Novel sulfobetaine monomer, preparation method and use thereof

Abstract

The present invention relates to a novel sulfobetaine monomer and a method for its preparation, 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 (co)polymers obtained from this novel sulfobetaine monomer, and to their use, for example as a flocculant, dispersant, thickener, absorbent or friction reducer.

Description

Technical Field

[0001] The field of the invention relates to zwitterionic monomers, more particularly to novel sulfobetaine monomers, as well as to processes for their preparation and their use for the production of (co)polymers. Background Art

[0002] Zwitterionic monomers are unique in that they have at least one anionic charge and at least one cationic charge on the same monomer unit. The cationic group is typically a quaternary ammonium. The anionic group is typically a carboxylic acid, sulfonic acid, phosphoric acid, phosphonic acid, or a salt thereof. These zwitterionic monomers are also characterized by a group that separates the anionic charge from the cationic charge. Hydrophilic or hydrophobic groups may also be present on the monomer unit.

[0003] Zwitterionic monomers are important because they impart specific properties to the polymers obtained therefrom.Sultaine monomers are a special type of zwitterionic monomers.

[0004] The sulfobetaine-type monomers described in the prior art generally have a structure according to the following formula (I), wherein x and y are integers, and R1 and R2 are selected from alkyl groups, cyclic groups or heterocyclic groups.

[0005]

[0006] Where R 3 =H or CH3

[0007] The most commonly cited molecule is the SPE monomer, particularly by Raschig as its The monomers are made from a part of the mer series. The structure of mer SPE corresponds to the structure of formula (I), wherein x=2, y=3 and R 3 =CH3.

[0008] Variations of these structures include the introduction of hydroxyl groups between the positive charge (quaternary ammonium) and the negative charge (sulfonate). Rashig sells SHPE monomers of, in particular, the following formula (II).

[0009]

[0010] There are also zwitterionic monomers having acrylamide groups, thus making it possible to obtain a stronger resistance to hydrolysis than zwitterionic monomers of the (meth)acrylic type. These structures are available from Rashig, for example in its In the mer series, the names are SPP (the following formula (III)) and SHPP (the following formula (IV)).

[0011]

[0012] These zwitterionic monomers can be obtained by different synthetic routes. For example, documents CN104926696, US3473998 and US4585846 describe the reaction between monomers with tertiary amines and sulfonic acid cyclic esters (also known as alkyl sultones). The length of the alkyl chain is generally 3 to 7 carbon atoms.

[0013] The most commonly used reagents are usually propane sultone and butane sultone. But these compounds are highly toxic reagents with carcinogenic, mutagenic and retoxicity classifications. Therefore, they are highly undesirable. In addition, alkyl sultones hydrolyze in aqueous media, which requires strict control of the water content in the reaction medium, thus making the reaction conditions difficult.

[0014] Documents US3,239,560 and CN105130851 describe the use of sodium hydroxyalkylsulfonate halides as reagents in order to abandon the use of cyclic esters of sulfonic acid. These hydroxyalkylsulfonate halides are obtained by the reaction between epichlorohydrin as a toxic compound and sodium sulfite, or sodium bisulfite, or sodium pyrosulfite. Therefore, the formation of zwitterionic monomers is carried out in two steps, and toxic compounds are always used. In addition, sodium hydroxyalkylsulfonate chloride is used together with tertiary amines to produce a certain amount of salt (NaCl), which must be removed from the reaction medium, which makes the reaction management more complicated. Finally, this type of reaction produces a non-negligible amount of by-products, which requires an additional step of purification by recrystallization of the sulfobetaine monomers synthesized in this way. Therefore, these methods are not satisfactory.

[0015] The document "Synthesis of a series of monomeric styrene sulfobetaine precursors" (Lukas Sonnenschein and Andreas Seubert, Tetrahedron Letters, Vol. 52, 2011, pp. 1101-1104) describes the use of sodium alkylsulfonate bromide as a reagent. In addition to the sulfobetaine monomers obtained, salts (NaBr) are also produced, which requires an additional stage of purification of the reaction medium. Therefore, this method is not satisfactory.

[0016] Therefore, it appears that obtaining new zwitterionic monomers, especially sulfobetaines, in good purity in high yields while minimizing the use of toxic reagents remains a major challenge. Summary of the invention

[0017] The applicant has discovered novel sulfobetaine monomers and methods for preparing the same, making it possible to achieve the above objectives.

[0018] The present invention relates to a sulfobetaine monomer of the following formula (V), or an acid form thereof, wherein SO3H replaces SO3 - More specifically, the present invention relates to a hydrated crystalline form of the monomer, the preparation of the monomer (hydrated crystalline form or non-hydrated crystalline form), the preparation of a (co)polymer of the monomer (hydrated crystalline form or non-hydrated crystalline form), and a (co)polymer of the monomer (especially its hydrated crystalline form) and its use.

[0019]

[0020] A monomer "and / or" its acid form is understood to mean the monomer or the acid form of the monomer, or the monomer and its acid form.

[0021] The present invention relates to molecules in the form of zwitterions, i.e. molecules containing at least one positive charge and at least one negative charge on the same molecule, and to molecules in the form of acids, the latter having a proton H + Neutralize SO3 - When the functional group is negatively charged, it is present in an acid medium. In the present application, the expression "sulfobetaine monomer of formula (V), or its acid form" is used to describe both molecules.

[0022] Another aspect of the invention relates to a method for preparing a 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 a salt thereof. The reaction is optionally, and preferably, carried out in the presence of at least one reagent that solubilizes the compound of formula (VII).

[0023] Advantageously, the reaction can also be carried out in the presence of at least one solvent.

[0024]

[0025] In formulae (V) to (XIV):

[0026] R1 and R4 are independently -H or -CH3,

[0027] R2 and R3 are independently a linear C1-C10 alkyl group or a branched C3-C10 alkyl group or a linear C2-C10 alkylene group,

[0028] R5 is -H, or a linear C1-C22 alkyl group or a branched C3-C22 alkyl group, or R5 and R6 form an optionally branched C4-C10 carbocyclic ring,

[0029] R6 is a straight-chain C1-C22 alkyl group or a branched C3-C22 alkyl group, or R6 and R5 form an optionally branched C4-C10 carbocyclic ring,

[0030] X1=-COO-, or -CONH-, or -CH2-,

[0031] X2=-COO-, or -CONH-,

[0032] n is an integer of 0-10.

[0033] Typically, a range of values ​​includes the boundaries that define them. Thus, the boundaries 0 and 10 are included in the range of "0 to 10".

[0034] In the present application, -COO- corresponds to a carbon atom connected to the first oxygen atom by a double covalent bond and to the second oxygen atom by a single covalent bond, i.e., the group -C(=O)O-. The -CONH- group corresponds to a carbon atom connected to the oxygen atom by a double covalent bond and to the nitrogen atom by a single covalent bond, the nitrogen atom itself being connected to the hydrogen atom by a covalent bond, i.e., the -C(=O)NH- group. The carbon of the C=O group of X2 (-COO- or -CONH-) naturally forms a covalent bond with the carbon of the -CHR4- group of formula (V). n=0 means that (--) n It is a single bond between X1 and NR2R3.

[0035] When R i (i=2 and / or 3) is a straight chain C2-C 10 When alkylene, it advantageously contains a single C=C double bond, more advantageously a -CH=CH2 group.

[0036] For example, C1-C 20 The radical advantageously corresponds to a hydrocarbon radical comprising from 1 to 20 carbon atoms. Advantageously, the hydrocarbon radical comprises only carbon and hydrogen atoms.

[0037] In the present application, the salts of the sulfobetaine monomers of the formula (V) and the salts of the compounds of the formula (VII) are water-soluble salts of these monomers, for example alkali metal salts, alkaline earth metal salts or ammonium salts.

[0038] "Alkaline" or "alkali metal" refers to a chemical element from the first column (Group 1) of the Periodic Table of the Elements, excluding hydrogen, i.e., an element selected from the group consisting of lithium, sodium, potassium, rubidium, cesium and francium, preferably sodium or potassium.

[0039] "Alkaline earth" or "alkaline earth metal" refers to a chemical element from the second column (Group 2) of the Periodic Table of the Elements, ie, an element selected from beryllium, magnesium, calcium, strontium, barium and radium, preferably calcium or magnesium.

[0040] Another aspect of the present invention relates to the use of a sulfobetaine monomer of formula (V) and / or a salt thereof for preparing a (co)polymer.

[0041] Another aspect of the present invention relates to (co)polymers obtained from sulfobetaine monomers of formula (V) and / or their acid forms.

[0042] The invention also relates to the use of (co)polymers obtained from sulfobetaine monomers of formula (V) and / or their acid forms as flocculants, dispersants, thickeners (rheology modifiers), absorbents (e.g. SAP-type superabsorbents, which swell in water), friction reducers, water retainers, mineral filler retainers or foaming and foam stabilizers. The (co)polymers may have one or more of these properties.

[0043] The present invention also relates to the use of (co)polymers obtained from sulfobetaine monomers of formula (V) and / or their acid forms in oil and gas recovery, water treatment, sludge treatment, improving the transport of aqueous fluids in pulp processing, papermaking, construction, mining, cosmetic preparations, detergent preparations, textile manufacturing, agriculture or medical hydrogel manufacturing.

[0044] Finally, the present invention also relates to a hygiene product composition, a cosmetic composition, a shampoo composition or a pharmaceutical composition comprising at least a sulfobetaine monomer of formula (V) and / or a (co)polymer thereof in acid form, as well as a process for the manufacture of said composition.

[0045] Sulfobetaine monomer

[0046] The present invention relates to a sulfobetaine monomer of the following formula (V), or an acid form thereof.

[0047]

[0048] According to one particular embodiment, the group R1 of formula (V) is a hydrogen atom.

[0049] According to a first specific embodiment of the invention, the sulfobetaine monomer has a structure of formula (V), wherein n is equal to 3. In this case, preferably, R2 and R3 are each a CH3 group, and X1 is CONH.

[0050] According to a second specific embodiment of the invention, the sulfobetaine monomer has a structure of formula (V), wherein n is equal to 0. In this case, preferably, R2 and R3 are each a CH3 group, and X1 is a -CH2- group.

[0051] According to a third specific embodiment of the invention, the sulfobetaine monomer has a structure of formula (V), wherein n is equal to 2. In this case, preferably, R2 and R3 are each a CH3 group, and X1 is -COO-.

[0052] Preferably, R4 is a hydrogen atom, and X2 is -CONH-. In this case, R5 and R6 are preferably CH3 groups. These preferred situations are generally applicable to formula (V), and are preferably applicable to one of the first three specific embodiments described above.

[0053] According to a fourth specific and preferred embodiment of the present invention, the sulfobetaine monomer is a monomer having the structure of the following formula (VIII) or its acid form. This monomer is called MAAMPS, more precisely 2-(3-((2-(methacryloyloxy)ethyl)dimethylamino)propionamido)-2-methylpropane-1-sulfonate.

[0054]

[0055] According to a fifth specific and preferred embodiment of the present invention, the sulfobetaine monomer is a monomer having a structure of the following formula (IX) or its acid form. This monomer is called a MAMMPS monomer, more precisely 2-(3-((2-(methacrylamidopropyl)dimethylamino)propionamido)-2-methylpropane-1-sulfonate.

