Process for obtaining bio-based diallyldialkylammonium halide

Abstract

The present invention relates to a process for obtaining diallyldialkylammonium halide comprising the reaction between allyl halide and dialkylamine, one or preferably both being at least partly of renewable and non-fossil origin. The invention also relates to a bio-based diallyldialkylammonium halide monomer, a bio-based polymer incorporating at least said monomer, and the use of said polymer in various technical fields.

Description

Title of the invention: Process for obtaining bio-sourced diallyldialkylammonium halide Field of the invention

[0001] The present invention relates to a process for obtaining bio-sourced diallyldialkylammonium halide comprising the reaction between an allyl halide and a dialkylamine, one of the two, preferably both, being at least partly of renewable and non-fossil origin. The invention relates to a bio-sourced diallyldialkylammonium halide monomer, preferably diallyldimethylammonium chloride, as well as a bio-sourced polymer obtained from at least one bio-sourced diallyldialkylammonium halide monomer according to the invention. The invention finally relates to the use of the bio-sourced polymers of the invention in different technical fields. Prior art

[0002] The radical polymerization reaction of at least one ethylenic monomer comprising a quaternary ammonium function which can be chosen from acrylamidopropyltrimethylammonium chloride (APTAC), methacrylamidopropyltrimethylammonium chloride (MAPTAC), dimethylaminoethyl acrylate (ADAME) or dimethylaminoethyl methacrylate (MADAME), all these compounds being salified or quaternized by halogenated alkyl derivatives or dialkyl sulfates is known to those skilled in the art. However, the polymers obtained have limited cationic charge densities.

[0003] Another method for preparing water-soluble cationic polymers with a high cationic charge density known to those skilled in the art is the radical polymerization reaction of at least one allylic monomer such as a diallyldialkyl ammonium halide. Among the allylic monomers, diallyldimethyl ammonium halides make it possible to obtain the polymers with the highest charge density, the most accessible allylic monomer on the market being diallyldimethyl ammonium chloride (DADMAC). In particular, DADMAC homopolymers are characterized by cationic charge densities greater than 6 meq / g-

[0004] Diallyldialkylammonium halides are monomers widely used in the manufacture of water-soluble polymers.

[0005] The reaction carried out in the process for preparing diallyldialkylammonium halide corresponds to the reaction scheme below, in which the allyl halide reacts with dialkylaminedimethylamine, in the presence of a base such as, for example, a metal hydroxide, as indicated by the reaction below.

[0006] [Chem.l] NH , „ HZC:= H2C^ X / \ + 2 \__x + HO-M ----- \ + / + MX R1 Rj --N-— Ri R2

[0007] R1 and R2 are independently either CH3 or a carbon chain, preferably alkyl, comprising from 2 to 20 carbon atoms. Preferably, R1 and R2 are CH3 groups. X is generally a Cl, Br or I atom, preferably Cl. M is generally a K or Na atom, preferably Na.

[0008] It is known to those skilled in the art that the reaction between allyl chloride and dimethylamine must be carried out in the presence of sodium hydroxide, in order to minimize the formation of allyl alcohol, as described in document US 4,670,594.

[0009] Allyl chloride is generally produced by the chlorination of propylene as described in EP 0 455 644. Propylene is an olefin of fossil origin, and is currently produced by steam cracking of naphtha, itself derived from the refining of crude oil. More recently, and with the advent of shale gas production, various processes for the dehydrogenation of propane to produce propylene have been described.

[0010] Propylene of fossil origin contains various impurities, which remain or are transformed in the process of producing allyl chloride and therefore diallyldimethyl ammonium chloride.

[0011] Dimethylamine is generally produced by reacting methanol with ammonia in the presence of a catalyst, as described in EP 0 125 616 and US 9,180,444. The dimethylamine thus produced contains impurities such as ammonia, monomethylamine and trimethylamine.

[0012] The impurities present in allyl chloride and dimethylamine, of fossil origin, are present in the diallyldimethylammonium chloride monomer. They can even react during the manufacturing process of this monomer and thus generate new impurities, in particular when trimethylamine reacts with allyl chloride to form allyl trimethyl ammonium chloride. This impurity is known to limit the molecular weight of polymers incorporating diallyldimethylammonium chloride.

[0013] We can also mention that the presence of residual ammonia in dimethylamine will form triallyl methylammonium chloride. This trifunctional molecule will induce branching (dimethylammonium chloride) or even crosslinking of the water-soluble polymers incorporating diallyldimethylammonium chloride.

[0014] Consequently, the impurities present in allyl chloride and dimethylamine will induce a degradation of the performances of the water-soluble polymers incorporating diallyldimethylammonium chloride, either by molecular weight limiting effects, or by the presence of branched or crosslinked polymers.

[0015] The problem which the invention proposes to solve is to propose a new and improved process for producing diallyldialkylammonium halide. Summary of the invention

[0016] Quite surprisingly, the applicant has observed that the use of allyl halide and dialkylamine, one of the two, preferably both, being at least partly of renewable and non-fossil origin, and preferably totally of renewable origin, in a process for obtaining diallyldialkylammonium halide, makes it possible to significantly improve the process and the quality of the monomer obtained, and thus improve their polymerization and the application performances of the polymers.

[0017] The applicant has particularly observed this improvement when the process is a process for obtaining diallyldialkylammonium halide by the so-called direct route which consists of not isolating the allyldialkylamine intermediate.

[0018] Without wishing to be bound by any theory, the applicant puts forward the possibility that the different nature of the impurities between the allyl halide of fossil origin and the allyl halide of renewable and non-fossil origin and / or between the dialkylamine of fossil origin and the dialkylamine of renewable and non-fossil origin is at the origin of these unexpected technical effects.

[0019] The invention firstly relates to a process for obtaining diallyldialkylammonium halide comprising the reaction between allyl halide and dialkylamine, one of the two, preferably both, being at least partly of renewable and non-fossil origin.

[0020] The invention also relates to a diallyldialkylammonium halide monomer having a biosourced carbon content of between 5% by weight and 100% by weight, relative to the total weight of carbon in said monomer, the biosourced carbon content being measured according to standard ASTM D6866-21, method B. The preferred monomers are biosourced diallyldimethylammonium halides, and particularly biosourced diallyldimethylammonium chloride.

[0021] The invention also relates to a polymer obtained by polymerization of at least one monomer obtained according to the process of the invention or as previously described, and the use of said polymers in different technical fields.

[0022] Thanks to the present invention, it is possible to achieve environmental objectives inherent in new technical innovations. In the present case, the use of raw material of renewable origin, in this case allyl halide and dialkylamine, makes it possible to significantly optimize the conversion process and the quality of the monomer obtained. Detailed description of the invention

[0023] In the context of the invention, the terms "of renewable and non-fossil origin" denote the origin of a chemical compound derived from biomass or synthesis gas (syngas), that is to say being the result of one or more chemical transformations carried out on one or more raw materials having a natural, and non-fossil, origin. The terms "biosourced" or "bio-resourced" can also be used to characterize the renewable and non-fossil origin of a chemical compound. The renewable and non-fossil origin of a compound includes renewable and non-fossil raw materials originating from the circular economy, and which have been previously recycled, one or more times, during a process of recycling material derived from biomass, such as, for example, materials resulting from the depolymerization of polymer or the transformation of pyrolysis oil.

[0024] According to the invention, the quality of “at least partly of renewable and non-fossil origin” of a compound means a biosourced carbon content preferably between 5% by weight and 100% by weight relative to the total weight of carbon of said compound.

[0025] In the context of the invention, ASTM D6866-21, method B, is used to characterize the bio-sourced nature of a chemical compound and to determine the bio-sourced carbon content of said compound. The value is expressed as a percentage by weight of bio-sourced carbon relative to the total weight of carbon in said compound.

[0026] ASTM D6866-21 is a test method that teaches how to experimentally measure the biobased carbon content of solid, liquid, and gaseous samples by radiocarbon analysis.

[0027] This standard primarily uses AMS (Accelerator Mass Spectrometry) technology. This technique is used to measure naturally occurring radionuclides in a sample, in which atoms are ionized, then accelerated to high energies, then separated, and individually counted in Faraday collectors. This high-energy separation is extremely effective at filtering out isobaric interference, so that AMS is able to accurately measure the abundance of carbon-14 relative to carbon-12 (14C / 12C) to an accuracy of 1.10 15.

[0028] Method B of ASTM D6866-21 uses AMS and IRMS (Isotope Ratio Mass Spectroscopy). The test method can directly distinguish carbon atoms from contemporary carbon from carbon atoms of fossil origin. A measure of the carbon-14 to carbon-12 content or the carbon-14 to carbon-13 content of a product is determined relative to a modern carbon-based reference material accepted by the radiocarbon dating community such as NIST Standard Reference Material (SRM) 4990C (oxalic acid).

