Process for obtaining bio-sourced diallyldialkylammonium halide

Description

Field of the invention

The present invention relates to a method for obtaining bio-sourced diallyldialkylammonium halide comprising the reaction between an allyl halide and a dialkylamine, one of the two, preferentially both, being at least partially renewable and non-fossil. The invention relates to a bio-sourced diallyldialkylammonium halide monomer, preferentially diallyldimethylammonium chloride, as well as a bio-sourced polymer obtained from at least one bio-sourced diallyldialkylammonium halide monomer according to the invention. Lastly, the invention relates to the use of the invention’s bio-sourced polymers in various technical fields.

Prior art

The radical polymerization reaction of at least one ethylenic monomer comprising a quaternary ammonium function which may be chosen from acrylamidopropyltrimethyl ammonium chloride (APTAC), methacrylamidopropyltrimethyl ammonium chloride (MAPTAC), dimethylaminoethyl acrylate (ADAME) or dimethylaminoethyl methacrylate (MADAME), all of which are salified or quaternized with halogenated alkyl derivatives or dialkyl sulfates, is known to the person skilled in the art. However, the polymers obtained have limited cationic charge densities.

Another method for preparing water-soluble cationic polymers of high cationic charge density known to the person skilled in the art is the radical polymerization reaction of at least one allylic monomer, such as a diallyldialkylammonium halide. Among the allylic monomers, diallyldimethyl ammonium halides allow to obtain 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.

Diallyldialkylammonium halides are widely used monomers in manufacturing water-soluble polymers.

The reaction used in the method for preparing diallyldialkylammonium halide follows the reaction diagram hereinafter, wherein the allyl halide is reacted with dialkylaminedimethylamine, in the presence of a base such as a metal hydroxide for example, as shown in the reaction below.

Ri are R2 are independently either CH ₃ or a carbon chain, preferably alkyl, comprising between 2 and 20 carbon atoms. Preferentially, Ri and R2 are CH ₃ groups. X is generally a Cl, Br or I atom, preferentially Cl. M is generally K or Na, preferentially Na.

The person skilled in the art knows that the reaction between allyl chloride and dimethylamine must be carried out in the presence of soda, in order to minimize the formation of allyl alcohol, as described in document US 4,670,594.

Allyl chloride is typically produced by chlorination of propylene as described in document EP 0 455 644. Propylene is a fossil-based olefin, and is currently produced by steam cracking of naphtha, itself derived from crude oil refining. More recently, and with the advent of shale gas production, various propane dehydrogenation methods to produce propylene have been described.

Fossil-based propylene contains various impurities, which remain or are transformed in the method for producing allyl chloride and thus diallyldimethyl ammonium chloride.

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

The impurities present in fossil-based allyl chloride and dimethylamine are present in the diallyldimethylammonium chloride monomer. They may even react during the manufacturing method of this monomer and thus generate new impurities, particularly where 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.

We can also mention that the presence of residual ammonia in dimethylamine will form triallyl methylammonium chloride. This trifunctional molecule will induce a branching and even a cross-linking of the water-soluble polymers incorporating diallyldimethylammonium chloride.

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 limitation effects, or by the presence of branched or cross-linked polymer.

The problem the invention proposes to resolve is to provide a new and improved method for producing diallyldialkylammonium halide.

Summary of the invention

Surprisingly, the applicant has observed that the use of allyl halide and dialkylamine, one of the two, preferentially both, being at least partially renewable and non-fossil, and preferentially totally renewable, in a method for obtaining diallyldialkylammonium halide, allows to substantially improve the method and the quality of the monomer obtained, thereby improving the polymerization and the application performance of the polymers.

The Applicant has particularly observed such improvement where the method is a method for obtaining diallyldialkylammonium halide by the so-called direct process that does not involve isolating the intermediate allyldialkylamine.

Without seeking to be bound by any particular theory, the Applicant raises the possibility that the different nature of the impurities between fossil-based allyl halide, and renewable and non fossil-based allyl halide, and/or between fossil-based dialkylamine, and renewable and non fossil dialkylamine is the cause of these unexpected technical effects.

First and foremost, the invention relates to a method for obtaining diallyldialkylammonium halide comprising the reaction between an allyl halide and dialkylamine, one of the two, preferentially both, being at least partially renewable and non-fossil.

The invention further relates to a diallyldialkylammonium halide monomer with a bio-sourced carbon content ranging between 5wt% and 100wt% relative to the total carbon weight in said monomer, the bio-sourced carbon content being measured according to ASTM D6866-21 Method B. The preferred monomers are bio-sourced diallyldimethylammonium halides, particularly bio-sourced diallyldimethylammonium chloride.

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

With the present invention, it is possible to achieve environmental objectives inherent in new technical innovations. In the present case, the use of renewable raw material, in this case allyl halide and dialkylamine, helps to significantly optimize the conversion method and the quality of the monomer obtained.

The Applicant has observed that when the dialkylamine is of bio-sourced origin, the amount of residual dialkylamine in the diallyldialkylammonium halide is greatly reduced.

The Applicant has observed that the dialkylamine of bio-sourced origin exhibits an improved reactivity with the allyl halide. As a result, the amount of side product allyl alcohol in the diallyldialkylammonium halide is also greatly reduced.

The Applicant has also observed that the amount of impurities decreases when the percentage of bio-sourced reagents (allyl halide and dialkylamine) increases.

The Applicant has also observed that when the allyl chloride is of bio-sourced origin, the amount of residual allyl alcohol in the diallyldialkylammonium halide is greatly reduced.

The Applicant has also observed that the allyl chloride of bio-sourced origin exhibits an improved reactivity with the dialkylamine. As a result, the amount of residual dialkylamine in the diallyldialkylammonium halide is also greatly reduced.

The Applicant has also observed that when the dialkylamine and the allyl chloride are of bio sourced origins there is a synergistic effect which makes it possible to more significantly reduce the quantities of residual dialkylamine and allyl alcohol in the diallyldialkylammonium halide.