[0056]

[0057] According to a sixth specific and preferred embodiment of the present invention, the sulfobetaine monomer is a monomer having a structure of the following formula (X) or its acid form. This monomer is called ALMPS, more precisely 2-(3-(allyldimethylamino)propionamido)-2-methylpropane-1-sulfonate.

[0058]

[0059] According to a seventh specific and preferred embodiment of the present invention, the sulfobetaine monomer is a monomer having a structure of the following formula (XI) or its acid form. This monomer is called AAMPS, more precisely 2-(3-((2-(acryloyloxy)ethyl)dimethylamino)propionamido)-2-methylpropane-1-sulfonate.

[0060]

[0061] According to an eighth specific and preferred embodiment of the present invention, the sulfobetaine monomer is a monomer having a structure of the following formula (XII) or its acid form. This monomer is called AMMPS, more precisely 2-(3-((2-acrylamidopropyl)dimethylamino)propionamido)-2-methylpropane-1-sulfonate.

[0062]

[0063] According to a ninth specific and preferred embodiment of the present invention, the sulfobetaine monomer is a monomer having a structure of the following formula (XIII) or its acid form. This monomer is called DAMPS, more precisely 2-(3-(diallylmethylamino)propionamido)-2-methylpropane-1-sulfonate.

[0064]

[0065] According to a tenth specific and preferred embodiment of the invention, the sulfobetaine monomer of formula (V) is in a hydrated crystalline form.

[0066] According to an eleventh specific and preferred embodiment of the present invention, the sulfobetaine monomer of formula (VIII) is in a hydrated crystalline form having an X-ray powder diffraction pattern comprising the following characteristic peaks:

[0067] 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. Uncertainties are typically on the order of + / - 0.05°.

[0068] Process P1 for preparing sulfobetaine monomers of formula (V)

[0069] The present invention also relates to a process P1 for preparing a 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 and preferably in the presence of at least one solubilizer and optionally in the presence of at least one solvent.

[0070]

[0071] In the preparation process according to the invention, the same preferences for the features R1 to R6, X1, X2 and n described previously for the sulfobetaine monomers apply to formulae (VI) and (VII).

[0072] Thus, the compound of formula (VI) is preferably selected from dimethylaminopropylmethacrylamide, dimethylethylaminopropylacrylamide, allyldimethylamine, diallylmethylamine, dimethylaminoethylmethacrylate, dimethylaminoethylacrylate. More preferably, the compound of formula (VI) is selected from dimethylaminopropylmethacrylamide, acrylamide, allyldimethylamine and dimethylaminoethylacrylate. Even more preferably, it is dimethylaminopropylmethacrylamide or dimethylaminopropylacrylamide.

[0073] As for the compound of formula (VII), using its acid form in method P1 is preferred to using its salt form. The compound of formula (VII) is preferably 2-acrylamido-2-methylpropanesulfonic acid and / or a salt thereof, preferably its acid form. According to a specific embodiment, 2-acrylamido-2-methylpropanesulfonic acid is in the form of its monohydrate, as described in document WO 2018 / 172676.

[0074] According to the method of the present invention, multiple amines (compound (VI)) can be reacted with the compound of formula (VII) in the same reaction. In other words, the method according to the present invention also covers the reaction of at least two compounds of formula (VI) with at least one compound of formula (VII). The reaction product will then contain a variety of different molecules of formula (V). Similarly, at least one compound of formula (VI) can be reacted with at least two compounds of formula (VII).

[0075] The reaction between the compound of formula (VI) and (VII) is preferably carried out in the presence of a reagent for solubilizing the compound of formula (VII) in the reaction medium. When there is at least one solubilizing agent in the reaction medium during the reaction, the reaction yield improves. The reaction can be carried out in the absence of a solubilizing agent, but is preferably carried out in the presence of at least one solubilizing agent.

[0076] In the context of the present invention, a solubilizing agent is a compound that allows the compound of formula (VII) to partially or completely dissolve in a reaction medium. The terms "solubiliser" and "solubilizing agent" are used equivalently in this application. In other words, a solubilizing agent is a reagent that makes the compound of formula (VII) solubilized in a reaction medium. Due to its presence, the solubility of the compound of formula (VII) in a reaction medium is improved. Here is how these compounds can more effectively participate in the reaction. Dissolution can be partial, the dissolved part reacts with the compound of formula (VI) to form a compound of formula (V), then another part of the compound of formula (VII) is dissolved and then reacted, and so on, so that substantially all compounds of formula (VII) are finally dissolved and reacted at the end of the reaction.

[0077] The solubilizing agent is preferably selected from water, alkanes, alcohols, amides, such as N-methylpyrrolidone, or a mixture of these compounds. More preferably, the solubilizing agent is selected from water, methanol, ethanol, isopropanol, dimethylformamide, or a mixture of these compounds. Even more preferably, the solubilizing agent is water.

[0078] The amount of the solubilizer is preferably 0 to 200 mass %, preferably 0.0001 to 150 mass %, even more preferably 0.001 to 100 mass %, even more preferably 0.1 to 80 mass % relative to the mass of the compound of formula (VII). The amount of the solubilizer (solubilizer) is preferably greater than 0.5 mass %, more preferably greater than 1 mass %, even more preferably greater than 2 mass %, even more preferably greater than 5 mass %.

[0079] The reaction can be optimized by adjusting the amount of solubilizing agent according to the exact properties of compounds (VI) and (VII). In other words, the best reactivity and yield obtained with the same amount of solubilizing agent depends on the properties of compounds (VI) and (VII), in particular compound (VII). Those skilled in the art can easily perform such optimization.

[0080] When compound (VI) is dimethylaminoethyl methacrylate or diallylmethylamine (DAMA) and compound (VII) is 2-acrylamido-2-methylpropanesulfonic acid and / or a salt thereof, the amount of the solubilizer is preferably 0% to 50% by mass, more preferably 0.01% to 40% by mass, relative to the total mass of compound (VI) and (VII) and the optional solubilizer and solvent. The amount of the solubilizer is preferably greater than 0.5% by mass, more preferably greater than 1% by mass, even more preferably greater than 2% by mass, even more preferably greater than 5% by mass. The solubilizer is preferably water.

[0081] When compound (VI) is dimethylaminoethyl acrylate and compound (VII) is 2-acrylamido-2-methylpropanesulfonic acid and / or a salt thereof, the amount of the solubilizer is preferably 0% to 20% by mass, more preferably 0.01% to 15% by mass, relative to the total mass of compounds (VI) and (VII) and any final solubilizer and solvent. The amount of the solubilizer is preferably greater than 0.5% by mass, more preferably greater than 1% by mass, and even more preferably greater than 2% by mass. The solubilizer is preferably water.

[0082] When compound (VI) is dimethylaminopropyl methacrylamide (DMAPMA) or dimethylaminopropyl acrylamide (DMAPAA) or allyl dimethylamine (ADMA), and compound (VII) is 2-acrylamido-2-methylpropanesulfonic acid and / or a salt thereof, the amount of the solubilizer is preferably 0% to 50% by mass, more preferably 0.01% to 30% by mass, relative to the total mass of compound (VI) and (VII) and any final solubilizer and solvent. The amount of the solubilizer is preferably greater than 0.5% by mass, more preferably greater than 1% by mass, even more preferably greater than 2% by mass, even more preferably greater than 5% by mass. The solubilizer is preferably water.

[0083] The preparation method according to the present invention can be carried out discontinuously (i.e. batchwise), in a semi-discontinuous manner (i.e. semi-batchwise) or continuously. It is preferably carried out batchwise. The addition of the compound of formula (VI) or (VII) and the optional solubilizing agent can be carried out separately or simultaneously. The compound of formula (VI) can be first added to the reactor, and then the compound of formula (VII), or vice versa. The first of these configurations is preferred (compound (VI) then compound (VII)). The addition of each component can be completed in a single step, multiple steps or gradually poured.

[0084] The compound of formula (VI), formula (VII) and optional solubilizing agent can be added to the reactor in any order. When using a solubilizing agent, the preparation method according to the present invention preferably comprises a first step, wherein the solubilizing agent is added and mixed with the compound of formula (VI), and in a second step, the compound of formula (VII) is added to the reaction medium.

[0085] The reaction between the compounds of formula (VI) and (VII) is preferably carried out under stirring. The stirring speed is preferably 10 to 1000 rpm.

[0086] The reaction temperature between the compounds of formula (VI) and (VII) is preferably between -20°C and 100°C, more preferably between 0°C and 50°C. The optimal reaction temperature is preferably between 10 and 40°C, even more preferably between 15 and 35°C, even more preferably between 15 and 25°C. Better performance is generally obtained under these optimal conditions.

[0087] The duration of the reaction between the compounds of formula (VI) and (VII) is advantageously from 0.5 hours to 10 days, preferably from 1 hour to 7 days, more preferably from 2 hours to 72 hours.

[0088] The molar ratio of the reactants is generally determined by a person skilled in the art to maximize the yield of the sulfobetaine monomer of formula (V) and / or its acid form. The molar ratio of the compound of formula (VI) to the compound of formula (VII) and / or one of its salts is preferably from 0.1:1 to 20:1, more preferably from 1.01:1 to 20:1, even more preferably from 1.1:1 to 15:1. The molar ratio may in particular be from 6:1 to 10:1, or from 8:1 to 10:1.

[0089] When the ratio is between 0.1:1 and 1:1, the additional compound is advantageously used so that the molar ratio between the amount of compound of formula (VI) added plus the amount of additional compound and the amount of compound of formula (VII) is advantageously greater than or equal to 1.

[0090] The additional compound is advantageously selected from alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal oxides, alkaline earth metal oxides, alkali metal carbonates, alkaline earth metal carbonates, alkali metal hydrogen carbonates, alkaline earth metal hydrogen carbonates or compounds of the formula NR 10 R 20 R 30 Amines, where R 10 , R 20 and R 30 Each is independently a hydrogen atom or a carbon chain containing 1 to 22 carbon atoms, such as an alkyl group in C1-C22. 10 , R 20 and R 30 Each is a hydrogen atom.

[0091] When the additional compound is an alkali metal hydroxide or an alkaline earth metal hydroxide, it is preferably selected from sodium hydroxide, potassium hydroxide, lithium hydroxide, magnesium hydroxide and calcium hydroxide. When the additional compound is an alkali metal oxide or an alkaline earth metal oxide, it is preferably calcium oxide or magnesium oxide. When the additional compound is an alkali metal carbonate, it is preferably sodium carbonate or potassium carbonate. When the additional compound is an alkali metal bicarbonate, it is preferably sodium bicarbonate or potassium bicarbonate. Preferably, the additional compound is sodium carbonate or potassium carbonate.

[0092] The reaction between the compounds of formula (VI) and (VII) takes place at a pressure of preferably 0.1 to 50 bar, more preferably 0.5 to 10 bar, even more preferably at atmospheric pressure. "Bar" is understood to mean a pressure corresponding to 10 5 Absolutely Pa.

[0093] According to one particular embodiment, a solvent may also be used in the process according to the invention. In the context of the present invention, a "solvent" is a compound which makes it possible to dilute the reaction medium without chemically modifying the reagents and without modifying itself.

[0094] The solvent may advantageously be selected from alkanes, ketones, nitriles, alcohols and ethers, more preferably the solvent is acetone. In a preferred embodiment, the solvent is a compound having a melting temperature below 15° C., more preferably below 5° C. In fact, solvents having a melting temperature above 15° C. reduce the yield of the reaction, especially when polar and aprotic solvents are involved.