[0029] The method of sample preparation is described in the standard and does not require any particular comment because it corresponds to a commonly used procedure.

[0030] The analysis, interpretation, and reporting of results are described below. Isotopic ratios of carbon-14 to carbon-12 or carbon-14 to carbon-13 are measured using AMS. Isotopic ratios of carbon-14 to carbon-12 or carbon-14 to carbon-13 are determined relative to a standard traceable to the NIST SRM 4990C modern reference standard. The "fraction of modern" (fM) represents the amount of carbon-14 in the tested product relative to the modern standard. It is most often referred to as percent modern carbon (pMC), the percentage equivalent to fM (e.g., fM 1 = 100 pMC).

[0031] All pMC values ​​obtained from radiocarbon analyses must be corrected for isotopic fractionation using a given stable isotope. The correction must be made using carbon-14 versus carbon-13 values ​​determined directly using AMS where possible. If this is not possible, the correction must be made using delta-13C (Δ13C) measured by IRMS, CRDS (Cavity Ring Down Spectroscopy) or any other equivalent technology that can provide accuracy to plus or minus 0.3 per thousand.

[0032] "Zero pMC" represents the complete absence of measurable 14C in a material above background signals, thus indicating a fossil (e.g., petroleum-based) carbon source. A value of 100 pMC indicates a fully "modern" carbon source. A pMC value between 0 and 100 indicates a proportion of carbon derived from a fossil source relative to a "modern" source.

[0033] The pMC may be greater than 100% due to the persistent, but diminishing, effects of 14C injection into the atmosphere caused by atmospheric nuclear testing programs. The pMC values ​​should be adjusted by a atmospheric correction factor (REF) to obtain the true biosourced content of the sample.

[0034] The correction factor is based on the excess 14C activity in the atmosphere at the time of testing. A REF value of 102 pMC was determined for 2015 based on CO2 measurements in the air in a rural area of ​​the Netherlands (Lutjewad, Groningen). The first version of this standard (ASTM D6866-04) in 2004 referenced a value of 107.5 pMC and the later version ASTM D6866-10 (2010) referenced a value of 105 pMC. These data points correspond to a decrease of 0.5 pMC per year. Therefore, on January 2 of each year, the values ​​in Table 1 below are used as the REF value until 2019, reflecting the same decrease of 0.5 pMC per year. The REF (pMC) values ​​for 2020 and 2021 were determined to be 100.0 based on continuous measurements in the Netherlands (Lutjewad, Groningen) until 2019. References for reporting carbon isotope ratio data are given below for 14C and 13C, respectively Roessler, N., Valenta, R.J., and van Cauter, S., “Time-resolved Liquid Scintillation Counting”, Liquid Scintillation Counting and Organic Scintillators, Ross, H., Noakes, JE, and Spaulding, JD, Eds., Lewis Publishers, Chelsea, MI, 1991, pp. 501-511. Allison, CE, Francy, RJ, and Meijer, HAJ, “Referenced and Intercomparison Materials for Stable Isotopes of Light Elements”, International Atomic Energy Agency, Vienna, Austria, IAEATECHDOC-825, 1995.

[0035] The calculation of the bio-based carbon content in % is carried out by dividing pMC by REF and multiplying the result by 100. For example, [102 (pMC) / 102 (REF)] x 100 = 100% bio-based carbon. The results are indicated as a percentage by weight of bio-based carbon relative to the total weight of carbon in said compound.

[0036] [Tables 1] Year REF pMC 2015 102.0 2016 101.5 2017 101.0 2018 100.5 2019 100.0 2020 100.0 2021 100.0

[0037] Table 1: Modern Carbon Percentage (pMC) Reference

[0038] In the context of the invention, the term "segregated" means a flow of material that is distinctive and distinguishable from other flows of material in a value chain (for example in a process for manufacturing a product), and therefore considered to be part of a set of material having an equivalent nature, such that we can follow and guarantee throughout this value chain the same origin of the material, or its manufacture according to the same standard or norm.

[0039] This corresponds, for example, to the purchase by a chemist of 100% bio-sourced dialkylamine exclusively from a single supplier who guarantees the 100% bio-sourced origin of the dialkylamine delivered, and the processing separately from other potential sources of dialkylamine by said chemist transforming this 100% bio-sourced dialkylamine to produce a chemical compound. If the chemical compound produced is only manufactured from said 100% bio-sourced dialkylamine, then the chemical compound is 100% of bio-sourced origin.

[0040] In the context of the invention, the term "non-segregated", as opposed to the term "segregated", means a material flow that cannot be distinguished from other material flows in a value chain.

[0041] In order to better understand this notion of segregation, it is useful to recall some basics concerning the circular economy and its practical application in processes, particularly chemical transformation.

[0042] According to ADEME (Agency for the Environment and Energy Management), The circular economy can be defined as an economic system of exchange and production that, at all stages of the product life cycle (goods and services), aims to increase the efficiency of resource use and reduce the impact on the environment while developing the well-being of individuals. In other words, it is an economic system dedicated to efficiency and sustainability that minimizes waste by optimizing the value generated by resources. It relies heavily on various conservation and recycling methods to move away from the current, more linear approach of "capture, produce and throw away".

[0043] In the field of chemistry, which is the science of transforming one substance into another, this translates into the reuse of a material that has already been used in the manufacture of a product. Theoretically, all chemical products can be isolated and therefore recycled separately from other chemical products. The reality, particularly in industrial terms, is more complex and means that even when isolated, the compound very often cannot be distinguished from the same compound from another source, making the traceability of the recycled material complex.

[0044] It is for this reason that different traceability models have been developed which take this industrial reality into account, allowing users in the chemical industry to manage their material flows with full knowledge of the facts, and allowing end customers to understand and know in a simple manner the origin of the materials used to produce an object or a foodstuff.

[0045] These models were developed to create transparency and trust throughout the value chain. Ultimately, this allows end users or customers to choose a more sustainable solution without having the ability themselves to control every aspect of the process, knowing the proportion of a desired component (for example of a bio-sourced nature) in an object or a foodstuff.

[0046] One of these models is "segregation" which we have previously defined. Some known examples for which this model applies are glass and certain metals for which it is possible to follow the material flows separately.

[0047] But chemicals are often used in complex combinations, and separate cycles are very often difficult to set up, particularly for reasons of prohibitive costs and ultra-complex flow management, which means that the “segregation” model is not always applicable.

[0048] Consequently, when it is not possible to distinguish the material flows, other models are applied, which will be grouped under the term "non-segregated" and which consist, for example, of taking into account in an accounting manner the proportion of a specific flow compared to the other flows, without physically separating the flows. We can cite, for example, the mass balance approach or the weights approach (in English "Mass Balance Approach").

[0049] The mass or weight balance approach involves accurately tracking the proportion of a category (e.g. "recycled") to a whole in a production system to ensure, based on an auditable ledger, a proportionate and appropriate allocation of the content of said category in a finished product.

[0050] This may correspond, for example, to the purchase by a chemist of 50% bio-sourced dialkylamine from a supplier guaranteeing, according to the mass or weight balance approach, that in the delivered dialkylamine, 50% of the dialkylamine has a bio-sourced origin, and de facto 50% does not have a bio-sourced origin, and the use by said chemist of this 50% bio-sourced dialkylamine with another flow of 0% bio-sourced dialkylamine, the two flows no longer being able to be distinguished at a time of production, due to a mixture for example. If the chemical compound produced is manufactured from 50% by weight of dialkylamine guarantees 50% bio-sourced, and 50% by weight of 0% bio-sourced dialkylamine, then the chemical compound is 25% bio-sourced.

[0051] To guarantee the figures displayed for the "bio-sourced" rate, for example, and to encourage the use of recycled raw materials in the production of new products, a set of rules shared and standardized on a global scale (ISCC+, ISO 14020) has been developed to reliably manage material flows.

[0052] In the context of the invention, the term "recycled" means the origin of a chemical compound resulting from a recycling process of a material considered to be waste, i.e. being the result of one or more transformations carried out during at least one recycling process on at least one material generally considered to be waste.

[0053] The term "water-soluble polymer" means a polymer which gives a clear aqueous solution when dissolved under stirring at 25°C and with a concentration of 20 gL 1 in water. Method according to the invention

[0054] The present invention therefore relates to a process for obtaining diallyldialkylammonium halide comprising the reaction between allyl halide and dialkylamine, one of the two (allyl halide and dialkylamine), preferably both, being at least partly of renewable and non-fossil origin.

