NOVEL SULFOBETAINE MONOMERS, PROCESS FOR PREPARING SAME, AND USES THEREOF

Abstract

The invention relates to a novel sulfobetaine monomer and to a process for the preparation thereof, advantageously by reaction between a vinyl-amine compound and a vinyl-sulfonic acid compound, preferably in the presence of a solubilizing agent. The invention also relates to the (co)polymers obtained from this novel type of sulfobetaine monomer, and to the use thereof, for example as a flocculant, dispersing agent, thickening agent, absorbent agent or friction-reducing agent.

Claims

1. A process for preparing a sulfobetaine monomer of formula (V) and/or its acid form by reaction between: a compound of formula (VI), and a compound of formula (VII) and/or one of its salts, optionally in the presence of at least one solubilizing agent of the compound of formula (VII), and optionally in the presence of at least one solvent, wherein the reaction is carried out with an amount of polymerization inhibitor of between 0 and less than 500 ppm relative to the total mass of the compounds of formulas (VI) and (VII), ##STR00019## ##STR00020## ##STR00021## In formulas (V), (VI) and (VII): R.sub.1 and R.sub.4 are, independently of each other, —H or — CH.sub.3, R.sub.2 and R.sub.3 are, independently of each other, a linear C1-C10 alkyl or branched C3-C10 alkyl or linear C2-C10 alkylene group, R.sub.5 is —H, or a linear C1-C22 alkyl or branched C3-C22 alkyl group, or R.sub.5 forms with R.sub.6 a C4-C10 carbon ring, optionally branched, R.sub.6 is a linear C1-C22 alkyl or branched C3-C22 alkyl group, or R.sub.6 forms with R.sub.5 a C4-C10 carbon ring, optionally branched, X.sub.1= —COO—, or —CONH— or — CH.sub.2—, X.sub.2= —COO— or —CONH—, n is an integer between 0 and 10.

2. The process according to claim 1, in which the polymerization inhibitor is present in an amount of less than 200 ppm.

3. The process according to claim 1 wherein the compound of formula (VI) is chosen from dimethylaminopropyl methacrylamide, dimethylaminopropyl acrylamide, allyldimethylamine, diallylmethyl amine, dimethylaminoethyl methacrylate, and dimethylaminoethyl acrylate.

4. The process according to claim 1 wherein the compound of formula (VII) is 2-acrylamido-2-methylpropane sulfonic acid and/or one of its salts.

5. The process according to claim 1 wherein the process is carried out in the presence of a solubilizing agent chosen from water, an alkane, an alcohol, an amide or a mixture of these compounds.

6. The process according to claim 5, wherein the solubilizing agent is water.

7. The process according to claim 5 wherein the amount of solubilizing agent is between 0 and 200% by mass relative to the mass of compound of formula (VII).

8. The process according to claim 1 wherein the molar ratio between the compound of formula (VI) and the compound of formula (VII) and/or one of its salts is between 1.01: 1 and 20:1.

9. The process according to claim 1 wherein the reaction between the compounds of formulas (VI) and (VII) is carried out in the presence of at least one solvent chosen from alkanes, ketones, nitriles, alcohols, and ethers.

10. The process according to claim 1 wherein the process comprises the following successive steps: a1) adding to a stirred reactor at least one compound of formula (VI), optionally at least one agent solubilizing the compound of formula (VII), and, optionally, a solvent to obtain a pre-reaction mixture; a2) adding at least one compound of formula (VII) and/or one of its salts to the pre-reaction mixture; a3) after reaction between the compounds of formulas (VI) and (VII), obtaining a sulfobetaine monomer of formula (V) and/or its acid form in the form of a solution or suspension of crystals.

11. A process for preparing a (co)polymer of sulfobetaine monomer of formula (V) and/or its acid form, comprising the following steps: preparing the sulfobetaine monomer of formula (V) and/or its acid form by a process according to claim 1, (co)polymerizing at least the sulfobetaine monomer obtained to form the (co)polymer.

12. A process for preparing a sulfobetaine monomer of formula (V) and/or its acid form, in a hydrated crystalline form, comprising the following successive steps: a1) adding to a stirred reactor at least one compound of formula (VI), optionally at least one agent solubilizing the compound of formula (VII), and optionally a solvent to obtain a pre-reaction mixture; a2) adding at least one compound of formula (VII) and/or one of its salts to the pre-reaction mixture; a3) after reaction, obtaining sulfobetaine monomers of formula (V) and/or its acid form in the form of a solution or suspension of crystals; a4) optionally, when the product of the reaction is a solution, extracting the compound of formula (V) in the form of crystals AA; a5) combining the crystals AA of compound of formula (V) in an aqueous solution to form a suspension A; a6) mixing suspension A for a period of between 1 minute and 20 hours; a7) obtaining a suspension B of crystals BB of compound of formula (V) in a hydrated form; a8) optionally isolating the crystals BB obtained from suspension B, ##STR00022## ##STR00023## ##STR00024## In formulas (V), (VI) and (VII): R.sub.1 and R.sub.4 are, independently of each other, —H or — CH.sub.3, R.sub.2 and R.sub.3 are, independently of each other, a linear C1-C10 alkyl or branched C3-C10 alkyl or linear C2-C10 alkylene group, R.sub.5 is —H, or a linear C1-C22 alkyl or branched C3-C22 alkyl group, or R.sub.5 forms with R.sub.6 a C4-C10 carbon ring, optionally branched, R.sub.6 is a linear C1-C22 alkyl or branched C3-C22 alkyl group, or R.sub.6 forms with R.sub.5 a C4-C10 carbon ring, optionally branched, X.sub.1= —COO—, or —CONH— or — CH.sub.2—, X.sub.2= —COO— or —CONH—, n is an integer between 0 and 10.

13. The process according to claim 12, wherein the reaction is carried out with an amount of polymerization inhibitor of between 0 and less than 500 ppm relative to the total mass of the compounds of formulas (VI) and (VII).

14. The process according to claim 13, wherein the polymerization inhibitor is present in an amount of less than 200 ppm.