[0095] One skilled in the art will be able to adjust the amount of solvent to optimize the reaction.

[0096] The reaction is carried out using an amount of polymerization inhibitor of 0 to less than 500 ppm relative to the total mass of the compounds of formulae (VI) and (VII).

[0097] When the reaction is carried out in the presence of an inhibitor, it is preferred to use an amount less than 500ppm, preferably less than 200ppm, more preferably less than 100ppm, and even more preferably less than or equal to 50ppm, relative to the total mass of the reactants (compounds of formula (VI) and (VII)). An amount greater than or equal to 10ppm, or even greater than or equal to 20ppm can be used. It has been observed that the use of an excessive amount of inhibitor reduces the yield of the reaction. Compared to the usual amount (generally greater than 5000ppm), the amount of inhibitor is reduced, preferably reduced to less than 500ppm, so that the reaction yield and the purity of the product obtained can be improved. Reducing the amount of inhibitor to 50ppm or less makes it possible to further improve the reaction yield and the purity of the product obtained, and more significantly than by maintaining the amount of inhibitor greater than 50ppm.

[0098] On the contrary, the methods of the prior art, in particular the documents CN 103274955, CN 107383287, Kazantsev et al., Russian Journal of General Chemistry, 2018, Vol. 88, No. 4, pp. 641-645, Kazantsev et al., Russian Journal of Organic Chemistry, 2000, Vol. 36, No. 3, pp. 343-349, and Shirshin et al., Russian Journal of Applied Chemistry, 1990, Vol. 72, No. 2, pp. 278-281, use an amount of inhibitor greater than or equal to 1000 ppm, typically 1000 ppm to 5000 ppm. Compared with the amounts described above in the context of the present invention, this translates into lower reaction yields and purity.

[0099] Preferably, the polymerization inhibitor is selected from the group consisting of monomethylhydroquinone ether (EMHQ), hydroquinone, benzoquinone, phenothiazine, phenylnaphthylamine, diphenylpicrylhydrazyl.

[0100] Preferably, the reaction is carried out in the absence of a polymerization inhibitor.

[0101] In the process of the present invention, the solubilizing agent promotes the dissolution of the compound of formula (VII) in the reaction medium. The dissolved molecules of formula (VII) then react with the compound of formula (VI) to form the sulfobetaine monomer of formula (V).

[0102] The reaction product obtained can be a crystal suspension of the compound of formula (V) or a solution of the compound of formula (V). In other words, the compound of formula (V) obtained at the end of the reaction is in solid (crystal) or liquid (dissolved) form. The physical state of the reaction product and therefore the compound of formula (V) depends on the presence or absence of solubilizing agent and / or solvent, and their amount in the reaction medium.

[0103] In the case where crystals of sulfobetaine monomers of formula (V) are obtained at the end of the reaction, they are then preferably separated from the reaction medium by a liquid / solid separation step. By way of example, but not limitation, mention may be made of the use of vertical or horizontal centrifuges, decanters, filter presses, belt filters, disc filters, drums under vacuum or pressure.

[0104] Preferably, the crystals obtained after the liquid / solid separation step are optionally washed once or multiple times and then dried. Any washing and drying method can be used. Therefore, the final product obtained is a crystalline powder of the compound of formula (V). It can be washed with alcohol or ketones such as acetone.

[0105] The process for preparing the sulfobetaine monomer of formula (V) and / or its acid form preferably comprises the following consecutive steps:

[0106] a1) adding at least one compound of formula (VI), optionally and preferably at least one solubilizer for the compound of formula (VII) and optionally a solvent to a stirred reactor to obtain a pre-reaction mixture;

[0107] a2) adding at least one compound of formula (VII) and / or a salt thereof to the pre-reaction mixture;

[0108] a3) after the reaction between the compounds of formula (VI) and (VII), which makes it possible to obtain the sulfobetaine monomer of formula (V) and / or its acid form, obtaining the sulfobetaine monomer of formula (V) and / or its acid form in the form of a suspension or solution of crystals.

[0109] When the reaction product is a suspension of crystals, the process according to the invention preferably comprises a subsequent step of isolating the crystals, optionally followed by one or more washing steps, optionally followed by a subsequent step of drying the crystals. When the reaction product is a monomer solution, a powder may be obtained after drying.

[0110] According to a specific embodiment of the present invention, the liquid obtained in the crystal separation step can be recycled. In other words, it can be implemented again in a new reaction according to the method of the present invention. In fact, the liquid can comprise a portion of compounds of formula (VI) and formula (VII) and optional solubilizing agents and / or solvents. In order to optimize the raw materials involved in the reaction, those skilled in the art will know how to implement this specific embodiment of the present invention and adjust the addition amount of compounds of formula (VI), formula (VII), and the addition amount of optional solubilizing agents and / or solvents for implementing the liquid during the new reaction of the present invention.

[0111] When the reaction product is a solution, it can be concentrated or diluted. In view of these situations, those skilled in the art will be able to adjust the reaction parameters to optimize the reaction and its yield. For this purpose, techniques known to those skilled in the art can be used.

[0112] Process P2 for preparing sulfobetaine monomer of formula (V) in hydrated crystalline form

[0113] According to one particular embodiment of the invention, a reaction product corresponding to a hydrated crystalline form of the compound of formula (V) is obtained. Process P2 also advantageously involves using the characteristics of process P1 described above.

[0114] According to this specific embodiment, two alternatives are possible.

[0115] A first alternative consists in carrying out steps a1) to a3 of process P1 using as solubilizer an amount of water sufficient to form a hydrated crystalline form of the compound of formula (V). More specifically, the amount of water used as solubilizer in the reaction according to the process of the invention is preferably at least 10% by mass, preferably at least 20% by mass, 30% by mass, 40% by mass, or even more preferably at least 50% by mass relative to the total mass of compounds (VI) and (VII) and optionally solubilizer and solvent. A person skilled in the art will know how to adjust the amount of water according to the properties of the compounds of formula (VI) and (VII) to obtain crystals of a hydrated crystalline form of the compound of formula (V).

[0116] According to the first embodiment, the second alternative comprises performing the following steps:

[0117] a1) adding at least one compound of formula (VI), optionally a solubilizing agent for at least one compound of formula (VII) and optionally a solvent to a stirred reactor to obtain a pre-reaction mixture;

[0118] a2) adding at least one compound of formula (VII) and / or a salt thereof to the pre-reaction mixture;

[0119] a3) after the reaction, a sulfobetaine monomer of formula (V) and / or its acid form is obtained in the form of a solution;

[0120] a4) extracting the compound of formula (V) in the form of crystalline AA;

[0121] a5) combining the crystals AA of the compound of formula (V) with an aqueous solution to form a suspension A;

[0122] a6) mixing the suspension A for 1 minute to 20 hours;

[0123] a7) obtaining a suspension B of crystals BB of the compound of formula (V) in hydrated form;

[0124] a8) optionally isolating the obtained crystals BB from the suspension B.

[0125] According to a second embodiment, the second alternative does not comprise step a4) but consists in carrying out the following steps:

[0126] a1) adding at least one compound of formula (VI), optionally a solubilizing agent for at least one compound of formula (VII) and optionally a solvent to a stirred reactor to obtain a pre-reaction mixture;

[0127] a2) adding at least one compound of formula (VII) and / or a salt thereof to the pre-reaction mixture;

[0128] a3) after the reaction, a sulfobetaine monomer of formula (V) and / or its acid form is obtained in the form of a suspension of crystals AA;

[0129] a5) combining the crystals AA of the compound of formula (V) with an aqueous solution to form a suspension A;

[0130] a6) mixing the suspension A for 1 minute to 20 hours;

[0131] a7) obtaining a suspension B of crystals BB of the compound of formula (V) in hydrated form;

[0132] a8) optionally isolating the obtained crystals BB from the suspension B.

[0133] A person skilled in the art will know how to adjust the reaction parameters so as to obtain, at the end of step a3), a suspension or solution of crystalline AA.

[0134] According to an embodiment of this second alternative embodiment, it is preferred to first isolate the compound of formula (V) in its crystalline form AA. To this end, an extraction step is performed when the reaction product is a solution, or a liquid / solid separation step is performed when the reaction product is a suspension. The extraction step can be performed using any technique known to those skilled in the art, such as evaporation, crystallization (e.g. by cooling) or membrane separation.

[0135] The obtained crystals AA are then combined with an aqueous solution to form a suspension A, which preferably contains at least 80% by mass of water, preferably at least 90% by mass, 95% by mass or more preferably at least 99% by mass of water. Preferably, the aqueous solution is water. The aqueous solution may contain up to 20% by mass, preferably 0 to 15% by mass, more preferably 0 to 10% by mass of an organic solvent.

[0136] The organic solvent is preferably selected from acids containing 1 to 8 carbon atoms (e.g. carboxylic acids), amides containing 1 to 8 carbon atoms, alcohols containing 1 to 8 carbon atoms, ketones containing 3 to 8 carbon atoms, ethers containing 2 to 8 carbon atoms, esters containing 2 to 8 carbon atoms, alkanes containing 1 to 8 carbon atoms, halogenated hydrocarbons containing 1 to 8 carbon atoms, nitriles containing 2 to 8 carbon atoms, or mixtures thereof.

[0137] Crystalline AA may be in powder form or shaped by methods such as compaction, granulation or extrusion.

[0138] The mass ratio of the aqueous solution to the crystalline AA is 1:0.5 to 1:2, preferably 1:1 to 1:1.5.

[0139] The combination of the aqueous solution and the crystalline AA can be accomplished in one step or in multiple steps.

[0140] The step of mixing the suspension A is usually carried out for 1 minute to 20 hours, preferably 30 minutes to 8 hours, more preferably 2 to 5 hours. The mixing temperature is generally 1° C. to 40° C. The lower limit of the temperature depends on the composition and physical properties of the solution or suspension A.

[0141] Various apparatuses can be used to mix the suspension A. By way of example, but not limitation, mention may be made of reactors with stirrers, loop reactors, static mixers, microreactors, piston reactors, paddle mixers, double cone mixers, ploughshare mixers or rotating disk mixers.

[0142] When the suspension A is mixed, crystals BB of the compound of formula (V) are formed in hydrated form. At the end of the crystallization conversion reaction, a suspension B containing crystals BB of the compound of formula (V) in hydrated form is obtained.

[0143] The step of separating the crystals BB of the compound of formula (V) in hydrated form can then be carried out by solid / liquid separation. The solid / liquid separation can be accomplished by, for example, but not limited to, using a horizontal or vertical centrifuge, a decanter, a filter press, a belt filter, a disc filter or a drum filter. The liquid / solid separation can also be carried out by gravity settling.

[0144] The composition obtained at the end of the separation step preferably comprises from 40 to 99% by mass, more preferably from 60 to 98% by mass, of crystals BB of the compound of formula (V) in hydrated form. The remainder of the composition is mainly water.

[0145] The crystals BB obtained at the end of the separation step can be dried. Preferably, however, the crystals BB are not dried.

[0146] For industrial optimization and recycling of compounds, the liquid phase obtained after liquid / solid separation comprising water, optionally non-crystalline sulfobetaine monomer of formula (V) and optionally organic solvent can be used in whole or in part as aqueous solution in contact with crystalline AA.

