spectrogram of the fluorine-containing hydrophobically associated polyacrylamide obtained in Example 1;

detailed description

A fluorine-containing hydrophobic association surface-active polyacrylamide. The production principle is: firstly synthesize HAPS, a surface-active fluorine-containing polymerizable macromonomer, and then polymerize HAPS, acrylamide and AMPS by soap-free emulsion to obtain fluorine-containing hydrophobic polyacrylamide. Associative polyacrylamide.

Below in conjunction with example the present invention will be further described:

Example one

Step 1: Synthesis of Surface Active Fluorinated Polymerizable Macromonomer HAPS

①. Synthesis of N-dimethylperfluoroalkylsulfonamide

Add 0.1mol dimethylamine, 0.08mol triethylamine and 100mL isopropanol into a three-necked flask equipped with a spherical reflux condenser, a thermometer and a stirrer, stir and mix evenly, and slowly pour into the reaction system through a constant pressure dropping funnel. 0.05mol perfluorooctanesulfonyl fluoride was added dropwise, then the temperature was raised to 40°C, and the reaction was continued for 6h. The reaction mixture was washed successively with water, 0.5% hydrochloric acid aqueous solution, and saturated brine, then dried over anhydrous sodium sulfate, and distilled under reduced pressure to obtain the product N-dimethylperfluorooctanesulfonamide.

②, Synthesis of hydroxypropyl chloroacrylate

Add 0.1mol of hydroxypropyl acrylate and 100mL of dichloromethane into a three-necked flask equipped with a spherical reflux condenser, a thermometer and a stirrer, pass nitrogen gas under stirring, and pour through a constant pressure dropping funnel at 25°C. Slowly add 0.15 mol of thionyl chloride dropwise to the reaction system. After the dropwise addition, react at 40° C. for 8 hours, and absorb the tail gas generated during the reaction with lye. After the reaction was completed, the system was cooled to room temperature, washed with NaOH aqueous solution until neutral, dried over anhydrous sodium sulfate, and distilled under reduced pressure to finally obtain hydroxypropyl chloroacrylate.

③. Synthesis of macromonomer HAPS

Add 0.01mol N-dimethylperfluoroalkylsulfonamide and 150ml of isopropanol into the three-necked flask, stir vigorously and blow nitrogen, slowly add 0.02mol hydroxypropyl chloroacrylate into the three-necked flask, dropwise is completed Then react for 28h. After the reaction is completed, the product is cooled, washed with 0.05% HCl and saturated brine, dried with anhydrous sodium sulfate, and distilled under reduced pressure to obtain HAPS, a surface-active fluorine-containing polymerizable macromonomer.

The second step: Synthesis of fluorine-containing hydrophobically associative polyacrylamide

Add HAPS monomer and AM to the AMPS aqueous solution with a pH of 7, and control the total mass fraction of AMPS, AM and HAPS monomer to 20%, wherein the molar ratio of AM, AMPS and HAPS monomer is 100:10:0.1; After ultrasonication for 30 minutes, stir rapidly, pass nitrogen gas for 30 minutes, add ammonium persulfate-sodium sulfite accounting for 0.05% of the total mass of the monomer as an initiator, and control the temperature at 40°C; after 6 hours of reaction, a colloidal product is obtained, which is washed several times with a small amount of ethanol , a white precipitate was obtained, which was dried and pulverized to obtain fluorine-containing hydrophobically associated polyacrylamide.

The infrared spectrum analysis of the finally obtained fluorine-containing hydrophobically associated polyacrylamide was carried out, and the infrared spectrum in Figure 1 was obtained.

Among them, 3430.36cm ^-1 and 3203.91cm ^-1 are NH stretching vibration peaks of amides, 1655.15cm ^-1 is carbonyl stretching vibration absorption peaks, 2933.03cm ^-1 and 2869.6cm ^-1 are CH symmetrical stretching vibrations of -CH ₂ peak, 1452.75cm ^-1 is the bending vibration of CH, 1307.91cm ^-1 is the stretching vibration of CN, 1185.18 and 1115.18cm ^-1 are the stretching vibration absorption peaks of –CF ₂ and CF ₃ , and 1040.49cm ^-1 is the absorption peak of –SO ₃ - Stretching vibration absorption peak.

Performance evaluation of fluorine-containing surface-active polymers: prepare 0.2% aqueous solution of surface-active polymers, and measure the surface tension of the polymers with a JK99B automatic tensiometer to be 30.2mN/m; The viscosity that obtains polymer is 518.2mpa.s;

Example two

Step 1: Synthesis of Surface Active Fluorinated Polymerizable Macromonomer HAPS

①. Synthesis of N-diethylperfluorobutanesulfonamide

Add 0.2 mol of diethylamine, 0.2 mol of triethylamine and 100 ml of isopropyl ether into a three-necked flask equipped with a spherical reflux condenser, a thermometer and a stirrer, stir and mix evenly, and slowly pour into the reaction system through a constant pressure dropping funnel. 0.1mol perfluorooctanesulfonyl fluoride was added dropwise, then the temperature was raised to 60°C, and the reaction was continued for 10h. The reaction mixture was washed successively with water, 0.5% hydrochloric acid aqueous solution, and saturated brine, then dried over anhydrous sodium sulfate, and distilled under reduced pressure to obtain the product N-diethylperfluorobutanesulfonamide.