15. A sulfobetaine monomer of formula (V) below, or its acid form, in a hydrated crystalline form, ##STR00025## in which R.sub.1 and R.sub.4 are, independently of each other, —H or — CH.sub.3, R.sub.2 and R.sub.3 are, independently of each other, a linear C1-C10 alkyl or branched C3-C10 alkyl or linear C2-C10 alkylene group, R.sub.5 is —H, or a linear C1-C22 alkyl or branched C3-C22 alkyl group, or R.sub.5 forms with R.sub.6 a C4-C10 carbon ring, optionally branched, R.sub.6 is a linear C1-C22 alkyl or branched C3-C22 alkyl group, or R.sub.6 forms with R.sub.5 a C4-C10 carbon ring, optionally branched, X.sub.1= —COO—, or —CONH— or — CH.sub.2—, X.sub.2= —COO— or —CONH—, n is an integer between 0 and 10.

16. The sulfobetaine monomer according to claim 15, wherein the sulfobetaine monomer is chosen from the group consisting of: the compounds of formula (V) for which n = 3 and X.sub.1 = —CONH—, the compounds of formula (V) for which n = 0 and X.sub.1 = —CH.sub.2—, and the compounds of formula (V) for which n = 2 and X.sub.1 = —COO—.

17. The sulfobetaine monomer according to claim 15 wherein R.sub.4 is a hydrogen atom, and X.sub.2 is —CONH—.

18. The sulfobetaine monomer according to claim 15, wherein -the sulfobetaine monomer has a structure chosen from the following structures of formula (VIII) to (XIII) or their acid form, ##STR00026## ##STR00027## ##STR00028## ##STR00029## ##STR00030## ##STR00031##

19. The process for preparing a (co)polymer of sulfobetaine monomer of formula (V) and/or its acid form, in a hydrated crystalline form, comprising the following steps: preparing the sulfobetaine monomer of formula (V) and/or its acid form, in a hydrated crystalline form, by a process according to claim 12 polymerizing the sulfobetaine monomer obtained to form the (co)polymer.

20. A (co)polymer of sulfobetaine monomer of formula (V) and/or its acid form according to claim 15.

21. (canceled)

22. A method for oil and gas recovery, water treatment, sludge treatment, pulp processing, papermaking, construction, mining, cosmetics formulation, detergent formulation, textile manufacturing, agriculture, or medical hydrogels manufacturing, said method comprising preparing a composition comprising the (co)polymer according to claim 20.

Description

BRIEF DESCRIPTION OF DRAWINGS

[0209] FIG. 1 illustrates the proton NMR spectrum of the AAMPS monomer.

[0210] FIG. 2 illustrates the proton NMR spectrum of MAMMPS monomer.

[0211] FIG. 3 illustrates the proton NMR spectrum of the AMMPS monomer.

[0212] FIG. 4 illustrates the proton NMR spectrum of MAAMPS monomer.

[0213] FIG. 5 illustrates the proton NMR spectrum of the ALMPS monomer.

[0214] FIG. 6 illustrates the proton NMR spectrum of the DAMPS monomer.

[0215] FIG. 7 illustrates the X-ray diffraction pattern of the MAAMPS monomer crystals in the hydrated crystalline form of Example 7.

[0216] FIG. 8 illustrates the X-ray diffraction pattern of MAAMPS monomer crystals in the anhydrous crystalline form of Example 10.

[0217] FIG. 9 illustrates the IR spectrum of the AAMPS monomer.

[0218] FIG. 10 illustrates the IR spectrum of MAMMPS monomer.

[0219] FIG. 11 illustrates the IR spectrum of AMMPS monomer.

[0220] FIG. 12 illustrates the IR spectrum of MAAMPS monomer.

[0221] FIG. 13 illustrates the IR spectrum of the ALMPS monomer.

[0222] FIG. 14 illustrates the IR spectrum of DAMPS monomer.

[0223] FIG. 15 corresponds to the observation of the crystals of the monomer MAAMPS of Example 7 in hydrated crystalline form under an optical microscope.

[0224] FIG. 16 corresponds to the observation of the crystals of the MAAMPS monomer of Example 10 in anhydrous crystalline form under an optical microscope.

[0225] FIG. 17 corresponds to the graph of the variation of Dh of Tests 1-1, 1-2, 1-3 of Example 17A, at a concentration of 1 mg/mL as a function of temperature.

[0226] FIG. 18 corresponds to the graph of the variation of Dh of Tests 2-1 and 2-2 of Example 17B, at a concentration of 1 mg/mL as a function of temperature.

[0227] FIG. 19 corresponds to the graph of the variation of Dh of Test 4-1 of Example 17D during the reversibility test of thermo-swelling and thermo-aggregating properties (temperature cycle from 15 to 90° C. then at 15° C.).

[0228] FIG. 20 corresponds to the graph of the variation of Dh of Test 4-2 of Example 17D during the reversibility test of thermo-swelling and thermo-aggregating properties (temperature cycle from 15 to 90° C. then at 15° C.).

[0229] FIG. 21 corresponds to the graph of the pressure differential variation dP for Test 5-1 of Example 17-E.

[0230] FIG. 22 corresponds to the graph of the pressure differential variation dP for Test 5-2 of Example 17-E at temperatures of 25° C. and 95° C.

EXAMPLES

[0231] In the examples, the amounts expressed in ppm are by mass, relative to the total mass of the monomers. This may, in particular, be the case with the amount of crosslinker.

[0232] Alternatively, unless otherwise indicated, the bulk viscosity is measured using a Brookfield viscometer, at a 12-rpm rotational speed at 25° C., at 1 mg/L in an aqueous solution containing 0.3 mol/L of NaCl.

Example 1: Process for Preparing AAMPS

[0233] 230 g of dimethyl aminoethyl acrylate (ADAME) and 50 g of water are charged in a 1000 mL glass reactor equipped with a stirrer and a condenser, The temperature of the mixture is maintained at 20° C. 410 g of acetone are added to the medium as a solvent.

[0234] 164 g of 2-acrylamido-2-methylpropane sulfonic acid are added to the previous mixture. The temperature is maintained at 20° C. and stirring is maintained at a speed of 300 rpm. The reaction takes place at atmospheric pressure. After 72 hours, the formation of product crystals forms a suspension in the reaction medium. The crystals are separated by Buchner-type vacuum filtration, the crystals are then washed directly in the filter with ethanol. The crystals thus obtained are placed in an oven at 40° C. under vacuum for 4 hours. 40.5 g of crystals are obtained; the yield is 15%, and the purity 90%.