The Applicant has also observed that when polymerizing diallyldialkylammonium halide monomers obtained from dialkylamine and/or allyl chloride, at least one of which is of renewable and non-fossil origin, polymers are obtained with a higher molecular weight than if the dialkylamine and allyl chloride are of fossil origin. Additionally, the resulting polymers exhibits improved coagulant properties as compared to polymers of fossil diallyldialkylammonium halide.

Detailed description of the invention

In the context of the invention, the terms “renewable and non-fossil” are used to designate the origin of a chemical compound derived from biomass or from synthesis gas (syngas), i.e. resulting from one or more chemical transformations carried out on one or more natural and non-fossil raw materials. The terms “bio-sourced” 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 stemming from the circular economy, which have been previously recycled, once or several times, in a biomass material recycling process, such as materials from polymer depolymerization or pyrolysis oil processing.

According to the invention, the “at least partially renewable and non-fossil” quality of a compound means a bio-sourced carbon content preferably between 5wt% and 100wt% relative to the total carbon weight of said compound.

In the context of the invention, the ASTM D6866-21 standard 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 weight percentage (wt%) of bio-sourced carbon relative to the total carbon weight in said compound.

The ASTM D6866-21 standard is a test method that teaches how to experimentally measure the bio-sourced carbon content of solids, liquids and gaseous samples by radiocarbon analysis.

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

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

The sample preparation method is described in the standard and does not require any special comment as it is a commonly used procedure.

Analysis, interpretation and reporting of results are described below. Isotope ratios of carbon- 14 to carbon- 12 content or carbon- 14 to carbon- 13 content are measured using AMS. Isotope ratios of carbon- 14 to carbon- 12 content or carbon- 14 to carbon- 13 content are determined relative to a standard traceable via the NIST SRM 4990C modem reference standard. The “fraction of modem” (fM) represents the amount of carbon- 14 in the tested product relative to the modem standard. It is most often referred to as percent modern carbon (pMC), the percentage equivalent to fM (e.g. fM 1 = 100 pMC). All pMC values obtained from radiocarbon analyses must be corrected for isotopic fractionation using a given stable isotope. The correction should be made using the carbon-14 to carbon-13 values determined directly using the AMS where possible. If this is not possible, the correction should be made using the delta 13C (513C) measured by IRMS, CRDS (Cavity Ring Down Spectroscopy) or any other equivalent technology that can provide accuracy to within plus or minus 0.3 per thousand.

“Zero pMC” represents the total absence of measurable 14C in a material above the 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 “modem” source.

The pMC may be higher than 100% due to the persistent, but diminishing, effects of 14C injection into the atmosphere caused by atmospheric nuclear testing programmes. The pMC values need to be adjusted by an atmospheric correction factor (REF) to obtain the actual bio sourced content of the sample.

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 had referenced a value of 107.5 pMC, while the later version ASTMD6866- 10 (2010) had referenced a value of 105 pMC. These data points represent a drop of 0.5 pMC per year. Consequently, on 2 January of each year, the values in Table 1 below were used as REF value until 2019, reflecting the same decrease of 0.5 pMC per year. The REF values (pMC) for 2020 and 2021 have been determined to be 100.0 based on continuous measurements in the Netherlands (Lutjewad, Groningen) until 2019. References for reporting carbon isotope ratio data are provided 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, FL, Noakes, J. E., and Spaulding, J. D., Eds., Lewis Publishers, Chelsea, MI, 1991, pp. 501-511. Allison, C. E., Francy, R. J., and Meijer, H. A. J., “Reference and Intercomparison Materials for Stable Isotopes of Light Elements”, International Atomic Energy Agency, Vienna, Austria, IAEATECHDOC- 825 , 1995.

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

Table 1: Reference of percentage of modern carbon (pMC) In the context of the invention, the term “segregated” means a material stream that is distinctive and distinguishable from other material streams in a value chain (e.g. in a product manufacturing method), and thus considered to belong to a set of materials having an equivalent nature, such that the same origin of the material, or its manufacture according to the same standard or norm, can be tracked and guaranteed throughout this value chain. For example, this may be the case of a chemist buying 100% bio-sourced dialkylamine exclusively from a single supplier who guarantees the 100% bio-sourced origin of the dialkylamine delivered, and said chemist processing this 100% bio-sourced dialkylamine separately from other potential dialkylamine sources to produce a chemical compound. If the chemical compound produced is made solely from said 100% bio-sourced dialkylamine, then the chemical compound is 100% bio-sourced.

In the context of the invention, the term “non-segregated”, in contrast to the term “segregated”, is understood to mean a material stream that cannot be differentiated from other material streams in a value chain.

In order to better understand this notion of segregation, it is useful to recall some basics about the circular economy and its practical application in methods, especially chemical transformation.

According to the French Environment and Energy Management Agency (ADEME), the circular economy can be defined as an economic system of trade and production which, at all stages of the life cycle of products (goods and services), seeks to increase efficiency in the use of resources and to reduce the environmental impact while developing the well-being of individuals. In other words, it is an economic system devoted to efficiency and sustainability that minimizes waste by optimizing value generated by resources. It relies heavily on a variety of conservation and recycling practices in order to break away from the current more linear “take-make-dispose” approach.

In the field of chemistry, which is the science of transforming one substance into another, this translates into reusing material that has already been used to make a product. Theoretically, all chemicals can be isolated and therefore recycled separately from other chemicals. The reality, particularly in industry, is more complex and means that even when isolated, the compound cannot often be differentiated from the same compound originating from another source, thus complicating the traceability of the recycled material.

For this reason, various traceability models have been developed taking into account this industrial reality, thereby allowing users in the chemical industry to manage their material streams with full knowledge of the facts, and allowing end customers to understand and know in a simple way the origin of the materials used to produce an object or a commodity.

These models have been developed to build 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 method, by knowing the proportion of a desired component (e.g. of a bio-sourced nature) in an object or commodity.