[0147] According to one embodiment, the reaction is carried out using an amount of polymerization inhibitor ranging from 0 to less than 500 ppm relative to the total mass of the compounds of formula (VI) and (VII).

[0148] When the reaction is carried out in the presence of an inhibitor, an amount of less than 500 ppm, preferably less than 200 ppm, more preferably less than 100 ppm, even more preferably less than or equal to 50 ppm relative to the total mass of the reactants (compounds of formula (VI) and (VII)) is used. An amount greater than or equal to 10 ppm, or even greater than or equal to 20 ppm may be used. As described above, the use of a small amount of inhibitor makes it possible to maximize the reaction yield and the purity of the resulting product.

[0149] Preferably, the polymerization inhibitor is selected from the group consisting of monomethylhydroquinone ether (EMHQ), hydroquinone, benzoquinone, phenothiazine, phenylnaphthylamine, diphenylpicrylhydrazyl.

[0150] Preferably, the reaction is carried out in the absence of a polymerization inhibitor.

[0151] Polymers obtained from sulfobetaine monomers

[0152] The present invention also relates to the use of sulfobetaine monomers of formula (V) and / or their acid forms in the preparation of (co)polymers, and to (co)polymers obtained from sulfobetaine monomers of formula (V) and / or their acid forms.

[0153] In other words, the present invention also relates to a process for preparing a sulfobetaine monomer of formula (V) and / or a (co)polymer thereof in acid form, the process comprising the following steps:

[0154] - preparing a sulfobetaine monomer of formula (V) and / or its acid form in hydrated or non-hydrated crystalline form by the above-mentioned preparation process P1 or P2,

[0155] - (co)polymerizing at least the sulfobetaine monomers obtained to form a (co)polymer.

[0156] According to one particular embodiment of the invention, the polymer is obtained only from sulfobetaine monomers of formula (V) and / or their acid forms.

[0157] According to another particular embodiment of the invention, the polymer is a copolymer comprising at least one sulfobetaine monomer of formula (V) and / or its acid form and at least one other generally water-soluble monomer.

[0158] The water-soluble monomer may be a nonionic monomer, which may in particular be selected from the group comprising: water-soluble vinyl monomers, in particular acrylamide; methacrylamide; N-isopropylacrylamide; N,N-dimethylacrylamide; N-vinylformamide; acryloylmorpholine; N,N-diethylacrylamide; N-tert-butylacrylamide; N-tert-octylacrylamide; N-vinylpyrrolidone; N-vinylcaprolactam; N-vinyl-imidazole, hydroxyethylmethacrylamide, hydroxypropyl acrylate, isoprenol and diacetoneacrylamide, 2-(diethylaminoethyl)methacrylate (DEAEMA) in salt form, maleic anhydride, hydroxyethylacrylamide (HEAA), N-vinylsuccinimide, monomers of formula (XIV), and mixtures thereof.

[0159]

[0160] R50 is an alkyl radical advantageously containing from 1 to 10 carbon atoms.

[0161] The nonionic monomers may also be selected from the following monomers:

[0162] DZD'

[0163] in:

[0164] -D is a polymerizable unsaturated chemical functional group of the acrylate, methacrylate, acrylamide, methacrylamide, vinyl or allyl type,

[0165] -D' represents hydrogen or an alkyl (advantageously C1-C22) or aryl (advantageously C1-C22) group,

[0166] -Z has the following structure: -(OE)w-(OP)x-(OBu)z-, where:

[0167] OE, OP, and OBu represent ethylene oxide, propylene oxide, and butylene oxide, respectively.

[0168] The arrangement between different patterns of OE and / or OP and / or OBu can be statistical, alternating, gradient or block,

[0169] w, x and z are mutually independent integers between 0 and 150, and w+x+z≠0.

[0170] Advantageously, the nonionic monomer is acrylamide.

[0171] Water-soluble monomers can also be selected from anionic monomers. Anionic monomers that can be used in the context of the present invention can be selected from a wide range of groups. These monomers can have vinyl functional groups, in particular acrylic acid, or maleic acid, fumaric acid, malonic acid, itaconic acid or allyl functional groups. They can also contain carboxylates, phosphonates, phosphates, sulfates, sulfonates or other groups with anionic charges. Anionic monomers can be in the form of acids, or in the form of alkaline earth metal salts, alkali metal salts or ammonium salts. Examples of suitable monomers include acrylic acid; methacrylic acid; itaconic acid; monomethyl itaconic acid; crotonic acid; maleic acid; fumaric acid; strong acid monomers, which have, for example, sulfonic acid or phosphonic acid type functional groups, such as vinyl sulfonic acid, vinyl phosphonic acid, allyl sulfonic acid, methyl allyl sulfonic acid, 2-methylenepropane-1,3-disulfonic acid, 2-sulfoethyl methacrylate, sulfopropyl acrylate, allyl phosphonic acid, styrene sulfonic acid; and water-soluble salts of these monomers, such as their alkali metal salts, alkaline earth metal salts or ammonium salts.

[0172] The water-soluble monomers may be cationic monomers of the vinyl type, in particular acrylamide, acrylic acid, allyl or maleic acid with an ammonium functional group, in particular quaternary ammonium, phosphonium or sulfonium. In particular, but not limited to, mention may be made of quaternized or salified dimethylaminoethyl acrylate (ADAME), quaternized or salified dimethylaminoethyl methacrylate (MADAME), quaternized or salified allylamine, quaternized or salified allyldimethylamine, quaternized or salified diallylmethylamine, dimethyldiallylammonium chloride (DADMAC), quaternized or salified dimethylaminopropylacrylamide, acrylamidopropyltrimethylammonium chloride (APTAC), quaternized or salified dimethylaminopropylmethacrylamide and methacrylamidopropyltrimethylammonium chloride (MAPTAC).

[0173] According to the invention, the (co)polymers may have linear, branched, network, star or comb structures. These structures can be obtained by selecting initiators, transfer agents, polymerization techniques such as controlled radical polymerization such as reversible addition fragmentation chain transfer (RAFT), nitroxide mediated polymerization (NMP) or atom transfer radical polymerization (ATRP), incorporation and / or concentration of structural monomers.

[0174] Crosslinking agents or branching agents can be used to construct the (co)polymers. They are advantageously selected in a non-limiting manner from methylene-bis-acrylamide (MBA), ethylene glycol diacrylate, tetraallyl ammonium polyethylene glycol chloride, diacrylamide, cyanomethyl acrylate, tetraallyl ammonium chloride (TAAC), triallylamine, epoxy resins and mixtures thereof.

[0175] Typically, the (co)polymer is obtained by a polymerization process that occurs in the usual manner, i.e. embodiments known to the person skilled in the art. In practice, it can be obtained according to all polymerization techniques known to the person skilled in the art. In particular, it can be polymerization in solution; gel polymerization; precipitation polymerization; (aqueous or inverse) emulsion polymerization; suspension polymerization; reactive extrusion polymerization; micellar polymerization; UV polymerization; or microwave polymerization.

[0176] According to a specific embodiment of the present invention, the (co)polymer can be subjected to a post-hydrolysis reaction. The post-hydrolysis reaction is a reaction of the (co)polymer after the (co)polymer is formed by polymerization of the monomers. This step comprises the reaction of a hydrolyzable functional group of a nonionic monomer (e.g., a monomer having an amide or ester functional group) with a base.

[0177] When the preparation of the (co)polymer includes a drying step such as spray drying, drum drying, drying by electromagnetic radiation (microwave or high frequency) or fluidized bed drying, the (co)polymer may be in liquid, gel or solid form.

[0178] The (co)polymer may have a molar mass advantageously between 10,000 and 30,000 Daltons.

[0179] The (co)polymers can be flocculants, dispersants, thickeners (rheology modifiers), absorbents (eg SAP-type superabsorbents, which swell in water), friction reducers, water-retaining and mineral filler retaining agents, or foaming and foam stabilizers.

[0180] The (co)polymer preferably contains at least 1 mol%, preferably at least 5 mol%, more preferably at least 10 mol%, even more preferably at least 20 mol%, even more preferably at least 30 mol%, even more preferably at least 50 mol% of sulfobetaine monomers of formula (V).

[0181] According to a particular embodiment of the present invention, the (co)polymer is a copolymer of a sulfobetaine monomer of formula (V) and / or its acid form and a nonionic monomer. In this case, the copolymer preferably contains 10 to 90 mol % of a sulfobetaine monomer of formula (V) and / or its acid form, and 10 to 90 mol % of a nonionic monomer, more preferably 30 to 90 mol % of a sulfobetaine monomer of formula (V) and / or its acid form, and 10 to 70 mol % of a nonionic monomer, even more preferably 50 to 90 mol % of a sulfobetaine monomer of formula (V) and / or its acid form, and 10 to 50 mol % of a nonionic monomer.

[0182] According to a particular embodiment of the present invention, the (co)polymer is a copolymer of a sulfobetaine monomer of formula (V) and / or its acid form and an anionic monomer. In this case, the copolymer preferably contains 5 to 95 mol % of a sulfobetaine monomer of formula (V) and / or its acid form, and 5 to 95 mol % of an anionic monomer, more preferably 5 to 70 mol % of a sulfobetaine monomer of formula (V) and / or its acid form, and 30 to 95 mol % of an anionic monomer, even more preferably 5 to 50 mol % of a sulfobetaine monomer of formula (V) and / or its acid form, and 50 to 95 mol % of an anionic monomer.

[0183] According to a particular embodiment of the present invention, the (co)polymer is a copolymer of a sulfobetaine monomer of formula (V) and / or its acid form and a cationic monomer. In this case, the copolymer preferably contains 5 to 95 mol% of a sulfobetaine monomer of formula (V) and / or its acid form, and 5 to 95 mol% of a cationic monomer, more preferably 5 to 70 mol% of a sulfobetaine monomer of formula (V) and / or its acid form, and 30 to 95 mol% of a cationic monomer, even more preferably 5 to 50 mol% of a sulfobetaine monomer of formula (V) and / or its acid form, and 50 to 95 mol% of a cationic monomer.

[0184] Use of sulfobetaine monomers of formula (V) and / or (co)polymers thereof in acid form

[0185] The present invention also relates to the use of (co)polymers obtained from sulfobetaine monomers of formula (V) and / or their acid forms as flocculants, dispersants, thickeners (rheology modifiers), absorbents (e.g. SAP-type superabsorbents, which swell in water), friction reducers, water retention agents, mineral filler retention agents or foaming agents and foam stabilizers.

[0186] The present invention also relates to the use of (co)polymers obtained from sulfobetaine monomers of formula (V) and / or their acid forms in oil and gas recovery, water treatment, sludge treatment, improving the transport of aqueous fluids in pulp processing, papermaking, construction, mining, cosmetic preparations, detergent preparations, textile manufacturing, agriculture or medical hydrogel manufacturing.

[0187] Finally, the present invention also relates to a hygiene product composition, a cosmetic composition, a shampoo composition or a pharmaceutical composition comprising at least a sulfobetaine monomer of formula (V) and / or a (co)polymer thereof in acid form, as well as a process for the manufacture of said composition.