[0235] An NMR analysis is carried out on the crystals obtained, and the structure of formula (IX) of the AAMPS monomer is confirmed as demonstrated by the proton NMR spectrum in FIG. 1. FIG. 9 illustrates the IR spectrum of the AAMPS monomer.

Example 2: Process for Preparing MAMMPS

[0236] 410 g of dimethylaminopropyl methacrylamide (DMAPMA) and 50 g of water are charged in a 1000 mL glass reactor equipped with a stirrer and a condenser. The temperature of the mixture is maintained at 20° C.

[0237] 164 g of 2-acrylamido-2-methylpropane sulfonic acid are added to the previous mixture. The contact time is 200 hours, the temperature is maintained at 20° C. and the stirring is maintained at a speed of 300 rpm. The reaction takes place at atmospheric pressure.

[0238] Crystals precipitate and a suspension of these crystals is obtained in the reaction mixture. The crystals are separated by Buchner-type vacuum filtration and washed with acetone. The crystals are then placed in an oven at 40° C. under vacuum for 6 hours. 273 g of crystals are obtained, and the yield is 92% with a product purity of 90%.

[0239] An NMR analysis is carried out on the crystals obtained, and the structure of formula (IX) of the MAMMPS monomer is confirmed, as demonstrated by the proton NMR spectrum in FIG. 2 and the IR spectrum in FIG. 10.

Example 3: Process for Preparing MAMMPS

[0240] 410 g of dimethylaminopropyl methacrylamide (DMAPMA) and 3 g of water are charged in a 1000 mL glass reactor equipped with a stirrer and a condenser. The temperature of the mixture is maintained at 20° C.

[0241] 164 g of 2-acrylamido-2-methylpropane sulfonic acid are added to the previous mixture. The contact time is 200 hours, the temperature is maintained at 20° C. and the stirring is maintained at a speed of 300 rpm. The reaction takes place at atmospheric pressure.

[0242] Crystals precipitate and a suspension of these crystals is obtained in the reaction mixture. The crystals are separated by Buchner-type vacuum filtration and washed with acetone. The crystals are then placed in an oven at 40° C. under vacuum for 6 hours. 179 g of crystals are obtained. The mass yield is 60% with a product purity of 75%.

Example 4: Process for Preparing MAMMPS

[0243] 270 g of dimethylaminopropyl methacrylamide (DMAPMA) and 50 g of water are charged in a 1000 mL glass reactor equipped with a stirrer and a condenser. The temperature of the mixture is maintained at 20° C.

[0244] 164 g of 2-acrylamido-2-methylpropane sulfonic acid are added to the previous mixture. 138 g of acetone are added to the reaction medium. The contact time is 200 hours, the temperature is maintained at 20° C. and the stirring is maintained at a speed of 300 rpm. The reaction takes place at atmospheric pressure.

[0245] Crystals precipitate and a suspension of these crystals is obtained in the reaction mixture. The crystals are separated by Buchner-type vacuum filtration and washed with acetone. The crystals are then placed in an oven at 40° C. under vacuum for 6 hours. 218 g of crystals are obtained. The mass yield is 73% with a product purity of 90%.

Example 5: Process for Preparing the AMMPS

[0246] 444 g of dimethylaminopropylacrylamide (DMAPAA) and 60 g of water are charged in a 1000 mL glass reactor equipped with a stirrer and a condenser. The temperature of the mixture is maintained at 20° C.

[0247] 197 g of 2-acrylamido-2-methylpropane sulfonic acid are added to the previous mixture. The contact time is 200 hours, the temperature is maintained at 20° C. and the stirring is maintained at a speed of 300 rpm. The reaction takes place at atmospheric pressure.

[0248] Crystals precipitate and a suspension of these crystals is obtained in the reaction mixture. The crystals are separated by Buchner-type vacuum filtration and washed with acetone. The crystals are then placed in an oven at 40° C. under vacuum for 6 hours. 363 g of crystals are obtained. The mass yield is 25% with a product purity of 45%.

[0249] An analysis is performed on the crystals obtained, and the structure of the AMMPS monomer is confirmed, as demonstrated by the proton NMR spectrum in FIG. 3 and the IR spectrum in FIG. 11.

Example 6: Process for Preparing MAAMPS

[0250] 563 g of dimethyl aminoethyl methacrylate (MADAME) and 38 g of water are charged in a 1000 mL glass reactor equipped with a stirrer and a condenser. The temperature of the mixture is maintained at 20° C.

[0251] 123 g of 2-acrylamido-2-methylpropane sulfonic acid are added to the previous mixture. The contact time is 170 hours, the temperature is maintained at 20° C. and the stirring is maintained at a speed of 300 rpm. The reaction takes place at atmospheric pressure.

[0252] Crystals precipitate and a suspension of these crystals is obtained in the reaction mixture. The crystals are separated by Buchner-type vacuum filtration and washed with acetone. The crystals are then placed in an oven at 40° C. under vacuum for 6 hours. 143 g of crystals are obtained. The yield is 66%, the purity of the product being 90%.

[0253] An NMR analysis is carried out on the crystals obtained, and the structure of formula (VIII) of the MAAMPS monomer is confirmed, as demonstrated by the proton NMR spectrum in FIG. 4 and the IR spectrum in FIG. 12.

Example 7: Process for Preparing MAAMPS

[0254] 400 g of dimethyl aminoethyl methacrylate (MADAME) and 247 g of water are charged in a 1000 mL glass reactor equipped with a stirrer and a condenser. The temperature of the mixture is maintained at 20° C.

[0255] 176 g of 2-acrylamido-2-methylpropane sulfonic acid are added to the previous mixture. The contact time is 170 hours, the temperature is maintained at 20° C. and the stirring is maintained at a speed of 300 rpm. The reaction takes place at atmospheric pressure.

[0256] Crystals precipitate and a suspension of these crystals is obtained in the reaction mixture. The crystals are separated by Buchner-type vacuum filtration and washed with acetone. The crystals are then placed in an oven at 40° C. under vacuum for 6 hours. 37 g of crystals are obtained. The yield is 12%, the purity of the product being 90%.