One such model is “segregation”, which we have defined earlier. Some known examples where this model applies are glass and some metals where it is possible to track material streams separately.

However, chemicals are often used in complex combinations, and separate cycles are very often difficult to implement, especially due to prohibitive costs and highly complex stream management, such that the “segregation” model is not always applicable.

Consequently, when it is not possible to differentiate between material streams, other models are applied, which are grouped together under the term “non-segregated” and which entail, for example, taking into account the proportion of a specific stream relative to other streams, without physically separating the streams. One example is the Mass Balance Approach.

The Mass Balance Approach involves accurately tracking the proportion of a category (e.g. “recycled”) relative to a whole in a production system in order to guarantee, on the basis of an auditable account ledger, a proportionate and appropriate allocation of the content of that category in a finished product. For example, this may be the case of a chemist buying 50% bio-sourced dialkylamine from a supplier who guarantees, according to the mass or weight balance approach, that in the dialkylamine delivered, 50% of the dialkylamine has a bio-sourced origin, and de facto 50% is not of bio-sourced origin, and the use by said chemist of this 50% bio-sourced dialkylamine with another stream of 0% bio-sourced dialkylamine, the two streams not being identifiable at some point during the production process, due to mixing for example. If the chemical compound produced is made from 50% bio-sourced 50% guaranteed dialkylamine, and 0% bio-sourced 50% dialkylamine, the chemical compound is 25% bio-sourced.

In order to guarantee the stated “bio-sourced” figures, for example, and to encourage the use of recycled raw materials in producing new products, a set of globally shared and standardised rules (ISCC+, ISO 14020) has been developed to reliably manage material streams.

In the context of the invention, the term “recycled” is understood to mean the origin of a chemical compound derived from a method for recycling a material considered as waste, i.e. resulting from one or more transformations carried out using at least one recycling method on at least one material generally considered as waste.

The term “water-soluble polymer” is understood to mean a polymer which gives a clear aqueous solution when dissolved by stirring at 25°C and with a concentration of 20 g.L ¹ in water.

Method according to the invention

The present invention relates to a method for obtaining diallyldialkylammonium halide comprising the reaction between an allyl halide and a dialkylamine, one of the two (allyl halide and dialkylamine), preferentially both, being at least partially renewable and non-fossil.

More specifically and preferentially, the compounds used to obtain the diallyldialkylammonium halide and containing the carbon atoms that will be found in the diallyldialkylammonium halide molecule are partially or totally renewable and non-fossil. These compounds are allyl halide and dialkylamine.

Allyl halide preferentially has a bio-sourced carbon content ranging between 5wt% and 100wt% relative to the total carbon weight in said allyl halide, the bio-sourced carbon content being measured according to ASTM D6866-21 Method B.

The dialkylamine preferentially has a bio-sourced carbon content ranging between 5wt% and 100wt% relative to the total carbon weight in said dialkylamine, the bio-sourced carbon content being measured according to ASTM D6866-21 Method B. In the whole invention, the bio-sourced carbon content of a compound for which it is specified that it is at least partially renewable and non-fossil, or for which the bio-sourced carbon content is specified, relative to the total carbon weight in said compound, ranges from 5wt% to 100wt%, and preferably from 10wt% to 100wt%, preferably from 15wt% to 100wt%, preferably from 20wt% to 100wt%, preferably from 25wt% to 100wt%, preferably from 30wt% to 100wt%, preferably from 35wt% to 100wt%, preferably from 40wt% to 100wt%, preferably from 45wt% to 100wt%, preferably from 50wt% to 100wt%, preferably from 55wt% to 100wt%, preferably from 60wt% to 100wt%, preferably from 65wt% to 100wt%, preferably from 70wt% to 100wt%, preferably from 75wt% to 100wt%, preferably from 80wt% to 100wt%, preferably from 85wt% to 100wt%, preferably from 90wt% to 100wt%, preferably from 95wt% to 100wt%, preferably from 97wt% to 100wt%, preferably from 99wt% to 100wt%, the bio sourced carbon content being measured according to ASTM D6866-21 Method B.

Preferentially, allyl halide has a bio-sourced carbon content ranging between 33.33wt% and 100wt%, preferably between 66.67% and 100%, more preferentially 100wt% relative to the total carbon weight in said allyl halide, the bio-sourced carbon content being measured according to ASTM D6866-21 Method B.

Preferentially, dialkylamine has a bio-sourced carbon content ranging between 50wt% and 100wt%, more preferentially 100wt% relative to the total carbon weight in said dialkylamine, the bio-sourced carbon content being measured according to ASTM D6866-21 Method B.

Preferably, the allyl halide is totally renewable and non-fossil. Preferably, the dialkylamine is totally renewable and non-fossil. Preferably, the allyl halide and the dialkylamine are totally renewable and non-fossil.

The allyl halide and/or dialkylamine may be non- segregated, partially segregated, or totally segregated, preferentially partially or totally segregated.

Where the allyl halide and/or the dialkylamine is/are totally renewable and non-fossil, it may be: a) Either totally recycled and a)l) Or totally segregated; a)2) Or partially segregated; a)3) Or non-segregated; b) Or partially of recycled origin and b)l) Or totally segregated; b)2) Or partially segregated; b)3) Or non-segregated; c) Or totally of non-recycled origin and c)l) Or totally segregated; c)2) Or partially segregated; c)3) Or non segregated.

In these various embodiments, where the (allyl halide and/or dialkylamine) compound is partially segregated, 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, or more preferably between 99:1 and 50:50.

Among these various embodiments, preference is given to the three a) embodiments, the three b) embodiments, and embodiment c)l). Among these embodiments, much greater preference is given to embodiments a)l), a)2), b)l), b)2) and c)l). The two most preferred embodiments are a)l) and b)l).