[0055] More specifically and preferably, the compounds used to obtain diallyldialkylammonium halide and containing the carbon atoms which will be found in the molecule for obtaining diallyldialkylammonium halide are partially or totally of renewable and non-fossil origin. These compounds are allyl halide and dialkylamine.

[0056] The allyl halide preferably has a biosourced carbon content of between 5% by weight and 100% by weight, relative to the total weight of carbon in said allyl halide, the biosourced carbon content being measured according to standard ASTM D6866-21, method B.

[0057] The dialkylamine preferably has a biosourced carbon content of between 5% by weight and 100% by weight, relative to the total weight of carbon in said dialkylamine, the biosourced carbon content being measured according to standard ASTM D6866-21, method B.

[0058] Throughout the invention, the biosourced carbon content of a compound for which it is specified that it is at least partly of renewable and non-fossil origin, or for which the biosourced carbon content is specified, relative to the total weight of carbon in said compound, is from 5% by weight to 100% by weight, and preferably from 10% by weight to 100% by weight, preferably from 15% by weight to 100% by weight, preferably from 20% by weight to 100% by weight, preferably from 25% by weight to 100% by weight, preferably from 30% by weight to 100% by weight, preferably from 35% by weight to 100% by weight, preferably from 40% by weight to 100% by weight, preferably from 45% by weight to 100% by weight, preferably from 50% by weight. weight to 100% by weight, preferably from 55% by weight to 100% by weight, preferably from 60% by weight to 100% by weight, preferably from 65% by weight to 100% by weight, preferably from 70% by weight weight to 100% by weight, preferably from 75% by weight to 100% by weight, preferably from 80% by weight to 100% by weight, preferably from 85% by weight to 100% by weight, preferably from 90% by weight to 100% by weight, preferably from 95% by weight to 100% by weight, preferably from 97% by weight to 100% by weight, preferably from 99% by weight to 100% by weight, the bio-based carbon content being measured according to ASTM D6866-21, method B.

[0059] Preferably, the allyl halide has a biosourced carbon content of between 33.33% by weight and 100% by weight, preferably between 66.67% and 100%, more preferably 100% by weight, relative to the total weight of carbon in said allyl halide, the biosourced carbon content being measured according to standard ASTM D6866-21, method B.

[0060] Preferably, the dialkylamine has a biosourced carbon content of between 50 and 100% by weight, more preferably 100% by weight, relative to the total weight of carbon in said dialkylamine, the biosourced carbon content being measured according to standard ASTM D6866-21, method B.

[0061] Preferably, the allyl halide is entirely of renewable and non-fossil origin. Preferably, the dialkylamine is entirely of renewable and non-fossil origin. Preferably, the allyl halide and the dialkylamine are entirely of renewable and non-fossil origin.

[0062] The allyl halide and / or the dialkylamine may be non-segregated, partially segregated, or fully segregated, preferably partially or fully.

[0063] When the allyl halide and / or the dialkylamine is (are) entirely of renewable and non-fossil origin, then they can be: a) Be entirely of recycled origin and a)l) Be totally segregated; a)2) Be partially segregated; a)3) Be non-segregated; b) Either partially of recycled origin and b)l) Be totally segregated; b)2) Be partially segregated; b)3) Be non-segregated; c) Is entirely of non-recycled origin and c)l) Be totally segregated; c)2) Be partially segregated; c)3) Be non-segregated.

[0064] In these different modes, when the compound (allyl halide and / or dialkylamine) is partially segregated, then the weight ratio between the part " segregated” and the “non-segregated” part is preferably between 99:1 and 10:90, preferably between 99:1 and 30:70, more preferably between 99:1 and 50:50.

[0065] Among these different modes, the three modes a), the three modes b) and the mode c)l) are preferred. Among these modes, the modes a)l), a)2), b)l), b)2) and c)l) are even more preferred. The two most preferred modes are a)1) and b)l).

[0066] The industrial reality is that it is not always possible to obtain industrial quantities of bio-sourced compound (allyl halide and / or dialkylamine) that is totally recycled and / or segregated or with a high degree of recycling and / or segregation. This is why the above-mentioned preferences are perhaps more difficult to implement at present. From a practical point of view, methods a)3), b)3), and methods c) are currently implemented more easily and on a larger scale. As techniques are evolving rapidly in the direction of the circular economy, there is no doubt that the preferred methods, which can already be applied, can be applied on a very large scale quickly.

[0067] When the compound (allyl halide and / or dialkylamine) is partially of renewable and non-fossil origin, then the part of renewable origin (biosourced) is distinguished from the non-biosourced part. Each can of course be according to the same methods a) b) and c) previously described.

[0068] With respect to the biosourced portion of the partially biosourced compound, the same preferences apply as in the case where the compound is totally biosourced.

[0069] But as regards the non-biosourced part of the partially biosourced compound, then it is even more preferable to have as large a recycled component as possible for a circular economy approach. This is why, in this case, methods a)l), a)2), b)l), b)2) are preferred, and particularly a)l) and b)l).

[0070] In the invention and in the various embodiments set out below, the allyl halide is preferably obtained from propylene derived at least in part, preferably totally from biomass, i.e. of renewable and non-fossil origin. The alkyl halide is preferably obtained from propylene and a halogenated compound such as, for example, Cl2.

[0071] In the invention and in the various embodiments set out below, the dialkylamine is preferably obtained from methanol derived at least in part, preferably totally from biomass, i.e. of renewable and non-fossil origin. The dialkylamine is preferably obtained from methanol and ammonia.

[0072] As regards the reaction between the allyl halide and a dialkylamine to form the diallyldialkylammonium halide, those skilled in the art may refer to already established knowledge. Preferably, the process for obtaining diallyldialkylammonium halide is by the so-called direct route which consists of not isolating the allyldialkylamine intermediate.

[0073] The allyl halide is preferably an allyl chloride, but it can also be an allyl bromide or an allyl iodide.

[0074] The dialkylamine is preferably dimethylamine, but can also be diethylamine, diisopropylamine, dipropylamine, dibutylamine, dihexylamine. The dialkylamine is preferably a secondary amine having two identical alkyl groups. The alkyl groups of the dialkylamine can be linear or branched.

[0075] The monomer obtained according to the process is preferably diallyldimethylammonium chloride, but it can also be diallyldiethylammonium chloride, diallyldimethylammonium bromide, diallyldiisopropylammonium chloride, diallyldipropylammonium chloride, diallyldibutylammonium chloride, diallyldihexylammonium chloride.

[0076] The description of the process below is made considering dimethylamine and allyl chloride, but the process can be generalized with a dialkylamine and an allyl halide. In a first step, dimethylamine, aqueous or anhydrous, is introduced into a reactor. In the case where anhydride dimethylamine is used, the person skilled in the art will know how to adjust the quantity of water to be added to have a dimethylamine solution at, preferably, 60% by weight.

[0077] In a second step, allyl chloride is continuously added to the reactor for a time generally between 1 and 24 hours, preferably between 2 and 12 hours. Simultaneously, an aqueous solution of sodium hydroxide, preferably at 50% concentration by weight, is added to the reactor, for a time preferably between 1 and 24 hours, more preferably between 2 and 12 hours.

[0078] The molar ratio between dimethylamine, allyl chloride and sodium hydroxide is generally between 1:2:2 and 1:10:10, preferably between 1:2:2 and 1:3:3. The rate of addition of allyl chloride and / or sodium hydroxide can be constant, gradual or with any other profile.

[0079] The pH of the reaction medium is generally between 6 and 12, preferably between 8 and 10. The reaction can be carried out under atmospheric pressure or under pressure. In the latter case, the pressure is preferably between 2 bars absolute and 10 bars absolute. The reaction temperature is generally between 10 and 120°C, preferably between 50 and 90°C. The reaction can be carried out in batch, semi-batch or continuous mode.

[0080] At the end of the reaction, the diallyldimethylammonium chloride is in aqueous solution in the presence of sodium chloride in suspended particulate form. The monomeric product can be used as is (aqueous solution + particulate NaCl), or undergo filtration in order to separate the sodium chloride.

[0081] In a non-limiting manner, the filtration equipment may be a nutsche filter, a filter press, a vertical or horizontal centrifuge, a rotary filter under vacuum or pressure. Filtration may also be carried out in the reactor if the latter is equipped at the drain with a suitable mesh screen to retain the sodium chloride crystals.

[0082] Optionally, the aqueous solution of diallyldimethylammonium chloride can be purified. In a non-limiting manner, the purification can be carried out by distillation, evaporation on falling film equipment, a thin film evaporator or in a reboiler, by addition of water vapor, at atmospheric pressure or under vacuum.