[0257] A microscope observation illustrated by FIG. 15 shows a particular form of crystals.

Example 8: Process for Preparing MAAMPS

[0258] 224 g of dimethyl aminoethyl methacrylate (MADAME) and 64 g of water are charged in a 1000 mL glass reactor equipped with a stirrer and a condenser. The temperature of the mixture is maintained at 20° C.

[0259] 328 g of 2-acrylamido-2-methylpropane sulfonic acid are added to the previous mixture. 163 g of acetone are added to the medium as well as 33 g of potassium carbonate. The contact time is 170 hours, the temperature is maintained at 20° C. and stirring is maintained at a speed of 300 rpm. The reaction takes place at atmospheric pressure.

[0260] Crystals precipitate and a suspension of these crystals is obtained in the reaction mixture. The crystals are separated by Buchner-type vacuum filtration and washed with acetone. The crystals are then placed in an oven at 40° C. under vacuum for 6 hours. 288 g of crystals are obtained. The yield is 50%, the purity of the product being 57%.

Example 9: Process for Preparing MAAMPS

[0261] 380 g of dimethyl aminoethyl methacrylate (MADAME) are charged in a 1000 mL glass reactor equipped with a stirrer and a condenser. The temperature of the mixture is maintained at 20° C.

[0262] 167 g of 2-acrylamido-2-methylpropane sulfonic acid are added to the previous mixture. 190 g of acetone are added in the medium as well. The contact time is 200 hours, the temperature is maintained at 20° C. and the stirring is maintained at a speed of 300 rpm. The reaction takes place at atmospheric pressure.

[0263] Crystals precipitate and a suspension of these crystals is obtained in the reaction mixture. The crystals are separated by Buchner-type vacuum filtration and washed with acetone. The crystals are then placed in an oven at 40° C. under vacuum for 6 hours. 29 g of crystals are obtained. The yield is 10%, the purity of the product being 60%.

Example 10: Process for Preparing MAAMPS

[0264] 226 g of dimethyl aminoethyl methacrylate (MADAME) are charged in a 1000 mL glass reactor equipped with a stirrer and a condenser. The temperature of the mixture is maintained at 20° C.

[0265] 600 g of an aqueous solution of 50% sodium 2-acrylamido-2-methylpropane sulfonate are added to the previous mixture. The contact time is 170 hours, the temperature is maintained at 20° C. and the stirring is maintained at a speed of 300 rpm. The reaction takes place at atmospheric pressure. The product obtained is dissolved in the reaction medium. The yield is 39%, the purity of the product being 35%.

[0266] A microscope observation illustrated by FIG. 16 shows a particular form of crystals different from those obtained in Example 7 and FIG. 15.

Example 11: Process for Preparing the ALMPS

[0267] 303 g of allyl dimethylamine (ADMA) are charged in a 1000 mL glass reactor equipped with a stirrer and a condenser. The temperature of the mixture is maintained at 20° C.

[0268] 246 g of 2-acrylamido-2-methylpropane sulfonic acid are added to the previous mixture as well as 10 g of acetone and 15 g of water. The contact time is 170 hours, the temperature is maintained at 20° C. and the stirring is maintained at a speed of 300 rpm. The reaction takes place at atmospheric pressure.

[0269] Crystals precipitate after adding acetone and a suspension of these crystals is obtained in the reaction mixture. The crystals are separated by Buchner-type vacuum filtration and washed with acetone. The crystals are then placed in an oven at 40° C. under vacuum for 6 hours. 273 g of crystals are obtained. The yield is 79%, the purity of the product being 90%.

[0270] An NMR analysis is carried out on the crystals obtained, and the structure of formula (X) of the ALMPS monomer is confirmed, as demonstrated by the NMR spectrum of the proton in FIG. 5 and the IR spectrum in FIG. 13.

Example 12: Process for Preparing the ALMPS

[0271] 369 g of allyl dimethylamine (ADMA) are charged in a 1000 mL glass reactor equipped with a stirrer and a condenser. The temperature of the mixture is maintained at 20° C.

[0272] 300 g of 2-acrylamido-2-methylpropane sulfonic acid are added to the previous mixture as well as 175 g of acetone. The contact time is 170 hours, the temperature is maintained at 20° C. and the stirring is maintained at a speed of 300 rpm. The reaction takes place at atmospheric pressure.

[0273] Crystals precipitate after adding acetone to the medium and a suspension of these crystals is obtained in the reaction mixture. The crystals are separated by Buchner type vacuum filtration and washed with acetone. The crystals are then placed in an oven at 40° C. under vacuum for 6 hours. 222 g of crystals are obtained. The yield is 52%, the purity of the product being 90%.

Example 13: Process for Preparing the ALMPS

[0274] 177 g of allyl dimethylamine (ADMA) are charged in a 1000 mL glass reactor equipped with a stirrer and a condenser. The temperature of the mixture is maintained at 20° C.

[0275] 144 g of 2-acrylamido-2-methylpropane sulfonic acid are added to the previous mixture as well as 180 g of acetone and 336 g of water. The contact time is 170 hours, the temperature is maintained at 20° C. and the stirring is maintained at a speed of 300 rpm. The reaction takes place at atmospheric pressure.

[0276] Crystals precipitate after adding acetone to the medium and a suspension of these crystals is obtained in the reaction mixture. The crystals are separated by Buchner type vacuum filtration and washed with acetone. The crystals are then placed in an oven at 40° C. under vacuum for 6 hours. 106 g of crystals are obtained. The yield is 52%, the purity of the product being 90%.

Example 14: Process for Preparing DAMPS

[0277] 120 g of diallylmethylamine (DAMA) are charged in a 1000 mL glass reactor equipped with a stirrer and a condenser. The temperature of the mixture is maintained at 20° C.

[0278] 112 g of 2-acrylamido-2-methylpropane sulfonic acid are added to the previous mixture as well as 75 g of acetone and 30 g of water. The contact time is 170 hours, the temperature is maintained at 20° C. and the stirring is maintained at a speed of 300 rpm. The reaction takes place at atmospheric pressure.