The industrial reality is such that it is not always possible to obtain industrial quantities of (allyl halide and/or dialkylamine) compound that are bio-sourced, totally recycled and/or segregated or highly recycled and segregated. Hence, the above preferences may be more difficult to implement at the moment. From a practical standpoint, embodiments a)3), b)3), and c) are currently implemented more easily and on a larger scale. With techniques evolving quickly towards the circular economy, there is no doubt that the already applicable preferred modes will soon be applicable on a very large scale.

Where the (allyl halide and/or dialkylamine) compound is partially renewable and non-fossil, a distinction is made between the renewable part (bio-sourced) and the non-bio-sourced part. Obviously, each can be according to the same embodiments a), b) and c) described hereinabove.

As concerns the bio-sourced part of the partially bio-sourced compound, the same preferences apply as in the case where the compound is fully bio-sourced.

However, as concerns the non-bio-sourced part of the partially bio-sourced compound, it is even more preferable to have as large a recycled component as possible for a circular economy approach. Hence, in this case, preference is given to embodiments a)l), a)2), b)l), b)2), particularly a)l) and b)l).

In the invention and in the various embodiments set forth below, the allyl halide is preferably obtained from propylene derived at least partially, preferentially totally from biomass, i.e., from renewable and non-fossil sources. The alkyl halide is preferentially obtained from propylene and a halogen compound such as Ck.

In the invention and in the various embodiments set forth below, the dialkylamine is preferentially obtained from methanol derived at least partially, preferentially totally from biomass, i.e., from renewable and non-fossil sources. Dialkylamine is preferentially obtained from methanol and ammonia.

With respect to the reaction between the allyl halide and a dialklymanine to form diallyldialkylammonium halide, the person skilled in the art may refer to the already established knowledge. Preferentially, the method for obtaining the diallyldialkylammonium halide is by the so-called direct process that involves not isolating the intermediate allyldialkylamine.

The allyl halide is preferentially an allyl chloride, but it can also be an allyl bromide or an allyl iodide.

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

The monomer obtained according to the method is preferentially diallyldimethylammonium chloride, but it can also be diallyldiethylammonium chloride, diallyldimethylammonium bromide, diallyldiisopropylammonium chloride, diallyldipropylammonium chloride, diallyldibutylammonium chloride, diallyldihexylammonium chloride.

The method is described hereinafter considering dimethylamine and allyl chloride, but the method can be generalized with a dialkylamine and an allyl halide. In a first step, dimethylamine, aqueous or anhydrous, is added into a reactor. In the case where dimethylamine anhydride is used, the person skilled in the art will know how to adjust the amount of water to be added to have a dimethylamine solution of, preferentially, 60wt%.

In a second step, allyl chloride is added continuously to the reactor for a time generally ranging between 1 and 24 hours, preferentially between 2 and 12 hours. Simultaneously, an aqueous sodium hydroxide solution, preferentially at 50wt% concentration, is added to the reactor, for a time preferentially ranging between 1 and 24 hours, more preferentially between 2 and 12 hours.

The molar ratio between dimethylamine, allyl chloride and sodium hydroxide generally ranges between 1:2:2 and 1:10:10, preferentially 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.

The reaction medium’s pH generally ranges between 6 and 12, preferentially 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 bar absolute and 10 bar absolute. The reaction temperature is generally between 10 and 120°C, preferably between 50 and 90°C. The reaction can be conducted in batch, semi-batch or continuous mode.

At the end of the reaction, the diallyldimethylammonium chloride is in aqueous solution in the presence of sodium chloride in suspended particulate form. The monomer product can be used as is (aqueous solution + particulate NaCl), or it can be filtered to separate the sodium chloride.

In a non-limiting manner, the filtration equipment can be a Nutsche filter, a filter press, a vertical or horizontal centrifuge, a rotary vacuum or pressure filter. The filtration can also be carried out in the reactor if the latter is equipped at the drain with a grid with a suitable mesh to retain the sodium chloride crystals.

Optionally, the aqueous solution of diallyldimethylammonium chloride can be purified. In a non-limiting manner, the purification can be performed by distillation, evaporation on a falling film type equipment, a thin film evaporator or in a reboiler, by addition of steam, at atmospheric pressure or under vacuum.

In a particular embodiment, the dialkylamine and/or allyl halide are partially or fully derived from a recycling method.

In this particular embodiment, the dialkylamine and/or allyl halide are obtained using a recycling process, such as from polymer depolymerization or by manufacturing from pyrolysis oil, the latter resulting from high-temperature, anaerobic combustion of used plastic waste. Thus, materials considered as waste can be used as a source to produce recycled compounds, which in turn can be used as raw material to manufacture the invention’s monomer. Since the monomer according to the invention is derived using a recycling method, the polymer according to the invention hereinafter described can cater to the virtuous circle of the circular economy.

Additionally, the method according to the invention preferentially comprises the following steps:

- Recycling at least one at least partially renewable and non-fossil raw material to obtain a dialkylamine and/or an allyl halide; - Reacting a dialkylamine and an allyl halide to obtain diallyldialkylammonium halide, the dialkylamine and/or allyl halide being derived partially or totally from recycling.

Monomer according to the invention

The invention further relates to a bio-sourced-diallyldialkylammonium halide with a bio sourced carbon content ranging between 5wt% and 100wt% relative to the total carbon weight in said monomer, the bio-sourced carbon content being measured according to ASTM D6866- 21 Method B. The same embodiments and preferences developed in the method section apply to this section of the monomer description.

The present invention equally relates to a bio-sourced-diallyldialkylammonium halide obtained by reaction between an allyl halide and a dialkylamine, said allyl halide and/or said dialkylamine being at least partially renewable and non-fossil.

The invention equally relates to a bio-sourced-diallyldialkylammonium halide obtained by reaction between an allyl halide and dialkylamine, said allyl halide and/or said dialkylamine having a bio-sourced carbon content of between 5 wt% and 100 wt% relative to the total carbon mass respectively in said allyl halide and/or said dialkylamine, the bio-sourced carbon content being measured according to ASTM D6866-21 Method B.