[0083] In a particular embodiment, the dialkylamine and / or the allyl halide are partially or totally derived from a recycling process.

[0084] In this particular embodiment, the dialkylamine and / or the allyl halide are derived from a recycling process, such as for example from the depolymerization of polymer or by manufacturing from pyrolysis oil, the latter being the result of combustion at high temperature and in an anaerobic environment of used plastic waste. Thus, materials considered as waste can serve as a source for producing recycled compounds which can in turn be used as raw material for manufacturing the monomer of the invention. The monomer according to the invention then being derived from a recycling process, then the polymer according to the invention, described below, can satisfy the virtuous circle of the circular economy.

[0085] Furthermore, the method according to the invention preferably comprises the following steps: - Recycle at least one material at least partly of renewable and non-fossil origin to obtain a dialkylamine and / or an allyl halide; - Reacting a dialkylamine and an allyl halide to obtain diallyldialkylammonium halide, the dialkylamine and / or the allyl halide being partially or totally derived from recycling. Monomer according to the invention

[0086] The invention also relates to a diallyldialkylammonium biohalide having a biosourced carbon content of between 5% by weight and 100% by weight, relative to the total weight of carbon in said monomer, the biosourced carbon content being measured according to ASTM D6866-21, method B. The same modes and preferences developed in the process part apply to this part of the description concerning the monomer.

[0087] The invention also relates to a diallyldialkylammonium biohalide obtained by reaction between allyl halide and dialkylamine, said allyl halide and / or said dialkylamine being at least partly of renewable and non-fossil origin.

[0088] The invention also relates to a diallyldialkylammonium biohalide obtained by reaction between allyl halide and dialkylamine, said allyl halide and / or said dialkylamine, have a biosourced carbon content of between 5% by weight and 100% by weight, relative to the total weight of carbon respectively in said allyl halide and / or said dialkylamine, the biosourced carbon content being measured according to ASTM D6866-21, method B.

[0089] Preferably, the allyl halide is entirely of renewable and non-fossil origin. Preferably, the dialkylamine is entirely of renewable and non-fossil origin. Preferably, the allyl halide and the dialkylamine are entirely of renewable and non-fossil origin.

[0090] By diallyldialkylammonium biohalide is meant a diallyldialkylammonium halide at least in part, preferably totally derived from biomass, that is to say being the result of one or more chemical transformations carried out on one or more raw materials having a natural origin. The diallyldialkylammonium biohalide can also be called biosourced or bio-resourced diallyldialkylammonium halide.

[0091] The allyl halide is preferably an allyl chloride, but it can also be an allyl bromide or an allyl iodide.

[0092] The dialkylamine is preferably dimethylamine, but can also be diethylamine, diisopropylamine, dipropylamine, dibutylamine, or dihexylamine.

[0093] The monomer according to the invention is preferably diallyldimethylammonium biochloride, but it can also be diallyldiethylammonium biochloride, diallyldimethylammonium biobromide, diallyldiisopropylammonium biochloride, diallyldipropylammonium biochloride, diallyldibutylammonium biochloride, diallyldihexylammonium biochloride

[0094] The subject of the invention is a bio-diallyldimethylammonium chloride having a bio-sourced carbon content of between 5% by weight and 100% by weight, relative to the total weight of carbon in said monomer, the bio-sourced carbon content being measured according to standard ASTM D6866-21, method B.

[0095] The dialkylamine and / or allyl halide may be non-segregated, partially segregated, or fully segregated. The same preferences developed in the process portion apply to this portion of the disclosure relating to the monomer.

[0096] In a particular embodiment, the dialkylamine and / or allyl halide may be partially or totally of recycled origin. The same preferences developed in the process part apply to this part of the description concerning the monomer. Polymer according to the invention

[0097] The invention relates to a polymer obtained by polymerization of at least one diallyldialkylammonium biohalide monomer obtained according to the process according to the invention. It also relates to a polymer obtained by polymerization of at least one diallyldialkylammonium biohalide monomer as previously described. The same modes and preferences developed in the "process" part apply to this part of the description concerning the polymer.

[0098] The polymer according to the invention is preferably water-soluble or water-swelling. The polymer can also be a superabsorbent.

[0099] The polymer according to the invention may be a homopolymer or a copolymer of at least one diallyldialkylammonium biohalide monomer obtained according to the process according to the invention, or of at least one diallyldialkylammonium biohalide monomer as previously described, and of at least one different additional monomer, the latter being advantageously chosen from at least one non-ionic monomer, and / or at least one anionic monomer, and / or at least one cationic monomer, and / or at least one zwitterionic monomer and / or at least one monomer comprising a hydrophobic group.

[0100] Thus, the copolymer may comprise at least one second monomer different from the first monomer (diallyldialkylammonium halide according to the invention), this second monomer being chosen from non-ionic monomers, anionic monomers, cationic monomers, zwitterionic monomers, monomers comprising a hydrophobic group, and mixtures thereof.

[0101] The non-ionic monomer is preferably chosen from acrylamide, methacrylamide, N-isopropylacrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, N-methylolacrylamide, N-vinylformamide (NVF), N-vinyl acetamide, N-vinylpyridine and N-vinylpyrrolidone (NVP), N-vinyl imidazole, N-vinyl succinimide, acryloyl morpholine (ACMO), acryloyl chloride, glycidyl methacrylate, glyceryl methacrylate, and diacetone acrylamide.

[0102] The anionic monomer is preferably chosen from acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, acrylamido undecanoic acid, 3-acrylamido 3-methylbutanoic acid, maleic anhydride, 2-acrylamido-2-methylpropane sulfonic acid (ATBS), vinyl sulfonic acid, vinyl phosphonic acid, allyl sulfonic acid, methallyl sulfonic acid, 2-sulfoethyl methacrylate, sulfopropylmethacrylate, sulfopropylacrylate, allylphosphonic acid, styrenesulfonic acid, 2-acrylamido-2-methylpropane disulfonic acid, and the water-soluble salts of these monomers such as their alkali metal, alkaline earth metal, or ammonium salts. It is preferably acrylic acid (and / or one of its salts), and / or ATBS (and / or one of its salts).

[0103] The cationic monomer is preferentially chosen from quaternized dimethylaminoethyl acrylate (ADAME), quaternized dimethylaminoethyl methacrylate (MADAME), dimethyldiallylammonium chloride (DADMAC), acrylamido propyltrimethyl ammonium chloride (APTAC), and methacrylamido propyltrimethyl ammonium chloride (MAPTAC).

[0104] The zwitterionic monomer may be a derivative of a vinyl-type unit, in particular acrylamide, acrylic, allyl or maleic, this monomer having an amine or ammonium function (advantageously quaternary) and an acid function of the carboxylic (or carboxylate), sulfonic (or sulfonate) or phosphoric (or phosphate) type.

[0105] Monomers having a hydrophobic character can also be used in the preparation of the polymer. They are preferably chosen from the group consisting of (meth)acrylic acid esters having an alkyl, arylalkyl, propoxylated, ethoxylated, or ethoxylated and propoxylated chain; (meth)acrylamide derivatives having an alkyl, arylalkyl, propoxylated, ethoxylated, ethoxylated and propoxylated, or dialkyl chain; alkyl aryl sulfonates, or by mono- or di-substituted amides of (meth)acrylamide having an alkyl, arylalkyl, propoxylated, ethoxylated, or ethoxylated and propoxylated chain; (meth)acrylamide derivatives having an alkyl, arylalkyl, propoxylated, ethoxylated, ethoxylated and propoxylated, or dialkyl chain; alkyl aryl sulfonates.

[0106] Each of these monomers can also be biosourced.

[0107] According to the invention, the polymer may have a linear, branched, star (star-shaped), comb (comb-shaped), dendritic or block structure. These structures may be obtained by selecting the initiator, the transfer agent, the polymerization technique such as controlled radical polymerization known as RAFT (reversible-addition fragmentation chain transfer), NMP (nitroxide-mediated polymerization) or ATRP (atom transfer radical polymerization), the incorporation of structural monomers, the concentration...

[0108] According to the invention, the polymer is advantageously linear or structured. By structured polymer is meant a non-linear polymer which has chains lateral so as to obtain, when this polymer is dissolved in water, a strong state of entanglement leading to very high low gradient viscosities. The polymer of the invention can also be crosslinked.