②, Synthesis of hydroxypropyl chloroacrylate

Add 0.5mol of hydroxypropyl acrylate and 150ml of acetone into a three-necked flask equipped with a spherical reflux condenser, a thermometer and a stirrer, and pass nitrogen gas under stirring. Slowly add 1 mol of thionyl chloride dropwise to the system. After the dropwise addition, react at 50° C. for 6 hours, and absorb the tail gas generated during the reaction with lye. After the reaction was completed, the system was cooled to room temperature, washed with NaOH aqueous solution until neutral, dried over anhydrous sodium sulfate, and distilled under reduced pressure to finally obtain hydroxypropyl chloroacrylate.

③. Synthesis of macromonomer HAPS

Add 0.1mol of N-diethyl perfluorobutyl sulfonamide and 150ml of isopropanol into the three-necked flask, stir vigorously and blow nitrogen into it, slowly drop 0.2mol of hydroxypropyl chloroacrylate into the three-necked flask, After the dropwise addition was completed, the reaction was carried out for 48h. The product was cooled, washed with 0.05% HCl and saturated brine respectively, dried with anhydrous sodium sulfate, and distilled under reduced pressure to obtain HAPS, a surface-active fluorine-containing polymerizable macromonomer.

The second step: Synthesis of fluorine-containing hydrophobically associative polyacrylamide

Add HAPS monomer and AM to the AMPS aqueous solution with a pH of 8, and control the total mass fraction of AMPS, AM and HAPS monomer to be 10%, wherein the molar ratio of AM, AMPS and HAPS monomer is 100:15:1.5; After ultrasonication for 30 minutes, stir rapidly, and nitrogen gas was introduced for 30 minutes, and potassium persulfate-sodium bisulfite accounting for 0.3% of the total mass of the monomer was added as an initiator, and the temperature was controlled at 45°C; after 10 hours of reaction, a colloidal product was obtained, and a small amount of ethanol was used to After repeated washing, a white precipitate was obtained, which was dried and pulverized to obtain fluorine-containing hydrophobic association polyacrylamide.

Performance evaluation of fluorine-containing surface-active polymers: prepare 0.4% aqueous solution of surface-active polymers, and measure the surface tension of the polymers with a JK99B type automatic tensiometer to be 23.9mN/m; The viscosity that obtains polymer is 7429.5mpa.s;

Example three

Step 1: Synthesis of Surface Active Fluorinated Polymerizable Macromonomer HAPS

①, N-methyl, ethyl perfluorohexylsulfonamide synthesis

Add 0.6mol of N-methylethylamine, 0.75mol of triethylamine and 150ml of acetone into a three-necked flask equipped with a spherical reflux condenser, a thermometer and a stirrer, stir and mix evenly, and pour into the reaction via a constant pressure dropping funnel. 0.4 mol of perfluorohexylsulfonyl fluoride was slowly added dropwise into the system; then the temperature was raised to 35° C., and the reaction was continued for 5 hours. The reaction mixture was washed successively with water, 0.5% hydrochloric acid aqueous solution, and saturated brine, then dried over anhydrous sodium sulfate, and distilled under reduced pressure to obtain the product N-methyl, ethyl perfluorohexylsulfonamide.

②, Synthesis of hydroxypropyl chloroacrylate

Add 0.5mol of hydroxypropyl acrylate and 130ml of tetrahydrofuran into a three-necked flask equipped with a spherical reflux condenser, a thermometer and a stirrer, pass nitrogen gas under stirring, and pass through a constant pressure dropping funnel at 25°C after completion Slowly add 0.75 mol of thionyl chloride dropwise to the reaction system. After the dropwise addition, react at 50° C. for 80 hours, and absorb the tail gas generated during the reaction with alkali solution. After the reaction was completed, the system was cooled to room temperature, washed with NaOH aqueous solution until neutral, dried over anhydrous sodium sulfate, and distilled under reduced pressure to finally obtain hydroxypropyl chloroacrylate.

③. Synthesis of macromonomer HAPS

Add 0.1 mol of N-methyl, ethyl perfluorohexyl sulfonamide and 80ml of isopropanol to the three-necked flask, stir vigorously and blow nitrogen, and slowly drop 0.15 mol of hydroxypropyl chloroacrylate into the three-necked flask , reacted for 40 hours after the dropwise addition; the product was cooled, washed with 0.05% HCl and saturated brine, dried with anhydrous sodium sulfate, and distilled under reduced pressure to obtain HAPS, a surface-active fluorine-containing polymerizable macromonomer.