Preferably, the allyl halide is totally renewable and non-fossil. Preferably, the dialkylamine is totally renewable and non-fossil. Preferably, the allyl halide and the dialkylamine are totally renewable and non-fossil.

Bio-sourced-diallyldialkylammonium halide is understood to mean a diallyldialkylammonium halide that is at least partially, preferentially totally derived from biomass, i.e. being the result of one or more chemical transformations carried out on one or more raw materials having a natural source. The bio-sourced-diallyldialkylammonium halide may also be referred to as bio sourced or bio-resourced diallyldialkylammonium halide.

The allyl halide is preferentially an allyl chloride, but it can also be an allyl bromide or an allyl iodide.

The dialkylamine is preferentially dimethylamine, but can also be diethylamine, diisopropylamine, dipropylamine, dibutylamine, or dihexylamine.

The monomer according to the invention is preferentially bio-sourced- diallyldimethylammonium chloride, but it can also be bio-sourced-diallyldiethylammonium chloride, bio-sourced-diallyldimethylammonium bromide, bio-sourced- diallyldiisopropylammonium chloride, bio-sourced-diallyldipropylammonium chloride, bio- sourced-diallyldibutylammonium chloride, bio-sourced-diallyldihexylammonium chloride

The invention further relates to a bio-sourced-diallyldimethylammonium chloride with a bio sourced carbon content ranging between 5wt% and 100wt% relative to the total carbon weight in said monomer, the bio-sourced carbon content being measured according to ASTM D6866- 21 Method B.

The dialkylamine and/or the allyl halide may be non-segregated, partially segregated, or fully segregated. The preferences developed in the method section apply to this section describing the monomer.

In a particular embodiment, the dialkylamine and/or the allyl halide may be partially or totally recycled. The preferences developed in the method section apply to this section describing the monomer.

Polymer according to the invention

The invention relates to a polymer obtained by polymerization of at least one diallyldialkylammonium halide monomer obtained according to the method according to the invention. It also relates to a polymer obtained by polymerization of at least one diallyldialkylammonium halide monomer as previously described. The same embodiments and preferences developed in the “methods” section apply to this section describing the.

The polymer according to the invention is preferably water-soluble or water-swellable. The polymer may also be a superabsorbent.

The polymer according to the invention may be a homopolymer or a copolymer with at least one bio-sourced-diallyldialkylammonium halide monomer obtained according to the method according to the invention, or with at least one of the previously described bio-sourced- diallyldialkylammonium halide monomers, and with at least one different additional monomer, the latter advantageously being chosen from at least one nonionic 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 grouping.

Thus, the copolymer may comprise at least a second monomer different from the first monomer (diallyldialkylammonium halide according to the invention), this second monomer being chosen from nonionic monomers, anionic monomers, cationic monomers, zwitterionic monomers, monomers comprising a hydrophobic grouping, and mixtures thereof. The nonionic monomer is preferably selected from acrylamide, methacrylamide, N- isopropyl acrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, N- methylol acrylamide, N-vinylformamide (NVF), N-vinylacetamide, N-vinylpyridine and N- vinylpyrrolidone (NVP), N-vinyl imidazole, N-vinyl succinimide, acryloyl morpholine (ACMO), acryloyl chloride, glycidyl methacrylate, glyceryl methacrylate, and diacetone acrylamide.

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), vinylsulfonic acid, vinylphosphonic acid, allylsulfonic acid, methallylsulfonic acid, 2- sulfoethylmethacrylate, sulfopropylmethacrylate, sulfopropylacrylate, allylphosphonic acid, styrene sulfonic 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 a salt thereof), and/or ATBS (and/or a salt thereof).

The cationic monomer is preferably chosen from quaternized dimethyl aminoethyl acrylate (ADAME), quaternized dimethylaminoethyl methacrylate (MADAME), dimethyldiallylammonium chloride (DADMAC), acrylamido propyltrimethyl ammonium chloride (APTAC), and methacrylamido propyltrimethyl ammonium chloride (MAPTAC).

The zwitterionic monomer can be a derivative of a vinyl-type unit, particularly acrylamide, acrylic, allylic 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.

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

Each of these monomers may also be bio-sourced. According to the invention, the polymer may have a linear, branched, star, comb, dendritic or block structure. These structures can be obtained by selecting the initiator, the transfer agent, the polymerization technique such as controlled radical polymerization referred to as RAFT (reversible addition-fragmentation chain transfer), NMP (Nitroxide Mediated Polymerization) or ATRP (Atom Transfer Radical Polymerization), incorporation of structural monomers, the concentration...

According to the invention, the polymer is advantageously linear and structured. A structured polymer refers to a non-linear polymer with side chains so as to obtain, when this polymer is dissolved in water, a pronounced state of entanglement leading to very substantial low gradient viscosities. The invention’s polymer may also be cross-linked.

Additionally, the polymer according to the invention polymer may be structured:

- By at least one structuring agent, which may be chosen from the group comprising polyethylenically unsaturated monomers (having at least two unsaturated functions), such as vinyl functions for example, particularly allyl, acrylic and epoxy functions, and one may mention, for example, methylene bis acrylamide (MBA), triallyamine, or tetraallylammonium chloride or 1,2 dihydroxy ethylene bis-(N-acrylamide), and/or

- By macroinitiators, such as polyperoxides, polyazoids and polytransfer agents, such as polymeric (co)polymers, and polyols, and/or

- Functionalized polysaccharides.

The amount of branching/cross-linking agent in the monomer mixture is advantageously less than 4wt% 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 0.00001wt% relative to the monomer content.

In a particular embodiment, the polymer according to the invention may be a semi -synthetic and thus semi-natural polymer. In this embodiment, the polymer may be synthesized by copolymerization by total or partial grafting of at least one monomer according to the invention, and at least one natural compound, said natural compound being preferably chosen from starches and their derivatives, polysaccharides and their derivatives, fibers, vegetable gums, animal gums or algal gums, and modified versions thereof. For example, vegetable gums can include guar gum, gum arabic, locust bean gum, gum tragacanth, guanidinium gum, cyanine gum, tara gum, cassia gum, xanthan gum, ghatti gum, karaya gum, gellan gum, cyamopsis tetragonoloba gum, soy gum, or beta-glucan or dammar. The natural compound can also be gelatin, casein, or chitosan. For example, algal gum can include sodium alginate or its acid, agar-agar, or carrageenan.