[0109] The polymer according to the invention can further be structured: - by at least one structural agent, which may be chosen from the group comprising monomers with polyethylene unsaturation (having at least two unsaturated functions), such as for example vinyl functions, in particular allylic, acrylic and epoxy and we can cite for example methylene bis acrylamide (MBA), triallyamine, or tetraallylammonium chloride or 1,2 dihydroxyethylene bis-(N-acrylamide), and / or - by macroinitiators such as polyperoxides, polyazos and polytransfer agents such as polymercaptant (co)polymers, and polyols, and / or - by functionalized polysaccharides.

[0110] The amount of branching / crosslinking agent in the monomer mixture is advantageously less than 4% by weight relative to the monomer content (weight), more advantageously less than 1%, and even more advantageously less than 0.5%. According to a particular embodiment, it may be at least equal to 0.00001% by weight relative to the monomer content.

[0111] In a particular embodiment, the polymer according to the invention may be a semi-synthetic and therefore semi-natural polymer. In this embodiment, the polymer may be synthesized by total or partial graft copolymerization of at least one monomer according to the invention, and at least one natural compound, said natural compound being preferentially chosen from starches and their derivatives, polysaccharides and their derivatives, fibers, vegetable gums, animal gums or algae gums, and their modified versions. Vegetable gums can be, for example, guar gum, gum arabic, locust bean gum, tragacanth gum, guanidinium gum, cyanine gum, tara gum, cassia gum, xanthan gum, gum ghatti, tragacanth gum, karaya gum, gellan gum, cyamopsis tetragonoloba gum, soybean gum, or even beta-glucan or dammar.The natural compound can also be gelatin, casein, or chitosan. Algal gum can be, for example, sodium alginate or its acid, agar-agar, or carrageenan.

[0112] The polymerization is generally carried out, without this being limiting, by copolymerization or by grafting. The person skilled in the art may refer to the common general knowledge in the field of semi-natural polymers.

[0113] The invention also relates to a composition comprising at least one polymer according to the invention and at least one natural polymer, said natural polymer being preferably chosen from the natural polymers previously exposed. The ratio in The weight ratio of synthetic polymer to natural polymer is generally between 90:10 and 10:90. The composition can be in liquid form, inverse emulsion form or powder form.

[0114] Generally speaking, the polymer does not require the development of a particular polymerization process. Indeed, it can be obtained using all the polymerization techniques well known to those skilled in the art. This may in particular involve solution polymerization; gel polymerization; precipitation polymerization; emulsion polymerization (aqueous or inverse); suspension polymerization; reactive extrusion polymerization; water-in-water polymerization; or micellar polymerization.

[0115] The polymerization is generally a free radical polymerization preferably by inverse emulsion polymerization or by gel polymerization. By free radical polymerization we include free radical polymerization using UV, azo, redox or thermal initiators as well as controlled radical polymerization (CRP) techniques or matrix polymerization techniques.

[0116] The polymer according to the invention can be modified after it has been obtained by polymerization. This is then referred to as post-modification of the polymer. All known post-modifications can be applied to the polymer according to the invention, and the invention also relates to the polymers obtained after said post-modifications. Among the possible post-modifications developed below, mention may be made of post-hydrolysis, post-modification by Mannich reaction, post-modification by Hoffman reaction and post-modification by glyoxalation reaction.

[0117] The polymer according to the invention can be obtained by carrying out a posthydrolysis reaction on a polymer obtained by polymerization of at least one monomer obtained by the process according to the invention or of at least one monomer as previously described in the “Monomer” section. Before post-hydrolysis, the polymer comprises, for example, monomeric units of acrylamide or methacrylamide. The polymer may also further comprise monomeric units of N-Vinylformamide. More specifically, post-hydrolysis consists of the reaction of hydrolyzable functional groups of advantageously non-ionic monomeric units, more advantageously amide or ester functions, with a hydrolysis agent. This hydrolysis agent may be an enzyme, an ion exchange resin, an alkali metal, or a suitable acidic compound. Preferably, the hydrolysis agent is a Br0nsted base. When the polymer comprises amide and / or ester monomeric units, then the post-hydrolysis reaction produces carboxylate groups. When the polymer comprises vinylformamide monomeric units, then the post-hydrolysis reaction produces amine groups.

[0118] The polymer according to the invention can be obtained by carrying out a Mannich reaction on a polymer obtained by polymerization of at least one monomer obtained by the process according to the invention or of at least one monomer as previously described in the “Monomer” section. More precisely, before the Mannich reaction the polymer advantageously comprises monomeric units of acrylamide and / or methacrylamide. The Mannich reaction is carried out in aqueous solution in the presence of a dialkyl amine and a formaldehyde precursor. More advantageously, the dialkyl amine is dimethylamine and the formaldehyde precursor is formaldehyde itself. After this reaction, the polymer contains tertiary amines.

[0119] The polymer according to the invention can be obtained by carrying out a Hoffman reaction on a polymer obtained by polymerization of at least one monomer obtained by the process according to the invention or of at least one monomer as previously described in the “Monomer” section. Before the Hoffman reaction, the polymer advantageously comprises monomeric units of acrylamide and / or methacrylamide. The so-called Hofmann degradation reaction is carried out in aqueous solution, in the presence of an alkaline earth and / or alkali metal hydroxide and an alkaline earth and / or alkali metal hypohalide.

[0120] This reaction, discovered by Hofmann at the end of the nineteenth century, allows the conversion of an amide function into a primary amine function with one less carbon atom. The reaction mechanism is detailed below.

[0121] In the presence of a Brpnsted base (for example sodium hydroxide), a proton is removed from the amide.

[0122] [Chem.2] S - S \ --riA *" ~ 'H

[0123] The amidate ion formed then reacts with the active chlorine (Cl2) of the hypochlorite (eg: NaCIO which is in equilibrium: 2 NaOH + Cl2 NaCIO + NaCl + H2O) to give an N-chloramide. The Brpnsted base (for example NaOH) removes a proton from the chloramide to form an anion. The anion loses a chloride ion to form a nitrene which undergoes a transposition into isocyanate.

[0124] [Chem.3] O z., F — k_X'

[0125] By reaction between the hydroxide ion and the isocyanate, a carbamate is formed.

[0126] [Chem.4] R—N—C=0 + 0H“ ------R—NH—C02“

[0127] After decarboxylation (removal of CO2) from the carbamate, a primary amine is obtained.

[0128] [Chem.5] + H R—N—CO----- R-NH. H -CO,

[0129] For the conversion of all or part of the amide functions of a (co)polymer comprising an amide group into an amine function, two main factors are involved (expressed in molar ratios). These are: - Alpha = (alkali and / or alkaline earth hypohalide / amide group) and - Beta = (alkali and / or alkaline earth hydroxide / alkali and / or alkaline earth hypohalide).

[0130] The polymer according to the invention can also be obtained by carrying out a glyoxalation reaction on a polymer obtained by polymerization of at least one monomer obtained by the process according to the invention or of at least one monomer as previously described in the “Monomer” section, said polymer comprising with the glyoxalation reaction at least one monomeric unit advantageously of acrylamide or methacrylamide. More precisely, the glyoxalation reaction consists of reacting at least one aldehyde on the polymer, thus making it possible to functionalize said polymer. Advantageously, the aldehyde may be chosen from the group comprising glyoxal, glutaraldehyde, furan-dialdehyde, 2-hydroxyadipaldehyde, succinaldehyde, starch dialdehyde, 2,2 dimethoxyethanal, diepoxy compounds, and combinations thereof. Preferably, the aldehyde compound is glyoxal.

[0131] According to the invention, the polymer may be in liquid, gel or solid form when its preparation includes a drying step such as “spray drying”, drum drying, radiation drying such as microwave drying, or even fluidized bed drying.

[0132] According to the invention, the water-soluble polymer preferably has a molecular weight of between 1000 and 40 million g / mol. The polymer may be a dispersant, and in this case its molecular weight is preferably between 1000 and 50,000 g / mol. The polymer may have a higher molecular weight, generally between 1 and 30 million g / mol. The molecular weight is understood as weight-average molecular weight. The polymer according to the invention may also be a superabsorbent capable of absorbing 10 to 500 times its weight in water.

[0133] The molecular weight is advantageously determined by the intrinsic viscosity of the (co)polymer. The intrinsic viscosity can be measured by methods known to those skilled in the art and can be calculated from the reduced viscosity values ​​for different (co)polymer concentrations by a graphical method consisting of plotting the reduced viscosity values ​​(y-axis) on the concentration (x-axis) and extrapolating the curve to zero concentration. The intrinsic viscosity value is plotted on the y-axis or using the least squares method. The molecular weight can then be determined by the Mark-Houwink equation: [q] = KM" [q] represents the intrinsic viscosity of the (co)polymer determined by the solution viscosity measurement method. K represents an empirical constant. M represents the molecular weight of the (co)polymer. a represents the Mark-Houwink coefficient. K and a depend on the particular (co)polymer-solvent system.