[0188] The (co)polymers obtained from the sulfobetaine monomers of formula (V) and / or their acid forms can be used in all underground formation treatments to enhance oil or gas recovery. They can be used to increase the viscosity of aqueous injection fluids and / or to reduce the level of frictional resistance that occurs when injecting said fluids into underground formations, and / or to keep particles suspended in the injection fluid.

[0189] These subsurface treatments include, but are not limited to, drilling operations, stimulation treatments such as fracturing operations, completion operations, polymer solution sweep enhanced oil recovery processes, conformity operations, and operations to reduce the permeability of a subsurface formation or to divert portions of a subsurface formation.

[0190] These (co)polymers are particularly suitable for use in fracturing operations and polymer solution sweep enhanced oil recovery processes.

[0191] The present invention also relates to a fracturing process, which comprises:

[0192] a. Prepared from a (co)polymer comprising at least a sulfobetaine monomer of formula (V) and / or its acid form

[0193] Fracturing fluid, the (co)polymer is preferably in the form of an inverse emulsion;

[0194] b. Optionally and preferably introducing at least one proppant into the fracturing fluid;

[0195] c. introducing fracturing fluid into a portion of the underground formation;

[0196] d. Fracturing underground formations with injected fluids;

[0197] e. Recover a mixture of gas, oil and aqueous fluids.

[0198] Thus, the fracturing fluid treated in step c) comes from step a) in the absence of step b) or from step b) in the presence of step b). The fracturing process is carried out according to methods known to the person skilled in the art. In particular, the fracturing fluid may contain all additives and compounds known to the person skilled in the art.

[0199] The present invention also relates to a polymer solution sweeping enhanced oil recovery method, which comprises:

[0200] a. Prepared from a (co)polymer comprising at least a sulfobetaine monomer of formula (V) and / or its acid form

[0201] injecting a fluid, the (co)polymer preferably being in the form of an inverse emulsion or a powder;

[0202] b. introducing an injection fluid into a portion of a subterranean formation;

[0203] c. Sweep the lower formation with injected fluid;

[0204] d. Recover a mixture of gas, oil and aqueous fluids.

[0205] The enhanced oil recovery method is carried out according to methods known to those skilled in the art. In particular, the injection fluid may contain all additives and compounds known to those skilled in the art.

[0206] The invention also relates to a method for treating water (dirty water and wastewater, etc.) with a (co)polymer comprising at least a sulfobetaine monomer of formula (V) and / or its acid form. Wastewater is "contaminated water" and consists of all water that may pollute the environment in which it is discharged by physical, chemical or biological pollutants. Usually, a distinction is made between domestic wastewater, industrial wastewater, agricultural wastewater, and rainwater and runoff. The treatment process is preferably a process for treating domestic wastewater or for treating industrial wastewater.

[0207] The invention also relates to a method for treating sewage sludge with a (co)polymer comprising at least a sulfobetaine monomer of formula (V) and / or its acid form. This includes, but is not limited to, sewage sludge from water treatment, tailings from the mining industry, tailings from the coal industry, tailings from oil sand operations and all tailings containing mineral waste.

[0208] The present invention also relates to a method for improving the transport of aqueous fluids using a (co)polymer comprising at least a sulfobetaine monomer of formula (V) and / or its acid form. This relates to, but is not limited to, the transport of water in pipes, the transport of aqueous suspensions of solid particles (e.g. mineral waste) and the transport of sludge in pipes.

[0209] The present invention also relates to a process for treating pulp with a (co)polymer comprising at least a sulfobetaine monomer of formula (V) and / or an acid form thereof.

[0210] The invention also relates to a process for producing paper, typically paper or paperboard sheets, using a (co)polymer comprising at least a sulfobetaine monomer of formula (V) and / or its acid form. In this case, the (co)polymer of the invention is typically used as a retention aid, dry strength agent or wet strength agent.

[0211] The present invention also relates to a hygiene product composition, a cosmetic composition, a shampoo composition or a pharmaceutical composition comprising at least a sulfobetaine monomer of formula (V) and / or a (co)polymer thereof in acid form, and a process for preparing said composition.

[0212] In the following examples, the Bruker 400MHz ASCEND TM NMR analysis was performed on an Avance III HD instrument.

[0213] The infrared measurement equipment was Perkin Elmer Spectrum 100 model with a Fourier transform (with an accuracy of 8 cm -1) for IR analysis. The solids obtained in Examples 1 and 2 were sieved at 100 μm. The particles remaining on the sieve were dried and placed in an oven at 60° C. for at least 4 hours. 10 mg of the solid were accurately weighed and mixed with 500 mg of potassium bromide (KBr). The mixture was then compacted in a hydraulic press at a pressure of at least 10 bar.

[0214] X-ray diffraction analysis was performed using a Rigaku MiniFlex II diffractometer equipped with a copper source. The solid obtained after the reaction was ground into powder in advance and analyzed by X-ray diffraction in the angular range of 10 to 90°.

[0215] The following abbreviations are used in this application:

[0216] ADAME: 2-(dimethylaminoethyl) acrylate

[0217] MADAME: 2-(dimethylaminoethyl) methacrylate

[0218] MAAMPS: 2-(3-((2-(methacryloyloxy)ethyl)dimethylamino)propionamido)-2-methylpropane-1-sulfonate

[0219] AAMPS: 2-(3-((2-(acryloyloxy)ethyl)dimethylamino)propionamido)-2-methylpropane-1-sulfonate

[0220] ALMPS: 2-(3-(allyldimethylamino)propionamido)-2-methylpropane-1-sulfonate

[0221] DAMPS: 2-(3-(diallylmethylamino)propionamido)-2-methylpropane-1-sulfonate

[0222] AMMPS: 2-(3-((2-acrylamidopropyl)dimethylamino)propionamido)-2-methylpropane-1-sulfonyl

[0223] Acid esters

[0224] MAMMPS: 2-(3-((2-methacrylamidopropyl)dimethylamino)propionamido)-2-methylpropane-1-sulfonate

[0225] DMAPS: [2-(Methacryloyloxy)-ethyl]-dimethyl-(3-sulfopropyl)-ammonium hydroxide

[0226] MBA: N'-Methylenebisacrylamide

[0227] EGDMA: Ethylene glycol dimethacrylate

[0228] AA: Acrylic acid

[0229] AM: Acrylamide

[0230] ADC: 2-Dimethylaminoethyl acrylate methyl chloride, also known as trimethyl (2-prop-2-enoyloxyethyl) ammonium chloride

[0231] AIBN: Azobisisobutyronitrile

[0232] HLB: Hydrophile-Lipophile Balance

[0233] DLS: Dynamic Light Scattering

[0234] Dh: hydrodynamic diameter

[0235] FPR = Total Retention Rate (Fiber + Mineral Filler)

[0236] FPAR = Mineral Filler Retention Rate

[0237] DDA: Drainage Vacuum

[0238] HVFR: High Viscosity Friction Reducer

[0239] GPT: Gallons per thousand (gallons per thousand, i.e. 1 pound / 1000 US gallons = 120 ppm by mass)

[0240] D: Darcy

[0241] The invention and the resulting advantages will emerge better from the following figures and examples, which are given for the purpose of illustrating the invention and not in a limiting manner. BRIEF DESCRIPTION OF THE DRAWINGS

[0242] Figure 1 The proton NMR spectrum of the AAMPS monomer is shown.

[0243] Figure 2 The proton NMR spectrum of the MAMMPS monomer is shown.

[0244] Figure 3 The proton NMR spectrum of the AMMPS monomer is shown.

[0245] Figure 4 The proton NMR spectrum of the MAAMPS monomer is shown.

[0246] Figure 5 The proton NMR spectrum of the ALMPS monomer is shown.

[0247] Figure 6 The proton NMR spectrum of the DAMPS monomer is shown.

[0248] Figure 7 An X-ray diffraction pattern of the MAAMPS monomer crystals in the hydrated crystalline form of Example 7 is shown.

[0249] Figure 8 An X-ray diffraction pattern of the anhydrous crystalline form of MAAMPS monomer crystals of Example 10 is shown.

[0250] Fig. 9 The IR spectrum of the AAMPS monomer is shown.

[0251] Fig.10 The IR spectrum of the MAMMPS monomer is shown.

[0252] Fig.11 The IR spectrum of AMMPS monomer is shown.

[0253] Fig.12 The IR spectrum of the MAAMPS monomer is shown.

[0254] Fig.13 The IR spectrum of the ALMPS monomer is shown.

[0255] Fig.14 The IR spectrum of the DAMPS monomer is shown.

[0256] Fig.15 Crystals corresponding to monomeric MAAMPS of Example 7 in hydrated crystalline form observed under an optical microscope.

[0257] Fig.16 Crystals corresponding to the MAAMPS monomer of Example 10 in anhydrous crystalline form observed under an optical microscope.

[0258] Fig.17 Graph of Dh as a function of temperature at a concentration of 1 mg / mL corresponding to Tests 1-1, 1-2, and 1-3 of Example 17A.

[0259] Fig.18 A graph of Dh as a function of temperature at a concentration of 1 mg / mL corresponding to Tests 2-1 and 2-2 of Example 17B.

[0260] Fig.19 Graph of Dh variation during reversibility test of thermal expansion and thermal aggregation (temperature cycle from 15°C to 90°C and then at 15°C) corresponding to Test 4-1 of Example 17D.

[0261] Fig. 20 Graph of Dh variation during reversibility testing of thermal expansion and thermal aggregation (temperature cycling from 15°C to 90°C and then at 15°C) corresponding to Test 4-2 of Example 17D.

[0262] Fig.21 Graph of differential pressure change dP corresponding to Test 5-1 of Example 17-E.

[0263] Fig. 22 Graph of the change in differential pressure dP at temperatures of 25°C and 95°C corresponding to Test 5-2 of Example 17-E. DETAILED DESCRIPTION

[0264] In the examples, the amounts indicated in ppm are by mass relative to the total mass of the monomers. This may be the case in particular for the amounts of crosslinkers.

[0265] Alternatively, unless otherwise stated, bulk viscosity was measured at 1 mg / L in an aqueous solution containing 0.3 mol / L NaCl using a Brookfield viscometer at 25° C. at a rotation speed of 12-rpm.

[0266] Example 1: Method for preparing AAMPS

[0267] 230 g of dimethylaminoethyl acrylate (ADAME) and 50 g of water were charged into a 1000 mL glass reactor equipped with a stirrer and a condenser, and the temperature of the mixture was maintained at 20° C. 410 g of acetone was added to the medium as a solvent.

[0268] 164 g of 2-acrylamido-2-methylpropanesulfonic acid were added to the previous mixture. The temperature was maintained at 20° C. and the stirring speed was maintained at 300 rpm. The reaction was carried out at atmospheric pressure. After 72 hours, the formation of product crystals formed a suspension in the reaction medium. The crystals were separated by vacuum filtration of the Büchner type and then washed with ethanol directly in the filter. The crystals thus obtained were placed in a vacuum oven at 40° C. for 4 hours. 40.5 g of crystals were obtained; yield 15%, purity 90%.

[0269] The obtained crystals were subjected to NMR analysis, as shown in Figure 1 The proton NMR spectrum in confirmed the structure of the formula (IX) of the AAMPS monomer. Fig. 9 The IR spectrum of the AAMPS monomer is shown.

[0270] Example 2: Method for preparing MAMMPS

[0271] 410 g of dimethylaminopropylmethacrylamide (DMAPMA) and 50 g of water were charged into a 1000 mL glass reactor equipped with a stirrer and a condenser. The temperature of the mixture was maintained at 20°C.