Polymerization is generally carried out, without this being limiting, by copolymerization or by grafting. The person skilled in the art will be able to refer to current general knowledge in the field of semi-natural polymers.

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 previously described natural polymers. The weight ratio between the synthetic polymer and the natural polymer is generally between 90:10 and 10:90. The composition may be in liquid, inverse emulsion or powder form.

In general, the polymer does not require development of a particular polymerization method. Indeed, it can be obtained according to all the polymerization techniques well known to the person skilled in the art. In particular, it can be solution polymerization; gel polymerization; precipitation polymerization; emulsion polymerization (aqueous or inverse); suspension polymerization; reactive extrusion polymerization; water-in-water polymerization; or micellar polymerization.

Polymerization is generally free radical polymerization preferably by inverse emulsion polymerization or gel polymerization. Free radical polymerization includes free radical polymerization using UV, azo, redox or thermal initiators as well as controlled radical polymerization (CRP) techniques or matrix polymerization techniques..

The polymer according to the invention can be modified after it being obtained by polymerization. This is known 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 polymers obtained after said post-modifications. Among the possible post modifications developed hereinafter, mention may be made of post-hydrolysis, post modification by Mannich reaction, post-modification by Hoffman reaction and post modification by glyoxalation reaction.

The polymer according to the invention can be obtained by performing a post-hydrolysis reaction on a polymer obtained by polymerization of at least one monomer obtained by the method according to the invention or at least one monomer as previously described in the “Monomer” section. Prior to post-hydrolysis, the polymer comprises acrylamide or methacrylamide monomer units, for example. The polymer may also further comprise monomeric units of N-Vinylformamide. More specifically, post-hydrolysis involves 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 acid compound. Preferably, the hydrolysis agent is a B runs ted base. Where the polymer comprises amide and/or ester monomer units, the post-hydrolysis reaction produces carboxylate groups. Where the polymer comprises vinylformamide monomer units, the post-hydrolysis reaction produces amine groups.

The polymer according to the invention can be obtained by performing a Mannich reaction on a polymer obtained by polymerization of at least one monomer obtained by the method according to the invention or at least one monomer as previously described in the “Monomer” section. More specifically, prior to the Mannich reaction, the polymer advantageously comprises acrylamide and/or methacrylamide monomer units. The Mannich reaction is performed 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.

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

Discovered by Hofmann at the end of the nineteenth century, this reaction is used to convert an amide function into a primary amine function with one carbon atom less. The detailed reaction mechanism is presented below.

In the presence of a Bronsted base (e.g., soda), a proton is extracted from the amide.

The amidate ion formed then reacts with the active chlorine (Ch) of the hypochlorite (e.g. NaCIO which is in equilibrium: 2 NaOH + Ck ^ NaCIO + NaCl + H2O) to produce an N- chloramide. The Bronsted base (e.g. NaOH) extracts a proton from the chloramide to form an anion. The anion loses a chloride ion to form a nitrene which undergoes isocyanate rearrangement.

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

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

H

R— N— C0 ₂ - R— NH ₂

-eo ₂

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).

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 method 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 monomer unit advantageously of acrylamide or methacrylamide. More specifically, the glyoxalation reaction involves a reaction of at least one aldehyde on the polymer, thus allowing said polymer to be functionalized. 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.

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 fluid bed drying.

According to the invention, the water-soluble polymer preferably has a molecular weight between 1000 and 40 million g/mol. The polymer may be a dispersant, in which case its molecular weight is preferably between 1000 and 50,000 g/mol. The polymer may have a higher molecular weight, typically 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 from 10 to 500 times its weight in water.

The molecular weight is advantageously determined by the intrinsic viscosity of the (co)polymer. The intrinsic viscosity can be measured by methods known to the person skilled in the art and can be calculated from the reduced viscosity values for different (co)polymer concentrations by a graphical method entailing plotting the reduced viscosity values (y-axis) against the concentration (x-axis) and extrapolating the curve down 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 using the Mark-Houwink equation:

[h] = K M“

[h] 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 specific (co)polymer-solvent system.

The co-monomers combined with the monomer according to the invention to obtain the polymer of the invention, are preferably at least partially, or more preferably totally renewable and non-fossil.

Thus, in a preferred embodiment, the invention relates to a polymer comprising:

- at least 5 mol%, preferably at least 10 mol%, preferably between 20 mol% and 99 mol%, more preferably between 30 mol% and 90 mol% of a first monomer, said monomer being a monomer according to the invention, and

- at least 1 mol%, preferably between 5 mol% and 90 mol%, more preferably between 10 mol% 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 partially renewable and non-fossil.

Thus, in a preferred embodiment, the invention relates to a polymer comprising:

- at least 5 mol%, preferably at least 10 mol%, preferably between 20 mol% and 99 mol%, more preferably between 30 mol% and 90 mol% of a first monomer, said monomer being a monomer according to the invention; and

- at least 1 mol%, preferably between 5 mol% and 90 mol%, more preferably between 10 mol% 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 partially renewable and non-fossil;

- at least 1 mol%, preferably between 5 mol% and 90 mol%, more preferably between 10 mol% and 80 mol% of at least one third monomer comprising an ethylenic unsaturation, said third monomer being different from the first and the second monomers, and being at least partially renewable and non-fossil.

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

In a preferred embodiment, the second and the possible other monomers have a bio-sourced carbon content ranging between 5wt% and 100wt%, preferably 10wt% and 100wt%, relative to the total carbon weight in the related monomer, the bio-sourced carbon content being measured according to ASTM D6866-21 Method B.