[0134] The co-monomers associated with the monomer according to the invention to obtain the polymer of the invention are preferably at least partly, more preferably totally of renewable and non-fossil origin.

[0135] Thus, in a preferred embodiment, the invention relates to a polymer comprising: - at least 5 mol%, preferably at least 10 mol%, preferably between 20% and 99 mol%, more preferably between 30% and 90% of a first monomer, said monomer being a monomer according to the invention, and - at least 1 mol%, preferably between 5% and 90 mol%, more preferably between 10% and 80 mol% of at least one second monomer comprising ethylenic unsaturation, said second monomer being different from the first monomer, and being at least partly of renewable and non-fossil origin.

[0136] Thus, in a preferred embodiment, the invention relates to a polymer comprising: - at least 5 mol%, preferably at least 10 mol%, preferably between 20% and 99 mol%, more preferably between 30% and 90% of a first monomer, said monomer being a monomer according to the invention, and - at least 1 mol%, preferably between 5% and 90% mol%, more preferably between 10% and 80% mol% of at least one second monomer comprising ethylenic unsaturation, said second monomer being different from the first monomer, and being at least partly of renewable and non-fossil origin, - at least 1 mol%, preferably between 5% and 90% mol%, more preferably between 10% and 80% mol% of at least one third monomer comprising ethylenic unsaturation, said third monomer being different from the first and second monomer, and being at least partly of renewable and non-fossil origin.

[0137] The polymer according to the invention may comprise four or more different monomers.

[0138] In a preferred embodiment, the second and any other monomers have a bio-sourced carbon content of between 5% by weight and 100% by weight, preferably 10% by weight and 100% by weight, relative to the total weight of carbon in the monomer concerned, the bio-sourced carbon content being measured according to ASTM D6866-21, method B.

[0139] In this preferred embodiment, the second and any other monomers are preferentially chosen from acrylamide, (meth)acrylic acid and / or one of its salts, an oligomer of acrylic acid, 2-acrylamido-2-methylpropane sulfonic acid (ATBS) and / or one of its salts, N-vinylformamide (NVF), N-vinylpyrrolidone (NVP), dimethylaminoethyl (meth)acrylate and its quaternized versions, a substituted acrylamide of formula CH2=CHCO-NR1R2, R1 and R2 being, independently of one another, a linear or branched carbon chain CnH2n+i, in which n is between 1 and 10.

[0140] Throughout the invention, it will be understood that the molar percentage of monomers (with the exception of any crosslinking agents) of the polymer is equal to 100%.

[0141] Preferably, the polymer according to the invention comprises a biosourced carbon content of between 5% by weight and 100% by weight, relative to the total weight of carbon in said polymer, the biosourced carbon content being measured according to standard ASTM D6866-21, method B.

[0142] The invention also relates to a polymer obtained according to a process comprising the following steps: - Recycle at least one material at least partly of renewable and non-fossil origin, or a material of fossil origin, to obtain allyl halide and / or dialkylamine; - Reacting the allyl halide and the dialkylamine thus obtained to obtain the diallyldialkylammonium halide; - Polymerizing said diallyldialkylammonium halide thus obtained, optionally with at least one second monomer comprising at least one ethylenic unsaturation, to obtain a polymer.

[0143] The dialkylamine and / or allyl halide may be non-segregated, partially segregated, or fully segregated. The same preferences developed in the process portion apply to this portion of the description relating to the polymer.

[0144] In a particular embodiment, the dialkylamine and / or allyl halide may be partially or totally of recycled origin. The same preferences developed in the process part apply to this part of the description concerning the polymer.

[0145] The invention also relates to the use of at least one monomer obtained by the process according to the invention for synthesizing a polymer. Use of the polymer according to the invention

[0146] The invention also relates to the use of the polymer according to the invention in the recovery of hydrocarbons (oil and / or gas); in the drilling and cementing of wells; in the stimulation of hydrocarbon wells (oil and / or gas), for example hydraulic fracturing, conforming, diversion; in the treatment of water in open, closed or semi-closed circuits; in the treatment of fermentation musts; in the treatment of sludge; in the manufacture of paper; in construction; in the treatment of wood; in the treatment of hydraulic composition (concrete, cement, mortar and aggregates); in the mining industry; in the formulation of cosmetic products; in the formulation of detergents; in the manufacture of textiles; in the manufacture of battery components; in geothermal energy; in the manufacture of hygienic diapers; or in agriculture.

[0147] The invention also relates to the use of the polymer according to the invention as a flocculant, coagulant, binding agent, fixing agent, viscosity reducing agent, thickening agent, absorbent agent, friction reducing agent, draining agent, drainage agent, charge retention agent, dehydrating agent, conditioning agent, stabilizing agent, fixing agent, film-forming agent, sizing agent, superplasticizing agent, clay inhibitor or dispersant. Process using the polymer according to the invention

[0148] The present invention also relates to the various processes described below in which the polymers of the invention make it possible to improve application performance.

[0149] The invention also relates to a method for enhanced recovery of oil or gas by sweeping an underground formation comprising the following steps: a. Preparing an injection fluid from a polymer according to the invention, with water or brine, b. Injecting the injection fluid into an underground formation, c. Sweeping the underground formation using the injected fluid, d. Recovering an aqueous mixture of oil and / or gas.

[0150] The invention also relates to a method for hydraulic fracturing of underground oil and / or gas reservoirs comprising the following steps: a. Prepare an injection fluid from a polymer according to the invention, with water or brine, and with at least one supporting agent, b. Injecting said fluid into the underground reservoir and fracturing at least a portion of it in order to recover oil and / or gas.

[0151] In the methods described above, the polymer is preferably a high molecular weight polymer (greater than 8 million daltons). It is preferably linear. It is preferably in the form of powder, inverse emulsion, partially dehydrated inverse emulsion, or in the form of "clear", that is to say a dispersion of solid particles of polymers in an aqueous or oily fluid. The powder form is preferably obtained by gel or by "spray drying" of an inverse emulsion. It may also be a composition comprising an inverse emulsion of a polymer according to the invention and solid particles of a polymer according to the invention.

[0152] The invention also relates to a method of stimulating an underground formation comprising the following steps: a. Prepare an injection fluid from a polymer according to the invention, with water or brine, b. Injecting the injection fluid into an underground formation, c. partially or completely plugging a portion of the underground formation with the injected fluid, said plugging being temporary or permanent.

[0153] The invention also relates to a method for drilling and / or cementing a well in an underground formation comprising the following steps: a. Preparing a fluid from a polymer according to the invention, with water or brine, b. Injecting said drilling and / or cementing fluid into the underground formation via the drilling head in at least one step of drilling or cementing a well.

[0154] Drilling and cementing a well are two successive steps in creating a well in an underground formation. The first step is drilling with drilling fluid, then the second step is cementing the well with the cementing fluid. The invention also relates to a method for injecting an intermediate fluid ("spacer fluid" in English) injected between the drilling fluid and the cementing fluid, said intermediate fluid comprising at least one polymer according to the invention. This intermediate fluid makes it possible to avoid contamination between the cementing fluid and the drilling fluid.

[0155] In drilling and cementing a well, the polymer of the invention may be used as a fluid loss additive in well cement compositions to reduce fluid loss from the cement compositions to permeable formations or zones in or through which the cement compositions are pumped. In primary cementing, loss of fluid, i.e., water, to permeable subterranean formations or zones may result in premature gelation of the cement composition, such that bridging of the annulus between the permeable formation or zone and the drill string cemented therein prevents the cement composition from being placed along the entire length of the annulus.

[0156] The invention also relates to a method for inerting clays in hydraulic compositions intended for construction, said method comprising a step consisting of adding to the hydraulic composition or to one of its constituents at least one clay inerting agent, characterized in that the clay inerting agent is a polymer according to the invention.

[0157] Clays can absorb water and cause poor performance of construction materials. When the polymer of the invention is used as a clay inhibitor, it makes it possible in particular to prevent the swelling of clays which could cause cracks weakening any construction.

[0158] The hydraulic composition may be a concrete, a cement, a mortar or an aggregate. The polymer is added to the hydraulic composition or to one of its constituents advantageously at a dosage of 2 to 200 ppm of inerting agent relative to the weight of aggregate.

[0159] In this method of inerting clays, the clays include, but are not limited to, swelling clays of the 2:1 type (such as smectite), or of the 1:1 type (such as kaolin) or of the 2:1:1 type (such as chlorite). The term "clay" generally refers to magnesium and / or aluminum silicate, including phyllo silicates having a lamellar structure. However, in the present invention the term "clay" also includes clays not having such a structure, such as amorphous clays.