The second step: Synthesis of fluorine-containing hydrophobically associative polyacrylamide

Add HAPS monomer and AM to the AMPS aqueous solution with a pH of 7.5, and control the total mass fraction of AMPS, AM and HAPS monomer to be 25%, wherein the molar ratio of AM, AMPS and HAPS monomer is 100:20:0.3; After ultrasonication for 30 minutes, stir rapidly, pass nitrogen gas for 30 minutes, add potassium persulfate-sodium bisulfite accounting for 0.8% of the total mass of the monomer as an initiator, and control the temperature at 400°C; after 6 hours of reaction, a colloidal product is obtained, and a small amount of ethanol After repeated washing, a white precipitate was obtained, which was dried and pulverized to obtain fluorine-containing hydrophobic association polyacrylamide.

Performance evaluation of fluorine-containing surface-active polymers: prepare 0.3% aqueous solution of surface-active polymers, and measure the surface tension of the polymers with a JK99B automatic tensiometer to be 27.4.2mN/m; The measured polymer viscosity is 3273.3mpa.s;

The above descriptions are only preferred embodiments of the present invention, and are not intended to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention shall be included in the protection of the present invention. within range.

Claims (10)

1. A fluorine-containing hydrophobic association surface-active polyacrylamide is characterized in that the molecular structure is as follows: Wherein, x=100, y=10-20, z=0.05-1.5, n=4, 6, 8, R, R' are alkyl groups. 2. the preparation method of fluorine-containing hydrophobic association surface-active polyacrylamide as claimed in claim 1, is characterized in that: comprise the steps: Step 1: Synthesis of Surface Active Fluorinated Polymerizable Macromonomer HAPS ①. Synthesis of N-dialkyl perfluoroalkylsulfonamides Mix organic amine, triethylamine and organic solvent evenly, then add perfluoroalkylsulfonyl fluoride, then raise the temperature to 30-60°C, and continue the reaction for 4-10 hours; the reaction mixture is washed, dried, and distilled under reduced pressure to obtain the product N - dialkyl perfluorooctane sulfonamide; Wherein, the mol ratio of raw materials used is as follows: Perfluoroalkylsulfonyl fluoride: organic amine: triethylamine is 1:1~2:1.2~2; ②, Synthesis of hydroxypropyl chloroacrylate Mix hydroxypropyl acrylate and organic solvent, add thionyl chloride at 20-35°C under nitrogen gas, react at 40°C-60°C for 4-10 hours; cool, wash, dry, and distill under reduced pressure Obtain hydroxypropyl chlorinated acrylate; Wherein, the mol ratio of raw materials used is as follows: Hydroxypropyl acrylate: thionyl chloride is 1:1.5~2; ③. Synthesis of macromonomer HAPS Mix N-dialkyl perfluoroalkyl sulfonamide and organic solvent, add hydroxypropyl chloroacrylate under the condition of nitrogen gas, react at 30-50°C for 20-48 hours, cool, wash, dry, reduce Pressure distillation to obtain surface active fluorine-containing polymerizable macromonomer HAPS; Wherein, the mol ratio of raw materials used is as follows: Hydroxypropyl chloroacrylate: N-dialkyl perfluoroalkyl sulfonamide is 1.5～2:1; The second step: Synthesis of fluorine-containing hydrophobically associative polyacrylamide Add HAPS monomer and AM to the AMPS aqueous solution with a pH of 7-8; control the total mass fraction of AMPS, AM and HAPS monomer to 5-25%; 0.2%~1% initiator, control the temperature at 30~50°C; after 4~10 hours of reaction, a colloidal product is obtained, washed to obtain a white precipitate, dried and pulverized to obtain fluorine-containing hydrophobic association polyacrylamide; Wherein, the molar ratio of AM, AMPS and HAPS monomers is 100:10-20:0.05-1.5. 3. The method according to claim 2, characterized in that: in step ① of the first step, the washing is successively washed with water, washed with 0.5% aqueous hydrochloric acid, washed with saturated saline, and dried with anhydrous sodium sulfate. 4. The method according to claim 2, characterized in that: in the step ②, when washing, use NaOH aqueous solution to wash to neutral; dry with anhydrous sodium sulfate. 5. The method according to claim 2, characterized in that: in step ③, the washing is sequentially washed with 0.05% HCl and saturated brine. 6. The method according to claim 2, characterized in that: in step 1. of the first step, the organic amine is dimethylamine, diethylamine, dipropylamine, di-n-butylamine, methylethylamine one or more of them. 7. method as claimed in claim 2, is characterized in that: in the step 1. of described first step, step 3., described organic solvent is a kind of in toluene, Virahol, isopropyl ether, acetone or xylene or several. 8. The method according to claim 2, characterized in that: in the step ②, the organic solvent is one or more of isopropanol, acetone, methylene chloride, pyridine or tetrahydrofuran. 9. The method according to claim 2, characterized in that: in step ① of the first step, the perfluoroalkylsulfonyl fluoride is perfluorobutylsulfonyl fluoride, perfluorohexylsulfonyl fluoride, perfluorohexylsulfonyl fluoride, One or more of fluorooctanesulfonyl fluoride. 10. The method according to claim 2, characterized in that: in the second step, the initiator is ammonium persulfate and sodium sulfite with a mass and number ratio of 1:1, or a persulfate with a mass and number ratio of 1:1. Potassium sulfate and sodium bisulfite.