In this preferred embodiment, the second and the possible other monomers are preferably chosen from acrylamide, (meth)acrylic acid and/or one of the salts, an oligomer of acrylic acid, 2-acrylamido-2-methylpropane sulfonic acid (ATBS) and/or a salt thereof, N-vinylformamide (NVF), N-vinylpyrrolidone (NVP), dimethylaminoethyl (meth)acrylate and quatemized versions thereof, a substituted acrylamide having the formula CH2=CHCO-NR ¹ R ² , R ¹ and R ² being, independently of each other, a linear or branched carbon chain C _n Th _n+i , wherein n is between 1 and 10.

In the whole invention, it will be understood that the molar percentage of the monomers (excluding any cross-linking agents) of the polymer is equal to 100%.

Preferably, the polymer according to the invention comprises a bio-sourced carbon content ranging between 5wt% and 100wt% relative to the total carbon weight in said polymer, the bio sourced carbon content being measured according to ASTM D6866-21 Method B.

The invention equally relates to a polymer obtained according to a method comprising the following steps:

- Recycling at least one material that is at least partially renewable and non-fossil, or a fossil material, to obtain the allyl halide and/or dialkylamine;

- Reacting the allyl halide and the dialkylamine thus obtained in order to obtain diallyldialkylammonium halide; - Polymerize said diallyldialkylammonium halide thus obtained, optionally with at least one second monomer comprising at least an ethylenic unsaturation to obtain a polymer.

The dialkylamine and/or the allyl halide may be non-segregated, partially segregated, or fully segregated. The preferences developed in the method section apply to this section describing the polymer.

In a particular embodiment, the dialkylamine and/or the allyl halide may be partially or totally recycled. The preferences developed in the method section apply to this section describing the polymer.

The invention also relates to the use of at least one monomer obtained by the method according to the invention in order to synthesize a polymer.

Using the polymer according to the invention

The invention also relates to the use of the polymer according to the invention in the recovery of hydrocarbons (oil and/or gas); in drilling and cementing of wells; in the stimulation of hydrocarbon wells (oil and/or gas), for example hydraulic fracturing, conformation, diversion; in the treatment of water in open, closed or semi-closed circuits; in the treatment of fermentation slurry, treatment of sludge; in paper manufacturing; in construction; in wood processing; in hydraulic composition processing (concrete, cement, mortar and aggregates); in the mining industry; in the formulation of cosmetic products; in the formulation of detergents; in textile manufacturing; in battery component manufacturing; in geothermal energy; in sanitary napkin manufacturing; or in agriculture.

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, absorbing agent, friction reducing agent, dewatering agent, draining agent, charge retention agent, dehydrating agent, conditioning agent, stabilizing agent, film forming agent, sizing agent, superplasticizing agent, clay inhibitor or dispersant.

Method using the polymer according to the invention

The present invention also relates to the various methods described hereinafter, wherein the polymers of the invention are used to improve application performance.

The invention also relates to a method for enhanced oil or gas recovery by sweeping a subterranean 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 a subterranean formation, c. Sweeping the subterranean formation with the injected fluid, d. Recovering an aqueous mixture of oil and/or gas.

The invention also relates to a method for hydraulic fracturing of subterranean oil and/or gas reservoirs comprising the following steps: a. Preparing an injection fluid from a polymer according to the invention, with water or brine, and with at least one proppant, b. Injecting said fluid into the subterranean reservoir and fracturing at least a portion thereof to recover oil and/or gas.

In the methods described hereinabove, 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 a powder, an inverse emulsion, a partially dehydrated inverse emulsion, or in the form of a “clear”, i.e. a dispersion of solid polymer particles in an aqueous or oily fluid. The powder form is preferably obtained by gel or spray drying of an inverse emulsion. It also involves a composition comprising an inverse emulsion of a polymer according to the invention and solid particles of a polymer according to the invention.

The invention also relates to a method of stimulation of a subterranean 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 a subterranean formation, c. Partially or totally plugging the subterranean formation with the injected fluid, said plugging being temporary or permanent.

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

Drilling and cementing a well are two successive steps in creating a well in a subterranean formation. The first step is drilling with the drilling fluid, while the second step is cementing the well with the cementing fluid. The invention also relates to a method of injecting an intermediate fluid (“spacer fluid”) injected between the drilling fluid and the cementing fluid, said intermediate fluid comprising at least one polymer according to the invention. This intermediate fluid prevents contamination between the cementing fluid and the drilling fluid.

When drilling and cementing a well, the polymer according to the invention can be used as a fluid loss additive in well cement compositions in order to reduce fluid loss from the cement compositions to permeable formations or zones into or through which the cement compositions are pumped. In primary cementing, loss of fluid, i.e., water, to permeable formations or subterranean zones can lead to premature gelling of the cement composition, so that bridging the annular space 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 ring.

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

Clays can absorb water and cause poor performance of building materials. When the polymer of the invention is used as a clay inhibitor, it allows in particular to avoid the clay swelling which may cause cracks thus weakening any building.

The hydraulic composition may be a concrete, cement, mortar or 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.

In this method of inerting clays, clays include, but are not limited to, 2:1 swelling clays (such as smectite), or 1:1 swelling clays (such as kaolin) or 2:1:1 swelling clays (such as chlorite). The term “clay” generally refers to magnesium and/or aluminum silicate, including phyllo silicates with a lamellar structure. However, in the present invention, the term “clay” also includes clays having no such structure, such as amorphous clays.

The invention also relates to a method for manufacturing a sheet of paper, cardboard or the like, whereby, before a sheet is formed, a step is performed entailing adding to a suspension of fibers, at one or more injection points, at least one polymer according to the invention. The polymer may provide dry strength or retention properties or wet strength. It may also improve paper formation, drainage and dewatering capabilities.

The method can be used successfully to manufacture packaging papers and cardboards, coating papers, sanitary and household papers, any type of paper, cardboard or the like. The post-modified polymers described in the “Polymers” section, in particular the post- modified polymers by Hoffman reaction or by glyoxalation reaction, are particularly advantageous in methods for manufacturing paper, cardboard or the like.