[0160] The invention also relates to a method for manufacturing a sheet of paper, cardboard or the like, according to which, before forming a sheet, a step is carried out of adding to a suspension of fibers, at one or more injection points, at least one polymer according to the invention. The polymer can provide retention or dry strength or wet strength properties. It can also improve paper formation, drainage and draining capacities.

[0161] The process can be used successfully for the manufacture of packaging papers and cardboards, coating support papers, sanitary and household papers, any type of paper, cardboard or the like.

[0162] The post-modified polymers described in the “Polymers” section, in particular the polymers post-modified by Hoffman reaction or by glyoxalation reaction, are particularly advantageous in the processes for manufacturing paper, cardboard or the like.

[0163] Retention properties mean the ability to retain suspended matter from the paper pulp (fibers, fines, fillers (calcium carbonate, titanium oxide), etc.) on the forming fabric, therefore in the fibrous mat that will constitute the final sheet. The mode of action of retention agents is based on the flocculation of these suspended matters in water. In fact, the flocs formed are more easily retained on the forming fabric.

[0164] Filler retention consists of specifically retaining fillers (small mineral species with little affinity for cellulose). The significant improvement in filler retention leads to clarification of white water by retaining the fillers in the sheet as well as increasing its grammage. This also makes it possible to substitute part of the fibers (the most expensive species in the composition of paper, cardboard or the like) with fillers (lower costs) to reduce manufacturing costs.

[0165] With regard to the drainage properties, this is the capacity of the fibrous mat to evacuate or drain the maximum amount of water so that the sheet dries as quickly as possible, particularly during the manufacture of the sheet.

[0166] These two properties (retention and drainage) being closely linked, one depending on the other, it is then a question of finding the best compromise between retention and drainage. Generally speaking, the person skilled in the art refers to a retention and drainage agent because these are the same types of products which make it possible to improve these two properties.

[0167] By fibrous suspension is meant the thick stock or the diluted stock which are based on water and cellulose fibers. The thick stock, having a mass concentration of dry matter greater than 1%, or even greater than 3%, is upstream of the mixing pump (fan-pump). The diluted stock ("Thin Stock" in English), having a mass concentration of dry matter generally less than 1%, is located downstream of the mixing pump.

[0168] The polymer can be introduced into the thick stock or into the thin stock. It can be added at the fan pump or the headbox. Preferably, the polymer is introduced before the headbox.

[0169] In the process for manufacturing paper, cardboard or the like according to the invention, the polymer according to the invention can be used alone or in combination with a secondary retention agent. Preferably, a secondary retention agent chosen from organic polymers and / or inorganic microparticles is added to the fibrous suspension.

[0170] This secondary retention agent added to the fibrous suspension is advantageously chosen from anionic polymers in the broad sense, which can therefore be (without being limiting) linear, branched, crosslinked, hydrophobic, associative and / or inorganic microparticles (such as bentonite, colloidal silica).

[0171] The invention also relates to a method for treating a suspension of solid particles in water resulting from mining or the exploitation of oil sands, comprising bringing said suspension into contact with at least one polymer according to the invention. Such a method can be carried out in a thickener, which is a retention zone, generally in the form of a tube section with a diameter of several meters with a conical bottom in which the particles can sediment. According to a specific embodiment, the aqueous suspension is transported by means of a pipe to a thickener, and the polymer is added to said pipe.

[0172] In another embodiment, the polymer is added to a thickener that already contains the slurry to be treated. In a typical mineral processing operation, slurries are often concentrated in a thickener. This results in a higher density slurry exiting the bottom of the thickener, and an aqueous fluid released from the treated slurry (called liquor) exiting as an overflow from the top of the thickener. In general, the addition of the polymer increases the concentration of the slurry and increases the clarity of the liquor.

[0173] According to another embodiment, the polymer is added to the particle suspension during the transport of said suspension to a deposition zone. Preferably, the polymer is added into the pipe which transports said suspension to a deposition zone. It is on this deposition zone that the treated suspension is spread for the purpose of its dehydration and solidification. The deposition zones can be unclosed, such as for example an undefined expanse of soil, or closed, such as for example a basin, a cell.

[0174] An example of these treatments during the transport of the suspension is the spreading of the suspension treated with the polymer according to the invention on the ground for the purpose of its dehydration and solidification and then the spreading of a second layer of treated suspension on the first solidified layer. Another example is the continuous spreading of the suspension treated with the polymer according to the invention so that the treated suspension falls continuously on the suspension previously discharged in the deposition zone, thus forming a pile of treated materials from which the water is extracted.

[0175] According to another embodiment, the water-soluble polymer is added to the suspension, and then a mechanical treatment is carried out, such as centrifugation, pressing or filtration.

[0176] The water-soluble polymer may be added simultaneously in different stages of the suspension treatment, i.e. for example in the pipe transporting the suspension to a thickener and in the sludge leaving the thickener which will be conducted either to a deposition zone or to a mechanical treatment apparatus.

[0177] The invention also relates to a method for treating municipal or industrial water comprising the introduction into said water to be treated of at least one polymer according to the invention. Effective water treatment requires the removal of dissolved compounds and dispersed and suspended solids from the water. This treatment is generally enhanced by chemicals such as coagulants and flocculants. These are generally added to the water stream before the separation unit, such as flotation and sedimentation.

[0178] The polymers according to the invention can be advantageously used to coagulate or flocculate particles suspended in municipal or industrial wastewater. They are generally used in combination with inorganic coagulants such as alum.

[0179] They can also be used to advantage to treat sludge resulting from the treatment of this wastewater. Sewage sludge (urban or industrial) is the main waste produced by a treatment plant from liquid effluents. The treatment of sludge generally consists of dehydrating it. This dehydration can be carried out by centrifugation, filter press, belt press filter, electrodehydration, reed drying bed, solar drying. It makes it possible to reduce the water concentration of the sludge.

[0180] In this process for treating municipal or industrial water, the polymer according to the invention is preferably linear or branched. It is preferably in the form of powder, inverse emulsion, or partially dehydrated inverse emulsion. The powder form is preferably obtained by gel or by spray drying from an inverse emulsion. The polymer is preferably a coagulant or a flocculant comprising dimethyldiallylammonium chloride (D AD MAC) according to the invention. More preferably, the polymer is a homopolymer of DADMAC or a copolymer of DADMAC and acrylamide.

[0181] The invention also relates to an additive for a cosmetic, dermatological or pharmaceutical composition, said additive comprising at least one polymer according to the invention. The invention also relates to the use of the polymer according to the invention in the manufacture of said compositions as a thickening (agent), conditioning (agent), stabilizing (agent), emulsifying (agent), fixing (agent) or film-forming agent. The invention also relates to cosmetic, dermatological or pharmaceutical compositions comprising at least one polymer according to the invention.

[0182] Reference may in particular be made to application FR2979821 in the name of L'OREAL for the manufacture of such compositions and the description of the other ingredients of such compositions. Said compositions may be in the form of a milk, a lotion, a gel, a cream, a cream gel, a soap, a bubble bath, a balm, a shampoo or a conditioner. The use of said compositions for the cosmetic or dermatological treatment of keratin materials such as the skin, scalp, eyelashes, eyebrows, nails, hair and / or mucous membranes, is also an integral part of the invention. Such use comprises the application of the composition to the keratin materials, optionally followed by rinsing with water.

[0183] The invention also relates to an additive for a detergent composition, said additive comprising at least one polymer according to the invention. The invention also relates to the use of the polymer according to the invention in the manufacture of said compositions as a thickening (agent), conditioning (agent), stabilizing (agent), emulsifying (agent), fixing (agent) or film-forming (agent). The invention also relates to detergent compositions for household or industrial use comprising at least one polymer according to the invention. Reference may in particular be made to the applicant's application WO2016020622 for the manufacture of such compositions and the description of the other ingredients of such compositions.

[0184] By "detergent compositions for household or industrial use" is meant compositions for cleaning various surfaces, in particular textile fibers, hard surfaces of any kind such as dishes, floors, windows, wooden, metal or composite surfaces. Such compositions correspond, for example, to detergents for washing clothes manually or in a washing machine, products for cleaning dishes manually or for dishwashers, detergent products for washing home interiors such as kitchen units, toilets, furnishings, floors, windows, and other cleaning products for universal use.

[0185] The polymer used as an additive, for example a thickener, for a cosmetic, dermatological, pharmaceutical, or detergent composition, is preferably crosslinked. It is preferably in the form of powder, inverse emulsion, or partially dehydrated inverse emulsion. The powder form is preferably obtained by “spray drying” from an inverse emulsion.