[0279] Crystals precipitate after adding acetone to the medium and a suspension of these crystals is obtained in the reaction mixture. The crystals are separated by Buchner-type vacuum filtration and washed with acetone. The crystals are then placed in an oven at 40° C. under vacuum for 6 hours. 135 g of crystals are obtained. The yield is 85%, the purity of the product being 90%.

[0280] An NMR analysis is carried out on the crystals obtained, and the structure of formula (X) of the DAMPS monomer is confirmed, as demonstrated by the proton NMR spectrum in FIG. 6 and the IR spectrum in FIG. 14

Example 15: Process for Preparing DAMPS

[0281] 120 g of diallylmethylamine (DAMA) are charged in a 1000 mL glass reactor equipped with a stirrer and a condenser. The temperature of the mixture is maintained at 20° C.

[0282] 112 g of 2-acrylamido-2-methylpropane sulfonic acid are added to the previous mixture as well as 75 g of acetone and 7.5 g of water. The contact time is 170 hours, the temperature is maintained at 20° C. and the stirring is maintained at a speed of 300 rpm. The reaction takes place at atmospheric pressure.

[0283] Crystals precipitate after adding acetone to the medium and a suspension of these crystals is obtained in the reaction mixture. The crystals are separated by Buchner-type vacuum filtration and washed with acetone. The crystals are then placed in an oven at 40° C. under vacuum for 6 hours. 135 g of crystals are obtained. The yield is 85%, the purity of the product being 90%.

Example 16: Analysis by X-Ray Diffraction

[0284] The solids obtained in Examples 7 and 10 are ground beforehand to form powders and are analyzed by X-ray diffraction over an angular range of 10 to 90°. The equipment used is a Rigaku MiniFlex II diffractometer equipped with a copper source.

[0285] It is possible to see that the solid obtained at the end of Example 7 (FIG. 7) has an X-ray diffraction diagram with the following characteristic peaks:

[0286] 6.19°, 7.66°, 8.70°, 10.20°, 10.73°, 11.85°, 12.38°, 13.98°, 15.39°, 16.11°, 16.76°, 17.23°, 17.72°, 18.23°, 18.66°, 19.24°, 19.63°, 20.06°, 20.53°, 21.02°, 21.65°, 22.31°, 23.00°, 24.02°, 25.17°, 26.11°, 26.36°, 27.36°, 28.07°, 29.08°, 29.48, 29.91° 2-theta degrees. The uncertainty is generally of the order of +/- 0.05°.

[0287] It is possible to see that the solid obtained at the end of Example 10 (FIG. 8) has an X-ray diffraction diagram with the following characteristic peaks:

[0288] 6.23°, 8.74°, 10.75°, 11.91°, 12.45°, 12.51°, 14.02°, 14.49°, 15.7°, 16.13°, 16.33°, 17.21°, 17.66°, 18.26°, 18.68°, 19.63°, 20.08°, 20.57°, 21.04°, 21.59°, 22.47°, 23.00°, 23.92°, 24.37°, 24.86°, 25.01°, 25.62°, 26.13°, 26.38°, 26.62°, 27.34°, 28.93°, 29.40° 2-theta degrees (+/- 0.05°).

[0289] It is thus possible to highlight a difference in crystalline structure for the same MAAMPS molecule, a sign of a polymorphism.

Additional Examples: Process for Preparing MAAMPS With a Decreasing Amount of MEHQ (Mono Methyl Ether of Hydroquinone) as a Polymerization Inhibitor

[0290] Example 9 is reproduced by adding 1000 ppm, 750 ppm, 500 ppm, 450 ppm, 250 ppm, and 50 ppm (relative to the amount of MADAME and 2-acrylamido-2-methylpropane sulfonic acid) of MEHQ in 190 g of acetone.

[0291] When 1000 ppm of MEHQ are added, the yield is 5% and the purity 42%.

[0292] When 750 ppm of MEHQ are added, the yield is 6% and the purity 45%.

[0293] When 500 ppm of MEHQ are added, the yield is 8% and the purity 51%.

[0294] The addition of polymerization inhibitor in large amounts, i.e., 750 ppm and 1000 ppm, leads to a drop in yield and purity. It is surprising to note that by using a reduced amount of MEHQ, i.e., less than 500 ppm, in particular 450 ppm, 250 ppm, or more preferably 50 ppm or less, the yield and the purity are improved compared to the tests carried out in the presence of 500 ppm or more of MEHQ.

Example 17: Preparation of Inverse Emulsion of Polymers Based on Sulfobetaine and Their Use In Conformance

[0295] The following series of examples deals with the preparation of polymer microparticles based on the sulfobetaines of the invention. These particles should show an increase in size, Dh (swelling/aggregation), as a function of temperature. Thus, these particles may be used as conformance additives for enhanced oil recovery (EOR) and make it possible: [0296] to reduce the permeability in areas of high temperatures and high permeability in order to increase the crude displacement efficiency of a water or chemical injection; and [0297] to reduce or totally block the production of water, at the production wells.

Synthesis Procedure

[0298] Cross-linked polymer particles of 2-(diethylamino)ethyl methacrylate and a polymerizable sulfobetaine were prepared by conventional free radical inverse emulsion polymerization. The procedure consists in: [0299] Preparing the organic phase: in a first reactor are introduced with stirring: [0300] a mineral oil containing saturated hydrocarbons [0301] surfactants of the sorbitan ester-type with an HLB of 3 to 7 [0302] Preparing the aqueous phase: in a second reactor are introduced with stirring and at room temperature: [0303] Deionized water [0304] zwitterionic monomers of the sulfobetaine type according to the invention or zwitterionic monomers described in the prior art [0305] comonomers: DEAEMA and crosslinker (on diacrylamido base and/or dimethacrylate) [0306] pH modifiers [0307] After obtaining a homogeneous organic phase, the aqueous phase is emulsified for a few tens of seconds in the organic phase under sustained mechanical and shearing agitation. A stable emulsion is obtained. [0308] The emulsion is transferred to a jacketed reactor fitted with a stirring system and then degassed via bubbling with nitrogen for 60 minutes. [0309] Polymerization may be initiated with a redox couple. [0310] After cooling of the reaction medium, the inverting surfactant having an HLB of 12 is introduced with gentle stirring.