[0272] 164 g of 2-acrylamido-2-methylpropanesulfonic acid was added to the previous mixture. The contact time was 200 hours, the temperature was maintained at 20° C., and the stirring speed was maintained at 300 rpm. The reaction was carried out under atmospheric pressure.

[0273] Crystals precipitate and a suspension of these crystals is obtained in the reaction mixture. The crystals are separated by Büchner type vacuum filtration and washed with acetone. The crystals are then placed in a vacuum oven at 40° C. for 6 hours. 273 g of crystals are obtained; the yield is 92% and the product purity is 90%.

[0274] The obtained crystals were subjected to NMR analysis. Figure 2 Proton NMR spectra and Fig.10 The IR spectrum in confirms the structure of formula (IX) of the MAMMPS monomer.

[0275] Example 3: Method for preparing MAMMPS

[0276] 410 g of dimethylaminopropylmethacrylamide (DMAPMA) and 3 g of water were charged into a 1000 mL glass reactor equipped with a stirrer and a condenser. The temperature of the mixture was maintained at 20°C.

[0277] 164 g of 2-acrylamido-2-methylpropanesulfonic acid was added to the previous mixture. The contact time was 200 hours, the temperature was maintained at 20° C., and the stirring speed was maintained at 300 rpm. The reaction was carried out under atmospheric pressure.

[0278] Crystals precipitate and a suspension of these crystals is obtained in the reaction mixture. The crystals are separated by Büchner type vacuum filtration and washed with acetone. The crystals are then placed in a vacuum oven at 40°C for 6 hours. 179 g of crystals are obtained. The mass yield is 60% and the product purity is 75%.

[0279] Example 4: Method for preparing MAMMPS

[0280] 270 g of dimethylaminopropylmethacrylamide (DMAPMA) and 50 g of water were charged into a 1000 mL glass reactor equipped with a stirrer and a condenser. The temperature of the mixture was maintained at 20°C.

[0281] 164 g of 2-acrylamido-2-methylpropanesulfonic acid was added to the previous mixture. 138 g of acetone was added to the reaction medium. The contact time was 200 hours, the temperature was maintained at 20° C., and the stirring speed was maintained at 300 rpm. The reaction was carried out under atmospheric pressure.

[0282] Crystals precipitate and a suspension of these crystals is obtained in the reaction mixture. The crystals are separated by Büchner type vacuum filtration and washed with acetone. The crystals are then placed in a vacuum oven at 40°C for 6 hours. 218 g of crystals are obtained. The mass yield is 73% and the product purity is 90%.

[0283] Example 5: Method for preparing AMMPS

[0284] 444 g of dimethylaminopropylacrylamide (DMAPAA) and 60 g of water were charged into a 1000 mL glass reactor equipped with a stirrer and a condenser. The temperature of the mixture was maintained at 20°C.

[0285] 197 g of 2-acrylamido-2-methylpropanesulfonic acid was added to the previous mixture. The contact time was 200 hours, the temperature was maintained at 20°C, and the stirring speed was maintained at 300 rpm. The reaction was carried out under atmospheric pressure.

[0286] Crystals precipitate and a suspension of these crystals is obtained in the reaction mixture. The crystals are separated by Büchner type vacuum filtration and washed with acetone. The crystals are then placed in a vacuum oven at 40°C for 6 hours. 363 g of crystals are obtained. The mass yield is 25% and the product purity is 45%.

[0287] The obtained crystals were analyzed, such as Figure 3 Proton NMR spectra and Fig.11 The IR spectrum confirmed the structure of the AMMPS monomer.

[0288] Example 6: Method for preparing MAAMPS

[0289] 563 g of dimethylaminoethyl methacrylate (MADAME) and 38 g of water were charged into a 1000 mL glass reactor equipped with a stirrer and a condenser. The temperature of the mixture was maintained at 20°C.

[0290] 123 g of 2-acrylamido-2-methylpropanesulfonic acid was added to the previous mixture. The contact time was 170 hours, the temperature was maintained at 20° C., and the stirring speed was maintained at 300 rpm. The reaction was carried out under atmospheric pressure.

[0291] Crystals precipitate and a suspension of these crystals is obtained in the reaction mixture. The crystals are separated by Büchner type vacuum filtration and washed with acetone. The crystals are then placed in a vacuum oven at 40°C for 6 hours. 143 g of crystals are obtained. The yield is 66% and the product purity is 90%.

[0292] The obtained crystals were subjected to NMR analysis, as shown in Figure 4 Proton NMR spectra and Fig.12 The IR spectrum in , confirmed the structure of formula (VIII) of the MAAMPS monomer.

[0293] Example 7: Method for preparing MAAMPS

[0294] 400 g of dimethylaminoethyl methacrylate (MADAME) and 247 g of water were charged into a 1000 mL glass reactor equipped with a stirrer and a condenser. The temperature of the mixture was maintained at 20°C.

[0295] 176 g of 2-acrylamido-2-methylpropanesulfonic acid was added to the previous mixture. The contact time was 170 hours, the temperature was maintained at 20° C., and the stirring speed was maintained at 300 rpm. The reaction was carried out under atmospheric pressure.

[0296] Crystals precipitate and a suspension of these crystals is obtained in the reaction mixture. The crystals are separated by Büchner type vacuum filtration and washed with acetone. The crystals are then placed in a vacuum oven at 40°C for 6 hours. 37 g of crystals are obtained. The yield is 12% and the product purity is 90%.

[0297] Fig.15 The microscopic observation shown shows a specific form of crystals.

[0298] Example 8: Method for preparing MAAMPS

[0299] 224 g of dimethylaminoethyl methacrylate (MADAME) and 64 g of water were charged into a 1000 mL glass reactor equipped with a stirrer and a condenser. The temperature of the mixture was maintained at 20°C.

[0300] 328 g of 2-acrylamido-2-methylpropanesulfonic acid was added to the previous mixture. 163 g of acetone and 33 g of potassium carbonate were added to the medium. The contact time was 170 hours, the temperature was maintained at 20°C, and the stirring speed was maintained at 300 rpm. The reaction was carried out under atmospheric pressure.

[0301] Crystals precipitate and a suspension of these crystals is obtained in the reaction mixture. The crystals are separated by Büchner type vacuum filtration and washed with acetone. The crystals are then placed in a vacuum oven at 40°C for 6 hours. 288 g of crystals are obtained. The yield is 50% and the product purity is 57%.

[0302] Example 9: Method for preparing MAAMPS

[0303] 380 g of dimethylaminoethyl methacrylate (MADAME) was charged into a 1000 mL glass reactor equipped with a stirrer and a condenser. The temperature of the mixture was maintained at 20°C.

[0304] 167 g of 2-acrylamido-2-methylpropanesulfonic acid was added to the previous mixture. 190 g of acetone was also added to the medium. The contact time was 200 hours, the temperature was maintained at 20°C, and the stirring speed was maintained at 300 rpm. The reaction was carried out under atmospheric pressure.

[0305] Crystals precipitate and a suspension of these crystals is obtained in the reaction mixture. The crystals are separated by Büchner type vacuum filtration and washed with acetone. The crystals are then placed in a vacuum oven at 40°C for 6 hours. 29 g of crystals are obtained. The yield is 10% and the product purity is 60%.

[0306] Example 10: Method for preparing MAAMPS

[0307] 226 g of dimethylaminoethyl methacrylate (MADAME) was charged into a 1000 mL glass reactor equipped with a stirrer and a condenser. The temperature of the mixture was maintained at 20°C.

[0308] 600 g of 50% aqueous solution of sodium 2-acrylamido-2-methylpropane sulfonate was added to the previous mixture. The contact time was 170 hours, the temperature was maintained at 20°C, and the stirring speed was maintained at 300 rpm. The reaction was carried out under atmospheric pressure.

[0309] The obtained product was dissolved in the reaction medium. The yield was 39% and the product purity was 35%.

[0310] Fig.16 The microscopic observations shown show that the Fig.15 The crystals obtained are different specific forms of crystals.

[0311] Example 11: Method for preparing ALMPS

[0312] 303 g of allyldimethylamine (ADMA) was charged into a 1000 mL glass reactor equipped with a stirrer and a condenser. The temperature of the mixture was maintained at 20°C.

[0313] 246 g of 2-acrylamido-2-methylpropanesulfonic acid, 10 g of acetone and 15 g of water were added to the previous mixture. The contact time was 170 hours, the temperature was maintained at 20°C, and the stirring speed was maintained at 300 rpm. The reaction was carried out under atmospheric pressure.

[0314] After the addition of acetone, crystals precipitate and a suspension of these crystals is obtained in the reaction mixture. The crystals are separated by Büchner type vacuum filtration and washed with acetone. The crystals are then placed in a vacuum oven at 40°C for 6 hours. 273 g of crystals are obtained. The yield is 79% and the product purity is 90%.

[0315] The obtained crystals were subjected to NMR analysis. Figure 5 Proton NMR spectra and Fig.13 The IR spectrum in confirms the structure of the ALMPS monomer of formula (X).

[0316] Example 12: Method for preparing ALMPS

[0317] 369 g of allyldimethylamine (ADMA) was charged into a 1000 mL glass reactor equipped with a stirrer and a condenser. The temperature of the mixture was maintained at 20°C.

[0318] 300 g of 2-acrylamido-2-methylpropanesulfonic acid and 175 g of acetone were added to the previous mixture. The contact time was 170 hours, the temperature was maintained at 20°C, and the stirring speed was maintained at 300 rpm. The reaction was carried out under atmospheric pressure.

[0319] After adding acetone to the medium, crystals precipitate and a suspension of these crystals is obtained in the reaction mixture. The crystals are separated by vacuum filtration of the Büchner type and washed with acetone. The crystals are then placed in a vacuum oven at 40°C for 6 hours. 222 g of crystals are obtained. The yield is 52% and the product purity is 90%.

[0320] Example 13: Method for preparing ALMPS

[0321] 177 g of allyldimethylamine (ADMA) was charged into a 1000 mL glass reactor equipped with a stirrer and a condenser. The temperature of the mixture was maintained at 20°C.

[0322] 144 g of 2-acrylamido-2-methylpropanesulfonic acid, 180 g of acetone and 336 g of water were added to the previous mixture. The contact time was 170 hours, the temperature was maintained at 20°C, and the stirring speed was maintained at 300 rpm. The reaction was carried out under atmospheric pressure.

[0323] After adding acetone to the medium, crystals precipitate and a suspension of these crystals is obtained in the reaction mixture. The crystals are separated by vacuum filtration of the Büchner type and washed with acetone. The crystals are then placed in a vacuum oven at 40°C for 6 hours. 106 g of crystals are obtained. The yield is 52% and the product purity is 90%.

[0324] Example 14: Method for preparing DAMPS

[0325] 120 g of diallylmethylamine (DAMA) was charged into a 1000 mL glass reactor equipped with a stirrer and a condenser. The temperature of the mixture was maintained at 20°C.

[0326] 112 g of 2-acrylamido-2-methylpropanesulfonic acid, 75 g of acetone and 30 g of water were added to the previous mixture. The contact time was 170 hours, the temperature was maintained at 20°C, and the stirring speed was maintained at 300 rpm. The reaction was carried out under atmospheric pressure.