[0186] The invention also relates to a thickener for a pigment composition used in textile printing, said thickener comprising at least one polymer according to the invention. The invention relates to a textile fiber sizing agent, said agent comprises at least one polymer according to the invention.

[0187] The invention also relates to a method for manufacturing superabsorbent from the monomer according to the invention, a superabsorbent obtained from at least one monomer according to the invention, the use of said superabsorbent for absorbing and retaining water in agricultural applications or for absorbing aqueous liquids in hygienic diapers. The superabsorbent agent is for example a polymer according to the invention.

[0188] The invention also relates to a method for manufacturing hygienic diapers in which a polymer according to the invention is used, for example as a super absorbent agent.

[0189] The invention also relates to the use of the polymer according to the invention as a binder for a battery. The invention also relates to a binder composition for a battery comprising the polymer according to the invention, an electrode material and a solvent. The invention also relates to a method for manufacturing a battery comprising the manufacture of a gel comprising at least one polymer according to the invention and its introduction into said battery. Mention may be made of lithium-ion batteries which are used in a whole series of products, in particular medical devices, electric cars, airplanes and, above all, consumer products such as laptops, cell phones and cameras.

[0190] In general, lithium ion batteries (LIBs) comprise an anode, a cathode, and an electrolyte material such as an organic solvent containing a lithium salt. More specifically, the anode and cathode (collectively, the "electrodes") are formed by mixing an electrode active material (anode or cathode) with a binder and a solvent to form a paste or slurry that is then applied and dried onto a current collector, such as aluminum or copper, to form a film on the current collector. The anode and cathode are then layered and wound before being housed in a pressurized case containing an electrolyte material, which together form a lithium-ion battery.

[0191] In a lithium battery, the binder plays several important roles in both mechanical and electrochemical performance. First, it helps disperse the other components in the solvent during the manufacturing process (some also acting as thickeners), allowing for even distribution. Second, it holds the various components together, including the active components, any conductive additives, and the current collector, ensuring that all of these parts remain in contact. Through chemical or physical interactions, the binder connects these separate components, holding them together and ensuring the mechanical integrity of the electrode without significantly impacting electronic or ionic conductivity. Third, it often serves as an interface between the electrode and the electrolyte. In this role, it can protect the electrode from corrosion or the electrolyte from depletion while facilitating the transport of ions across this interface.

[0192] Another important point is that binders must have a certain degree of flexibility so that they do not crack or develop defects. Brittleness can create problems during battery manufacturing or assembly.

[0193] Considering all the roles it plays in an electrode (and in the battery as a whole), the choice of binder is crucial to ensure good battery performance.

[0194] The invention also relates to a method for manufacturing a hygienic diaper in which a polymer according to the invention is used, for example as a super absorbent agent.

[0195] As discussed earlier, the circular economy is an economic system dedicated to efficiency and sustainability that minimizes waste by optimizing the value generated by resources. It relies heavily on various conservation and recycling methods to move away from the current, more linear approach of “capture, make, and throw away.”

[0196] Thus, since the recycling of materials is an important and growing concern, recycling processes are developing rapidly and allow the production of materials that can be used to produce new compounds or new objects. The recycling of materials is independent of the origin of the material as long as it is recyclable; it is considered to be technical progress. The origin of the material to be recycled can be renewable and non-fossil, but it can also be fossil.

[0197] Particular objects are described below.

[0198] A first particular object relates to a process for obtaining diallyldialkylammonium halide comprising the reaction between allyl halide and dialkylamine characterized in that one of the two, preferably both, is (are) derived at least in part, preferably totally from a process of recycling a material of renewable and non-fossil origin, or from a material of fossil origin.

[0199] Preferably, the allyl halide and the dialkylamine are entirely of renewable and non-fossil origin, so they are preferably entirely “segregated”, that is to say, originating from a separate sector and treated separately. In an alternative mode, they are partly “segregated”, and partly “non-segregated”. In this case, the weight ratio between the “segregated” part and the “non-segregated” part is preferably between 99:1 and 10:90, preferably between 99:1 and 30:70, more preferably between 99:1 and 50:50. In another alternative mode, it is entirely “non-segregated”.

[0200] A second particular subject relates to a diallyldialkylammonium halide obtained by reaction between allyl halide and dialkylamine, said allyl halide being derived at least in part, preferably totally from a process of recycling a material of renewable and non-fossil origin, or from a material of fossil origin, and / or, preferably and, said dialkylamine being derived at least in part, preferably totally from a process of recycling a material of renewable and non-fossil origin, or from a material of fossil origin.

[0201] A third particular subject relates to a diallyldialkylammonium halide obtained by reaction between allyl halide and dialkylamine, said allyl halide being derived at least in part, preferably totally from a process of recycling a material of renewable and non-fossil origin, or from a material of fossil origin, and / or, preferably and, said dialkylamine being derived at least in part, preferably totally from a process of recycling a material of renewable and non-fossil origin, or from a material of fossil origin.

[0202] A fourth particular object relates to a polymer obtained by polymerization of at least one diallyldialkylammonium halide as just previously described.

[0203] A fifth particular object relates to the use of a polymer obtained by polymerization of at least one diallyldialkylammonium halide as just previously described, in the recovery of oil and / or gas; in the drilling and cementing of wells; in the stimulation of oil and / or gas wells (for example hydraulic fracturing, conformation, diversion); in the treatment of water in open, closed or semi-closed circuit; in the treatment of fermentation musts; in the treatment of sludge; in the manufacture of paper; in construction; in the treatment of wood; in the treatment of hydraulic composition (concrete, cement, mortar and aggregates); in the mining industry; in the formulation of cosmetic products; in the formulation of detergents; in the manufacture of textiles; in the manufacture of battery components; in geothermal energy; or in agriculture.

[0204] A sixth particular object concerns the use of a polymer obtained by polymerization of at least one diallyldialkylammonium halide as just previously described, as flocculant, coagulant, binding agent, fixing agent, viscosity reducing agent, thickening agent, absorbent agent, friction reducing agent, dewatering agent, drainage agent, charge retention agent, dehydrating agent, conditioning agent, stabilizing agent, fixing agent, film-forming agent, sizing agent, superplasticizing agent, clay inhibitor or dispersant.

[0205] A seventh particular object relates to a polymer obtained according to a process comprising the following steps: - Recycle at least one material at least partly of renewable and non-fossil origin, or a material of fossil origin, to obtain allyl halide and / or dialkylamine; - Reacting the allyl halide and the dialkylamine thus obtained to obtain the diallyldialkylammonium halide; - Polymerizing said diallyldialkylammonium halide thus obtained, optionally with at least one second monomer comprising at least one ethylenic unsaturation, to obtain a polymer.

[0206] The allyl halide and / or the dialkylamine are preferably completely “segregated”, that is to say, originating from a separate process and treated separately.

[0207] In an alternative mode they are partly “segregated”, and partly “non-segregated”. In this case the weight ratio between the “segregated” part and the “non-segregated” part is preferably between 99:1 and 10:90, preferably between 99:1 and 30:70, more preferably between 99:1 and 50:50. In another alternative mode it is totally “non-segregated”.

Claims

Claims

1. A process for obtaining diallyldialkylammonium halide comprising the reaction between allyl halide and dialkylamine, one of the two, preferably both, being at least partly of renewable and non-fossil origin.

2. A method according to claim 1, characterized in that the allyl halide has a bio-sourced carbon content of between 5% by weight and 100% by weight, relative to the total weight of carbon in said allyl halide, the bio-sourced carbon content being measured according to ASTM D6866-21, method B.

3. A method according to claim 1, characterized in that the dialkylamine has a biosourced carbon content of between 5% by weight and 100% by weight, relative to the total weight of carbon in said dialkylamine, the biosourced carbon content being measured according to standard ASTM D6866-21, method B.

4. Method according to one of claims 1 to 3, characterized in that the diallyldialkylammonium halide has a biosourced carbon content of between 5% by weight and 100% by weight, relative to the total weight of carbon in said diallyldialkylammonium halide, the biosourced carbon content being measured according to standard ASTM D6866-21, method B.

5. Process according to one of claims 1 to 4, characterized in that the allyl halide is allyl chloride.

6. Process according to one of claims 1 to 5, characterized in that the dialkylamine is dimethylamine.

7. Process according to one of claims 1 to 6, characterized in that the allyl halide and / or the dialkylamine are partially segregated or completely segregated.

8. Method according to one of claims 1 to 7, characterized in that the allyl halide and / or the dialkylamine are partially or totally derived from a recycling process.