Characterization of the Hydrodynamic Diameter (Dh) of Polymer Particles by Dynamic Light Scattering (DLS)

[0311] The sizes of the polymer particles (Dh) at ambient temperature and their evolution with temperature were characterized by DLS using the ZETASIZER NANO ZS marketed by Malvern and equipped with a 4 mW-632.8 nm Helium Neon laser. The polymer particles were analyzed at a concentration of 1 mg/mL in brine (0.3 mol/L NaCl). The cuvettes used are made of quartz. Data is analyzed using Malvern DTS software. In the context of temperature rises, data is collected at 5° C. temperature intervals with a sample equilibrium time of 5 minutes.

[0312] Before they can be used as conformance additives in many fields: [0313] It is preferable that the Dh values of the polymer populations increase as quickly as possible, and ideally at temperatures between 30 and 50° C. [0314] The aggregates of particles formed with the increase in temperature are advantageously characterized by the highest possible Dh values.

Characterization of the Reversibility Properties of Polymer Particles

[0315] The reversibility properties of the particles will be evaluated by studying the variation of the hydrodynamic diameters (Dh) of the polymer particles during temperature cycles. Particle Dh reversibility data will be collected between 2 temperatures (15 and 90° C.) by performing ramp-up and down cycles between these 2 temperatures. The temperature ramp-up or down time between the terminals is 10 minutes.

[0316] The lower the variations in Dh before and after a temperature cycle (15° C. => 90° C. => 15° C.) (less than or equal to 10%), the more reversible the performance of thermo-swelling/thermo-aggregation.

Example 17-A: Elaboration of Particles From Sulfobetaines

[0317] The objectives of this test are to confirm the thermo-swelling and thermo-aggregating performances of the particles prepared from the monomers of the invention, in order to use them in conformance (see paragraph on “characterization of Dh”).

[0318] A first series of polymers, crosslinked with 40 ppm of MBA, were produced according to the procedure described above. Table 1 summarizes the chemical compositions and characteristics of the various tests of Example 17-A.

TABLE-US-00001 Test # Molar composition Sulfobetaine Comonomer Nature Mol % Nature Mol % 1-1 Invention MAAMPS 30 DEAEMA 70 1-2 Invention MAMMPS 30 DEAEMA 70 1-3 Prior art DMAPS 30 DEAEMA 70 1-4 Counter-example MAAMPS prepared with OMSO and obtained according to counter-example 1 30 DEAEMA 70

TABLE-US-00002 Compositions and characteristics of Tests 1-1, 1-2 1-3 and 1-4 Test # Characterizations Active matter (%) Dh (nm) - 25° C. - 1 mg/mL in 0.3 M NaCl Bulk viscosity (12 rpm) Visual observation of stability t = 0 t= 1 month t= 6 months t= 12 months 1-1 Invention 30 121 < 2000 cPs Stable Stable Stable Stable 1-2 Invention 30 135 < 2000 cPs Stable Stable Stable Stable 1-3 Prior art 30 180 < 2000 cPs Stable Stable Stable Demixion 1-4 Counter-example 30 172 < 2000 cPs Stable Stable Stable Demixion

[0319] Bulk viscosity is measured using a Brookfield viscometer (rotation speed: 12 rpm).

[0320] The graph in FIG. 17 highlights the variations in Dh for each of the tests, at a concentration of 1 mg/mL as a function of temperature.

[0321] This example demonstrates that the emulsions prepared from the monomers of the invention (Tests 1-1 and 1-2) are more storage-stable.

[0322] The highest Dh values were obtained with the polymer particles prepared from the monomers of the invention. The thermo-swelling and thermo-aggregating performances of the polymer particles of the counter-example are significantly lower than those obtained with the polymer particles of the invention. The thermo-swelling/thermo-aggregating activation temperatures of the polymer particles prepared from the monomers of the invention are more suited to areas of average field temperatures.

[0323] In conclusion, the particles prepared from the monomers of the invention (Tests 1-1 and 1-2) generate better thermo-swelling/thermo-aggregating performance than those of the prior art (Test 1-3) and of the counter-example (Test 1-4).

Example 17-B: Elaboration of Particles From Sulfobetaines

[0324] The objectives of this test were to confirm the thermo-swelling and thermo-aggregating performances of the particles (prepared from the monomers of the invention) at a molar composition different from that of Example 17-A.

[0325] A new series of crosslinked polymer particles based on sulfobetaines were developed. Table 2 below summarizes the chemical compositions of the polymers (crosslinked with 10 ppm of MBA) and the characteristics of the various tests of Example 17-B. The synthesis protocol is that described at the beginning of Example 17.

TABLE-US-00003 Test # Molar composition Sulfobetaine Comonomer Nature Mol % Nature Mol % 2-1 Invention MAAMPS 10 DEAEMA 90 2-2 Invention MAMMPS 10 DEAEMA 90

TABLE-US-00004 Compositions and characteristics of Tests 2-1, 2-2 Characterizations Active Dh (nm) - 25° C. Bulk Visual observation of stability Test # matter (%) - 1mg/ml in 0.3 M NaCL viscosity (12 rpm) t = 0 t = 1 month t = 6 months t = 12 months 2-1 Invention 30 115 < 2000 cPs Stable Stable Stable Stable 2-2 Invention 30 120 < 2000 cPs Stable Stable Stable Stable

[0326] The graph in FIG. 18 highlights the variations of the Dh of each of the tests, at a concentration of 1 mg/mL as a function of the temperature.

[0327] This new example highlights high final Dh values and activation temperatures compatible with most reservoirs (subterranean formations).

[0328] This demonstrates once again that the emulsions prepared from the monomers of the invention (Tests 2-1 and 2-2) generate, once dispersed in brines, thermo-swelling/thermo-aggregating performances at monomeric molar compositions different from those of Example 17-A.

Example 17-C Preparation of Particles From Sulfobetaines Crosslinked With Dimethacrylates

[0329] The objectives of this test are to confirm the thermo-swelling and thermo-aggregating performances of the particles prepared from the monomers of the invention, but crosslinked with a crosslinker different from that of Test 17-B.