[0327] After adding acetone to the medium, crystals precipitate and a suspension of these crystals is obtained in the reaction mixture. The crystals are separated by vacuum filtration of the Büchner type and washed with acetone. The crystals are then placed in a vacuum oven at 40°C for 6 hours. 135 g of crystals are obtained. The yield is 85% and the product purity is 90%.

[0328] The obtained crystals were subjected to NMR analysis. Figure 6 Proton NMR spectra and Fig.14 As confirmed by the IR spectrum in, the structure of the DAMPS monomer of formula (X) was confirmed.

[0329] Example 15: Method for preparing DAMPS

[0330] 120 g of diallylmethylamine (DAMA) was charged into a 1000 mL glass reactor equipped with a stirrer and a condenser. The temperature of the mixture was maintained at 20°C.

[0331] 112 g of 2-acrylamido-2-methylpropanesulfonic acid, 75 g of acetone and 7.5 g of water were added to the previous mixture. The contact time was 170 hours, the temperature was maintained at 20°C, and the stirring speed was maintained at 300 rpm. The reaction was carried out under atmospheric pressure.

[0332] After adding acetone to the medium, crystals precipitate and a suspension of these crystals is obtained in the reaction mixture. The crystals are separated by vacuum filtration of the Büchner type and washed with acetone. The crystals are then placed in a vacuum oven at 40°C for 6 hours. 135 g of crystals are obtained. The yield is 85% and the product purity is 90%.

[0333] Example 16: X-ray diffraction analysis

[0334] The solids obtained in Examples 7 and 10 were ground into powders beforehand and analyzed by X-ray diffraction in the angular range from 10 to 90°. The instrument used was a Rigaku MiniFlex II diffractometer equipped with a copper source.

[0335] It can be seen that the solid obtained at the end of Example 7 ( Figure 7 ) has the following characteristic peaks:

[0336] 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. Uncertainties are typically on the order of + / - 0.05°.

[0337] It can be seen that the solid obtained at the end of Example 10 ( Figure 8 ) has the following characteristic peaks:

[0338] 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°).

[0339] Thus, differences in the crystal structures of the same MAAMPS molecule can be highlighted, which is a hallmark of polymorphism.

[0340] Other embodiments: A method for preparing MAAMPS using a reduced amount of MEHQ (monomethyl ether of hydroquinone) as an inhibitor.

[0341] Example 9 was repeated 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-methylpropanesulfonic acid) of MEHQ in 190 g of acetone.

[0342] When 1000 ppm MEHQ was added, the yield was 5% and the purity was 42%.

[0343] When 750 ppm MEHQ was added, the yield was 6% and the purity was 45%.

[0344] When 500 ppm MEHQ was added, the yield was 8% and the purity was 51%.

[0345] Addition of large amounts of inhibitor, i.e., 750 ppm and 1000 ppm, resulted in decreased yield and purity. It was surprisingly noted that by using reduced amounts of MEHQ, i.e., less than 500 ppm, particularly 450 ppm, 250 ppm, or more preferably 50 ppm or less, the yield and purity were improved compared to tests conducted in the presence of 500 ppm or more MEHQ.

[0346] Example 17: Preparation of sulfobetaine-based polymer inverse emulsion and its use in consistency.

[0347] The following series of examples relate to the preparation of polymer microparticles based on sulfobetaine of the present invention. These particles should show an increase in size Dh with temperature (expansion / aggregation). Therefore, these particles can be used as a consistency additive for enhanced oil recovery (EOR) and enable the following:

[0348] - Reduce the permeability of high temperature and high permeability areas to improve the efficiency of crude oil displacement by injecting water or chemicals;

[0349] and

[0350] -Reduce or completely stop water production from production wells.

[0351] Synthesis process:

[0352] Crosslinked polymer particles of 2-(diethylamino)ethyl methacrylate and polymerizable sulfobetaine were prepared by conventional free radical inverse emulsion polymerization. The process comprises:

[0353] - Preparation of the organic phase: In the first reactor, introduce under stirring:

[0354] *Mineral oil containing saturated hydrocarbons

[0355] *Sorbitan ester surfactants with HLB range of 3 to 7

[0356] - Preparation of the aqueous phase: In a second reactor, under stirring and at room temperature, introduce:

[0357] * Deionized water

[0358] * Zwitterionic monomers of the sulfobetaine type according to the present invention or zwitterionic monomers described in the prior art

[0359] Ionic monomer

[0360] * Comonomers: DEAEMA and crosslinkers (diacrylamide and / or dimethacrylate based)

[0361] *pH adjuster

[0362] -After obtaining a uniform organic phase, the aqueous phase is emulsified in the organic phase under continuous mechanical and shear stirring for several tens of seconds to obtain a stable emulsion.

[0363] - The emulsion was transferred to a jacketed reactor equipped with a stirring system and then degassed by bubbling with nitrogen for 60 minutes.

[0364] -Polymerization can be initiated using redox couples.

[0365] - After the reaction medium has cooled, an inverting surfactant with an HLB of 12 is introduced under gentle stirring.

[0366] Characterization of the hydrodynamic diameter (Dh) of polymer particles by dynamic light scattering (DLS)

[0367] The size (Dh) of the polymer particles at ambient temperature and its evolution with temperature were characterized by DLS using a ZETASIZER NANO ZS sold by Malvern and equipped with a 4mW-632.8nm HeNe laser. The polymer particles were analyzed at a concentration of 1 mg / mL in saline (0.3mol / L NaCl). The cuvette used was made of quartz. The data were analyzed using Malvern DTS software. Data were collected at 5°C temperature intervals with a sample equilibration time of 5 minutes at elevated temperatures.

[0368] Before they can be used as consistency additives in many areas:

[0369] - It is preferred that the Dh value of the polymer population increases as quickly as possible, ideally at a temperature of 30 to 50°C.

[0370] The particle aggregates formed with increasing temperature are advantageously characterized by the highest possible Dh value.

[0371] Characterization of the reversibility of polymer particles

[0372] The reversibility of the particles will be evaluated by studying the change in the hydrodynamic diameter (Dh) of the polymer particles during temperature cycling. The Dh reversibility data of the particles will be collected between 2 temperatures (15 and 90°C) by performing ramp-up and ramp-down cycles between these 2 temperatures. The temperature ramp-up or ramp-down time between the endpoints is 10 minutes.

[0373] The smaller the change in Dh before and after temperature cycling (15°C=>90°C=>15°C) (less than or equal to 10%), the more reversible the thermal expansion / thermal aggregation performance is.

[0374] Example 17-A: Preparation of Granules from Sultaine

[0375] The purpose of this test is to confirm the thermal expansion and thermal aggregation properties of the particles prepared from the monomers of the invention in order to use them in a consistent manner (see the paragraph on "Dh Characterization").

[0376] A first series of polymers crosslinked with 40 ppm MBA was produced according to the above procedure. Table 1 summarizes the chemical compositions and characteristics of the various tests for Example 17-A.

[0377]

[0378]

[0379] Table 1: Composition and properties of Tests 1-1, 1-2, 1-3 and 1-4

[0380] The bulk viscosity was measured using a Brookfield viscometer (rotation speed: 12 rpm).

[0381] Fig.17 The graph in highlights the change in Dh over time at a concentration of 1 mg / mL for each test.

[0382] This example shows that the emulsions prepared from the monomers of the invention (Tests 1-1 and 1-2) are more storage stable.

[0383] The highest Dh values ​​were obtained for polymer particles prepared with the monomers of the present invention. The thermal expansion and thermal aggregation properties of the polymer particles of the comparative examples were significantly lower than those obtained with the polymer particles of the present invention. The thermal expansion / thermal aggregation activation temperature of the polymer particles prepared with the monomers of the present invention was more suitable for the region of the mean field temperature.

[0384] In summary, the particles prepared from the monomers of the present invention (Tests 1-1 and 1-2) yield better thermal expansion / thermal aggregation properties than the particles of the prior art (Test 1-3) and the comparative example (Test 1-4).

[0385] Example 17-B: Preparation of Granules from Sultaine

[0386] The purpose of this test is to confirm the thermal expansion and thermal aggregation properties of particles (prepared from monomers of the present invention) at a different molar composition than Example 17-A.

[0387] A series of new crosslinked polymer particles based on sulfobetaine was developed. Table 2 below summarizes the chemical composition and various test characteristics of the polymer of Example 17-B (crosslinked with 10 ppm MBA). The synthesis scheme was as described at the beginning of Example 17.

[0388]

[0389]

[0390] Table 2: Composition and properties of tests 2-1 and 1-2.

[0391] Fig.18 The graph in highlights the change in Dh over time at a concentration of 1 mg / mL for each test.

[0392] This new example highlights a final high Dh value and activation temperature that is compatible with most reservoirs (subsurface formations).

[0393] This again demonstrates that the emulsions prepared from the monomers of the present invention (Tests 2-1 and 2-2), once dispersed in saline, produce thermal expansion / thermal aggregation properties at monomer molar compositions different from that of Example 17-A.

[0394] Example 17-C Preparation of particles from sulfobetaine crosslinked with dimethacrylate

[0395] The purpose of this test is to confirm the thermal expansion and thermal aggregation properties of particles prepared from monomers of the present invention but crosslinked with a different crosslinker than Test 17-B.

[0396] Table 3 below summarizes the novel chemical composition and various test characteristics of the polymer crosslinked with 10 ppm EGDMA of Example 17-C. The polymer synthesis protocol was as described at the beginning of Example 17.

[0397]

[0398]

[0399] Table 3: Composition and properties of Tests 3-1 and 3-2

[0400] It is observed that an increase in temperature causes a very significant increase in Dh. This third example shows that the emulsions prepared from the monomers of the invention perform well even when they are crosslinked with crosslinkers of the methacrylate type.

[0401] Example 17-D: Consistency of cross-linked polymer particles based on MAAMPS or MAMMPS sulfobetaine Reversibility

[0402] The purpose of this test is to confirm the reversibility of the thermal expansion and thermal aggregation properties of the particles based on continuous temperature increase and decrease cycles.

[0403] The novel chemical composition and various test characteristics of the copolymers of the examples crosslinked with 40 ppm MBA are summarized in Table 4 below.

[0404]

[0405]

[0406] Table 4: Composition and properties of Tests 4-1 and 4-2

[0407] The reversibility of the thermal expansion / thermal aggregation properties of the polymer particles was evaluated according to the protocol described at the beginning of Example 17. The results obtained are summarized in Fig.19 (Test 4-1) and 20 (Test 4-2). The reversibility of thermal expansion and thermal aggregation was determined by temperature rise and fall cycles between 15°C and 90°C.

[0408] It is observed that the Dh values ​​before and after the temperature cycle are equal. This fourth example shows that the polymer particles of the emulsion prepared from the monomers of the present invention have reversible properties of thermal expansion and thermal aggregation (depending on the temperature). This reversibility obtained with the particles prepared from the monomers of the present invention makes it possible to adjust the performance according to the temperature changes of the same reservoir.

[0409] Example 17-E: MAAMPS or MAMMPS sulfobetaine-based cross-linked polymer particles in porous media performance

[0410] The purpose of this test is to confirm the thermal expansion and thermal aggregation properties of particles in porous media.

[0411] Table 5 below summarizes the chemical compositions of Tests 5-1 and 5-2 (copolymers with 40 ppm MBA crosslinking). The synthesis protocol was as described above.

[0412]

[0413] Table 5: Composition and properties of Tests 5-1 and 5-2

[0414] The characteristics of the injection test in a porous medium for the injection of a dispersion of 1000 active ppm of polymer 5-1 were:

[0415] - Flow rate (Q) = 12 cm 3 / h

[0416] - Cut: 50s -1

[0417] -Internal speed: 2.4m / day

[0418] -Porosity: 33%

[0419] -Permeability: 1290mD

[0420] Record the pressure inside a porous medium as a function of pore volume. Fig.21 Evolution of the pressure difference dP between the inlet and outlet of a porous medium.

[0421] It is important to note that the total pressure difference dP is constant, which confirms that the particles of Test 5-1 are well injected and spread in the porous medium at room temperature.

[0422] Record the pressure inside a porous medium as a function of temperature. Fig. 22 Evolution of the pressure difference dP between the inlet and outlet of the porous medium as the temperature changes from 25°C to 95°C.

[0423] Fig. 22 The graph in highlights the increase in pressure difference within the cross section with temperature (from 25° C. to 95° C.). This confirms that the thermal expansion and thermal aggregation properties of the particles of Test 5-1 vary with temperature.

[0424] In summary, this Example 17-E demonstrates that polymer particle emulsions prepared from the monomers of the present invention have propagation, thermal expansion, and thermal aggregation properties in porous media.

[0425] Example 18: Dishwashing liquid formulated with MAAMPS copolymer

[0426] The detergent industry uses a variety of raw materials, including surfactants, to formulate foaming products. One skilled in the art may add excipients to the formulation to increase the foaming properties of the formulation, or even stabilize the foam formed.

[0427] The purpose of this new test is to evaluate the foaming and stability properties of the foam formed in the presence of greasy residues by an additive prepared from one of the monomers of the present invention.

[0428] Acrylamide (AM) and MAAMPS copolymers were prepared by conventional free radical polymerization in aqueous solution.

[0429] The chemical compositions are summarized in Table 6.

[0430]

[0431]

[0432] Table 6: Chemical composition of Test 6-1

[0433] First, an aqueous stock solution containing 20% ​​by mass of a surfactant (a mixture of sodium lauryl ether sulfate and amine oxide) was prepared, and then different sub-solutions (from A to E) were prepared by adding different mass percentages of copolymer 6-1, and are listed in Table 7.

[0434]

[0435] Table 7: Composition of polymer 6-1 in surfactant solution

[0436] Solutions A to E were then prepared according to the formulations detailed in Table 8.

[0437]

[0438] Table 8: Composition of Tests F, G, H, I and J

[0439] Preparation F, G, H, I and J are packaged in graduated test tubes respectively. At the beginning, the volume of each solution accounts for 1 / 3 of the test tube volume. Then nine cycles are carried out on each test tube, each cycle is twenty turns (30rpm). At the end of each cycle, 5mL olive oil is added to each test tube (that is, a total of 40mL at the end of the process). Then the foam height of test G, H, I, J is measured and compared with the foam height of test F.

[0440] The obtained results are summarized in Table 9.

[0441]

[0442] Table 9: Foam Gain for Tests F, G, H, I and J

[0443] The results obtained show a significant increase in foam compared to Reference F. This new example demonstrates the foaming performance and foam stabilization properties of the copolymers prepared from the sulfobetaine monomers of the present invention.

[0444] Example 19: Retaining Agents in Paper Applications

[0445] The paper industry prepares pulp. Usually, retention additives and drainage additives are added to the formulation.

[0446] The purpose of this new test is to evaluate the performance of total retention (FPR, fiber + mineral filler), mineral filler retention (first pass ash retention (FPAR)) and vacuum drainage (dynamic drainage analyzer (DDA)). For FPR and FPAR, the higher the value, the better the performance. For DDA, the lower the drainage value, the better the performance.

[0447] The following polymers were synthesized according to the procedure described in Example 1. The formulation tested 7-0 did not contain any polymer. Table 10 summarizes the chemical composition and properties of the various tests (concentration in paper formulation was 0.25 mass %).

[0448] The molar masses of the different copolymers are comparable and of the same order of magnitude.

[0449]

[0450]

[0451] Table 10: Tested composition and properties

[0452] The tests according to the invention produced higher FPAR and FPR values ​​than the reference, and lower DDA values ​​than the reference. This new example shows that the terpolymers prepared from the sulfobetaine monomers of the invention exhibit good performance in terms of total retention, filler retention and vacuum drainage.

[0453] Example 20: High Viscosity Additive (HVFR) for Hydraulic Fracturing

[0454] The hydraulic fracturing industry uses many additives, including friction reducers (high viscosity friction reducers (HVFRs)) that induce high viscosity in saline media. The purpose of this example was to formulate hydraulic fracturing fluids with additives (of the present invention and the prior art) and observe the "bulk" viscosity levels achieved.

[0455] The polymers described in Table 11 were synthesized following the procedure described in Example 1. Table 11 summarizes the chemical composition and properties of each test. The molar masses of the different copolymers are comparable and of the same order of magnitude.

[0456]

[0457] Table 11: Composition and properties tested

[0458] Table 12 summarizes the Van der Waals viscosities at 4 and 6 gallons per thousand (GPT) for the various brines. Brine 1 consisted of sodium chloride (30 g / L) and calcium chloride (3 g / L). Brine 2 consisted of sodium chloride (85 g / L) and calcium chloride (33 g / L).

[0459]

[0460]

[0461] Table 12: Fanning viscosity

[0462] Fanning viscosity (in centipoise (cP)) was measured at 20°C using a Chandler Engineering Model 3500 Viscometer equipped with an R1B1 module (Rotor 1Bob 1). Shear rates of 511 and 102 s were inferred by applying angular velocities of 300 and 60 rpm, respectively. -1 The Fanning viscosity value below.

[0463] Regardless of the cut (100 or 511s -1 ) and dosage (4 or 6 gpm), Tests 8-1 and 8-2 produced higher Van der Waals viscosities than Test 8-3. This new example shows that emulsion formulated (HVFR) type hydraulic fracturing fluids produced from the monomers of the present invention have higher Van der Waals viscosities than fluids prepared from prior art emulsions, thus providing better performance in the intended application.

Claims

1. A method for preparing a sulfobetaine monomer of formula (V) and / or its acid form by reacting: - a compound of formula (VI), and - a compound of formula (VII) and / or a salt thereof, in the presence of at least one agent that solubilizes a compound of formula (VII), wherein the agent that solubilizes a compound of formula (VII) The compound solubilizing agent is water, the amount of which is 5 to 80% by mass relative to the mass of the compound of formula (VII), and wherein the reaction is carried out using a polymerization inhibitor, the polymerization inhibitor is monomethyl hydroquinone ether, Its amount is 10 to less than 500 ppm relative to the total mass of the compounds of formula (VI) and (VII), In formulae (V), (VI) and (VII): R1 and R4 are independently -H or -CH3, R2 and R3 are independently a linear C1-C10 alkyl group or a branched C3-C10 alkyl group or a linear C2-C10 alkylene group, wherein the alkylene group contains a -CH=CH2 group, R5 is -H, or a linear C1-C22 alkyl group or a branched C3-C22 alkyl group, or R5 and R6 form a C4-C10 carbocyclic ring, R6 is a straight-chain C1-C22 alkyl group or a branched C3-C22 alkyl group, or R6 and R5 form a C4-C10 carbocyclic ring, X1=-COO-, or -CONH-, or -CH2-, X2=-COO- or -CONH-, n is an integer of 0-10.

2. The method of claim 1, wherein the polymerization inhibitor is present in an amount of less than 200 ppm.

3. The method according to claim 1 or 2, characterized in that The compound of formula (VI) is selected from dimethylaminopropylmethacrylamide, dimethylaminopropylacrylamide, allyldimethylamine, diallylmethylamine, dimethylaminoethylmethacrylate and dimethylaminoethylacrylate.

4. The method according to claim 1 or 2, characterized in that The compound of formula (VII) is 2-acrylamido-2-methylpropanesulfonic acid and / or a salt thereof.

5. The method according to claim 1 or 2, characterized in that The molar ratio between the compound of formula (VI) and the compound of formula (VII) and / or a salt thereof is from 1.01:1 to 20:

1.

6. The method according to claim 1 or 2, characterized in that The method comprises the following consecutive steps: a1) adding at least one compound of formula (VI) and at least one agent for solubilizing the compound of formula (VII) to a stirred reactor to obtain a pre-reaction mixture, wherein the agent for solubilizing the compound of formula (VII) is water in an amount of 5 to 80% by mass relative to the mass of the compound of formula (VII); a2) adding at least one compound of formula (VII) and / or a salt thereof to the pre-reaction mixture; a3) After the reaction between the compounds of formula (VI) and (VII), a sulfobetaine monomer of formula (V) and / or its acid form is obtained in the form of a suspension or solution of crystals.

7. A method for preparing a sulfobetaine monomer of formula (V) and / or a (co)polymer thereof in acid form, the method comprising the following steps: - preparing a sulfobetaine monomer of formula (V) and / or its acid form by a process according to any one of claims 1 to 6, - (co)polymerizing at least the sulfobetaine monomers obtained to form a (co)polymer.

8. A process for preparing a sulfobetaine monomer of formula (V) and / or its acid form in hydrated crystalline form, said process comprising the following consecutive steps: a1) adding at least one compound of formula (VI), a polymerization inhibitor monomethyl hydroquinone ether and at least one agent for solubilizing the compound of formula (VII) to a stirred reactor to obtain a pre-reaction mixture, wherein the agent for solubilizing the compound of formula (VII) is water in an amount of 5 to 80% by mass relative to the mass of the compound of formula (VII); a2) adding at least one compound of formula (VII) and / or a salt thereof to the pre-reaction mixture; a3) after the reaction, obtaining a sulfobetaine monomer of formula (V) and / or its acid form in the form of a suspension or solution of crystals; a4) optionally, when the reaction product is a solution, extracting the compound of formula (V) in the form of crystals AA; a5) combining the crystals AA of the compound of formula (V) with an aqueous solution to form a suspension A; a6) mixing the suspension A for 1 minute to 20 hours; a7) obtaining a suspension B of crystals BB of the compound of formula (V) in hydrated form; a8) optionally isolating the obtained crystals BB from the suspension B, In formulae (V), (VI) and (VII): R1 and R4 are independently -H or -CH3, R2 and R3 are independently a linear C1-C10 alkyl group or a branched C3-C10 alkyl group or a linear C2-C10 alkylene group, wherein the alkylene group contains a -CH=CH2 group, R5 is -H, or a linear C1-C22 alkyl group or a branched C3-C22 alkyl group, or R5 and R6 form a C4-C10 carbocyclic ring, R6 is a straight-chain C1-C22 alkyl group or a branched C3-C22 alkyl group, or R6 and R5 form a C4-C10 carbocyclic ring, X1=-COO-, or -CONH-, or -CH2-, X2=-COO- or -CONH-, n is an integer from 0 to 10, The reaction is carried out using an amount of the polymerization inhibitor of 10 to less than 500 ppm relative to the total mass of the compounds of formulae (VI) and (VII).

9. The method of claim 8, wherein the polymerization inhibitor is present in an amount less than 200 ppm.

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