[0330] Table 3 below summarizes the new chemical compositions of the polymers crosslinked with 10 ppm of EGDMA and the characteristics of the various tests of Example 17-C. The polymer synthesis protocol is that described at the beginning of Example 17.

TABLE-US-00005 Test # Molar composition Sulfobetaine Comonomer Nature Mol % Nature Mol % 3-1 Invention MAAMPS 10 DEAEMA 90 3-2 Invention MAMMPS 10 DEAEMA 90

TABLE-US-00006 Compositions and characteristics of Tests 3-1 and 3-2 Test # Characterizations Active matter (%) Dh (nm) - 25° C. - 1 mg/mL in 0.3 M NaCl Bulk viscosity (12 rpm) Dh (nm) Ambient temperature 80° C. 3-1 Invention 30 115 < 2000 cPs 140 7000 3-2 Invention 30 120 < 2000 cPs 135 6500

[0331] It is observed that the increase in temperature induces a very significant increase in Dh. This third example demonstrates that the emulsions prepared from the monomers of the invention perform well even when they are crosslinked with a crosslinker of the methacrylate type.

Example 17-D: Reversibility of the Conformance Performances of the Particles of Crosslinked Polymers Based on MAAMPS or MAMMPS Sulfobetaines

[0332] The objectives of this test are to confirm the reversibility properties of the thermo-swelling and thermo-aggregating performances of the particles according to successive temperature ramp-up and down cycles.

[0333] Table 4 below summarizes the new chemical compositions of the crosslinked copolymers with 40 ppm of MBA and the characteristics of the various tests of the example. The synthesis protocol is that described at the beginning of Example 17.

TABLE-US-00007 Test # Molar composition Sulfobetaine Comonomer Nature Mol % Nature Mol % 4-1 Invention MAAMPS 30 DEAEMA 70 4-2 Invention MAMMPS 30 DEAEMA 70

TABLE-US-00008 Compositions and characteristics of Tests 4-1 and 4-2 Test # Characterizations Active matter (%) Dh (nm) - 15° C. - 1 mg/mL in 0.3 M NaCl Dh (.Math.m) - 90° C. - 1 mg/mL in 0.3 M NaCl) Bulk viscosity (12 rpm) 4-1 Invention 30 121 >5 < 2000 cP 4-2 Invention 30 135 >5 < 2000 cP

[0334] The reversibility of the thermo-swelling/thermo-aggregating properties of the polymer particles was evaluated according to the protocol described at the beginning of Example 17. The results obtained are collated in the graphs of FIG. 19 (Test 4-1) and 20 (Tests 4-2). The reversibility properties of thermo-swelling and thermo-aggregating were established with temperature ramp-up and down cycles between 15° C. and 90° C.

[0335] It is observed that the Dh values before and after the temperature cycles are equivalent. This fourth example demonstrates that the polymer particles of the emulsions prepared from the monomers of the invention have reversible properties (depending on the temperature) of thermo-swelling and thermo-aggregation. This reversibility property obtained with the particles prepared from the monomers of the invention, makes it possible to modulate the performances according to the temperature variations of the same reservoir.

Example 17-E: Performances in a Porous Medium of Crosslinked Polymer Particles Based on MAAMPS or MAMMPS Sulfobetaines

[0336] The objectives of this test are to confirm the thermo-swelling and thermo-aggregating performances of particles in porous media.

[0337] Table 5 below summarizes the chemical composition of Tests 5-1 and 5-2 (crosslinked copolymers with 40 ppm of MBA). The synthesis protocol is that described above.

TABLE-US-00009 Compositions and characteristics of Tests 5-1 and 5-2 Test # Molar composition Sulfobetaine Comonomer Nature Mol % Nature Mol % 5-1 Invention MAMMPS 30 DEAEMA 70 5-2 Prior art DMAPS 30 DEAEMA 70

[0338] The characteristics of the injection test in a porous medium used for the injection of the dispersion at 1000 active ppm of polymer 5-1 are: [0339] Flow (Q) = 12 cm.sup.3/h [0340] Shear: 50 s.sup.-1 [0341] Internal velocity: 2.4 m/day [0342] Porosity: 33% [0343] Permeability: 1290 mD

[0344] The evolution of the pressure inside the porous medium as a function of the pore volume is recorded. FIG. 21 corresponds to the graph of evolution of the pressure differential dP between the inlet and the outlet of the porous medium.

[0345] It should be noted that the total pressure differential dP is constant, which confirms that the particles of Test 5-1 inject and propagate well in porous media at room temperature.

[0346] The evolution of the pressure inside the porous medium as a function of the temperature is recorded. FIG. 22 corresponds to the graph of the evolution of the pressure differential dP between the inlet and the outlet of the porous medium, as a function of the temperature with a change from 25° C. to 95° C.

[0347] The graph in FIG. 22 highlights an increase in the pressure differential inside the section with temperature (from 25° C. to 95° C.). This confirms the thermo-swelling and thermo-aggregating performances of the particles of Test 5-1 as a function of temperature.

[0348] In conclusion, this Example 17-E demonstrates that the emulsions of polymer particles prepared from the monomers of the invention have propagating, thermo-swelling and thermo-aggregating properties in a porous medium.

Example 18: Dishwashing Liquid Formulated From a MAAMPS Copolymer

[0349] The detergent industry formulates foaming products from many raw materials including surfactants. Excipients may be added to the formulations by a person skilled in the art in order to increase the foaming properties of the formulations, or even to stabilize the foam formed.

[0350] The objectives of this new test are to evaluate the foaming and stabilizing properties of the foams formed in the presence of greasy residues, of additives prepared from one of the monomers of the invention.

[0351] An acrylamide (AM) and MAAMPS copolymer was prepared by conventional radical polymerization in solution in water. The chemical composition is collated in Table 6.

TABLE-US-00010 Chemical composition of Test 6-1 Test # Molar composition Characterizations Sulfobetaine Comonomer Active matter (%) Nature Mol % Nature Mol % 6-1 Invention MAAMPS 50 AM 50 20

[0352] First, an aqueous stock solution containing 20% by mass of surfactants (mixture of Sodium Lauryl Ether Sulfate, Amine Oxide) is prepared. The different daughter solutions (from A to E) are then formulated by adding different % by mass of the copolymer 6-1, and listed in Table 7.

TABLE-US-00011 Composition of polymer 6-1 in surfactant solutions Surfactant solutions % by mass of copolymer 6-1 A 0 B 0.1 C 0.25 D 0.5 E 1

[0353] Solutions A to E are then prepared according to the formulas detailed in Table 8.

TABLE-US-00012 Composition of Tests F, G, H, I and J Tests Composition Deionized water (mL) Tested daughter solutions Reference Weighted masses (g) F 200 A 0.2 G 200 B 0.2 H 200 C 0.2 I 200 D 0.2 J 200 E 0.2

[0354] Formulations F, G, H, I, and J are respectively packaged in graduated test tubes. At the beginning, the volume of each of the solutions occupies ⅓ of the volume of the test tube. Nine cycles of twenty rotations (30 rpm) each are then carried out on each of the test tubes. At the end of each cycle, five milliliters of olive oil are added to each test tube (i.e., a total of 40 mL, at the end of the procedure). The foam heights of Tests G, H, I, J are then measured and compared with that of Test F. The results obtained are collated in Table 9.

TABLE-US-00013 Foam gain of Tests G, H, I and J Tests % Increase in foam height compared to Test F G +88% H +106% I +53% J +24%

[0355] The results obtained show a significant increase in foam compared to reference F. This new example confirms the foaming and foam-stabilizing properties of the copolymer prepared from the sulfobetaine monomers of the invention.

Example 19: Retaining Agent in Paper Applications

[0356] The paper industry formulates paper pulp. Retaining and drainage additives are generally added to the formulations.

[0357] The objectives of this new test are to evaluate the properties of total retention (FPR, fibers + mineral fillers), mineral filler retention (First Pass Ash Retention (FPAR)) and vacuum drainage (Dynamic Drainage Analyzer (DDA)). Regarding FPR and FPAR, the higher the values, the better the performance. For DDA, the lower the drainage value, the better the performance.

[0358] The polymers below were synthesized following the procedure described in Example 1. The formulation of the 7-0 Test does not contain any polymer. Table 10 summarizes the chemical compositions and the performances (concentration of 0.25% by mass in the paper formulation) of the various tests. The molar masses of the different copolymers are comparable and of the same order of magnitude.

TABLE-US-00014 Compositions and performances of the tests Test # Molar composition Performances Comonomer 1 Comonomer 2 Sulfobetaine FPR (%) FPAR (%) DDA (%) Nature Mol % Nature Mol % Nature Mol % 7-6 References TEST WITHOUT POLYMER 71.8 4.2 36.1 7-7 Invention ADC 15 AM 80 MAAMPS 5 84.1 60.8 20.2 7-8 Invention ADC 15 AM 80 MAMMPS 5 81.6 46 23 7-10 Invention ADC 38 AM 57 MAAMPS 5 78.2 32.1 21.6 7-11 Invention ADC 38 AM 57 MAMMPS 5 77.3 27.3 25.1

[0359] The tests according to the invention generate higher FPAR and FPR values than the reference, and lower DDA values than the reference. This new example demonstrates that the terpolymers prepared from the sulfobetaine monomers of the invention demonstrate good performance in total retention, filler retention and vacuum drainage.

Example 20: High Viscosity Additive (HVFR) for Hydraulic Fracturing

[0360] The hydraulic fracturing industry uses many additives including friction reducers which induce high viscosities in saline aqueous media (High-Viscosity Friction Reducer (HVFR)). The objectives of this example are to formulate hydraulic fracturing fluids from additives (of the invention and the prior art) and to see the “bulk” viscosity levels obtained.

[0361] The polymers described in Table 11 were synthesized by following the procedure described in Example 1. Table 11 summarizes the chemical compositions and the characteristics of each of the tests. The molar masses of the different copolymers are comparable and of the same order of magnitude.

TABLE-US-00015 Compositions and performances of the tests Test # Molar composition Characterizations Comonomer 1 Comonomer 2 Sulfobetaine Active matter (%) Bulk visco. (cP) Nature Mol % Nature Mol % Nature Mol % 8-4 Invention ADC 15 AM 80 MAAMPS 5 35 1280 8-5 Invention ADC 15 AM 80 MAMMPS 5 35 1320 8-6 Prior art ADC 15 AM 85 – 0 35 1280

[0362] Table 12 summarizes Fann viscosities at 4 and 6 Gallon Per Thousand (GPT) in different brines. Brine 1 is composed of sodium chloride (30 g/L) and calcium dichloride (3 g/L). Brine 2 is composed of sodium chloride (85 g/L) and calcium dichloride (33 g/L).

TABLE-US-00016 Fann viscosities Fann viscosity (cP) Fann viscosity (cP) Brine 1 Brine 2 Test 4 GPT @ 511 s.sup.-1 6 GPT @ 511 s.sup.-1 4 GPT @ 100 s.sup.-1 6 GPT @ 100 s.sup.-1 4 GPT @ 511 s.sup.-1 6 GPT @ 511 s.sup.-1 4 GPT @ 511 s.sup.-1 6 GPT @ 100 s.sup.-1 8-1 Invention 3.8 5.3 4.8 7.1 4.4 6.8 5.5 9.5 8-2 Invention 2.8 3.3 3.2 5.7 3 4.9 3.5 5.7 8-3 Prior art 2.5 2.5 2.5 2.5 2.5 3 2.5 2.5

[0363] The Fann viscosities, in centipoise (cP) are measured at 20° C. using the Chandler Engineering model 3500 viscometer which is equipped with the R1B1 module (Rotor 1 Bob 1). The values of the Fann viscosities at shear rates of 511 and 102 s.sup.-1 are extrapolated by applying the angular velocities of 300 and 60 rpm respectively.

[0364] Tests 8-1 and 8-2 generate higher Fann viscosities than for Tests 8-3, whatever the shear (100 or 511 s-1) and the dosage (4 or 6 Gallon per Thousand). This new example demonstrates that hydraulic fracturing fluids of the (HVFR) type, formulated from emulsions produced from the monomers of the invention, have higher Fann viscosities than those of fluids prepared from emulsions of the prior art and thus offer better performance in the intended application.