Retention properties are understood to mean the capability to retain the suspended materials of the paper pulp (fibers, fines, fillers (calcium carbonate, titanium oxide), ...) on the forming fabric, thus in the fibrous mat that will make up the final sheet. The mode of action of the retention agents is based on the flocculation of these suspended materials in water. Indeed, the floes formed are more easily retained on the forming sheet.

The retention of fillers involves retaining specifically the fillers (small mineral species with little affinity with cellulose). Substantial improvement of retention of fillers leads to a clarification of white water by retaining the fillers in the sheet and by increasing its grammage. It also gives the possibility to replace part of the fibers (the most expensive species in the composition of paper, cardboard or similar) with fillers (lower costs) in order to reduce manufacturing costs.

As concerns dewatering (or drainage) properties, it 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, in particular during manufacturing of the sheet.

These two properties (retention and drainage) being intricately linked, one depending on the other, the issue is therefore to find the best compromise between retention and drainage. Generally, the person skilled in the art refers to a retention and drainage agent because these are the same types of products used to improve these two properties.

Fibrous suspension is understood to mean thick pulp or diluted pulp which are composed of water and cellulose fibers. The thick stock, with a dry matter concentration of more than 1% or even more than 3%, is located upstream of the fan pump. The thin stock, with a dry mass concentration of generally less than 1%, is located downstream of the fan pump.

The polymer can be added to the thick stock or to the thin stock. It can be added at the level of the fan pump or the headbox. Preferably, the polymer is added before the headbox.

In the method for making paper, cardboard or the like according to the invention, the polymer according to the invention may be used alone or in combination with a secondary retention agent. Preferably, a secondary retention agent selected from organic polymers and/or inorganic microparticles is added to the fiber suspension. 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, cross-linked, hydrophobic, associative and/or inorganic microparticles (such as bentonite, colloidal silica).

The invention also relates to a method for treating a suspension of solid particles in water resulting from mining or oil sands operations, comprising contacting said suspension with at least one polymer according to the invention. Such a method can be carried out in a thickener, which is a holding zone, generally in the form of a tube section of several meters in diameter with a conical bottom wherein the particles can settle. 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.

According to another embodiment, the polymer is added to a thickener that already contains the suspension to be treated. In a typical mineral processing operation, the suspensions are often concentrated in a thickener. This results in a higher density sludge that exits the bottom of the thickener, and an aqueous fluid released from the treated suspension (called liquor) that exits by overflow, from the top of the thickener. Generally, the addition of the polymer increases the concentration of the sludge and increases the clarity of the liquor.

According to another embodiment, the polymer is added to the particulate suspension during transport of said suspension to a deposition area. Preferably, the polymer is added in the pipe that conveys said suspension to a deposition zone. It is on this deposition area that the treated suspension is spread in preparation for dewatering and solidification. The deposition areas can be either open, such as an unconfmed area of soil, or enclosed, such as a basin, cell.

An example of such treatments during transport of the suspension is spreading the suspension treated with the polymer according to the invention on the soil in preparation for dewatering and solidification and then spreading a second layer of treated suspension on top of the solidified first layer. Another example is the continuous spreading of the suspension treated with the polymer according to the invention in such a way that the treated suspension falls continuously on the suspension previously discharged in the deposition area, thus forming a mass of treated material from which water is extracted.

According to another embodiment, the water-soluble polymer is added to the suspension and a mechanical treatment is performed, such as centrifugation, pressing or filtration. The water-soluble polymer can be added simultaneously in different stages of the suspension treatment, i.e., for example, in the pipe carrying the suspension to a thickener and in the sludge exiting the thickener which will be conveyed either to a deposition area or to a mechanical treatment device.

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. Generally, this treatment is enhanced by chemicals such as coagulants and flocculants. These are usually added to the water stream ahead of the separation unit, such as flotation and sedimentation.

The polymers according to the invention can be advantageously used to coagulate or flocculate suspended particles in municipal or industrial wastewater. Generally, they are used in combination with inorganic coagulants such as alum.

They can also be used advantageously to treat the sludge produced from the treatment of this wastewater. Sewage sludge (be it urban or industrial) is the main waste produced by a treatment plant from liquid effluents. Generally, sludge treatment involves dewatering it. This dewatering can be performed by centrifugation, filter press, belt press, electro-dewatering, sludge drying reed beds, solar drying. It is used to decrease sludge water concentration.

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

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 manufacturing said compositions as a thickening (agent), conditioning (agent), stabilizing (agent), emulsifying (agent), fixing (agent) or film-forming agent. The invention equally relates to cosmetic, dermatological or pharmaceutical compositions comprising at least one polymer according to the invention. In particular, reference may be made to application FR2979821 on behalf of L'OREAL for the manufacture of such compositions and description of the other ingredients of such compositions. The said compositions may be in the form of a milk, a lotion, a gel, a cream, a gel cream, a soap, a bubble bath, a balm, a shampoo or a conditioner. The use of said compositions for the cosmetic or dermatological treatment of keratinous 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 application of the composition to the keratinous materials, possibly followed by rinsing with water.

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

“Detergent compositions for household or industrial use” are understood to mean compositions for cleaning various surfaces, particularly textile fibers, hard surfaces of any kind such as dishes, floors, windows, wood, metal or composite surfaces. Such compositions include, for example, detergents for washing clothes manually or in a washing machine, products for cleaning dishes manually or for dishwashers, detergent products for washing house interiors such as kitchen elements, toilets, furnishings, floors, windows, and other cleaning products for universal use.

The polymer used as an additive, e.g., thickener, for a cosmetic, dermatological, pharmaceutical, or detergent composition is preferably cross-linked. It is preferably in the form of a powder, an inverse emulsion or a partially dehydrated inverse emulsion. The powder form is preferably obtained by spray drying from an inverse emulsion.

The invention equally relates to a thickener for pigment composition used in textile printing, said thickener comprising at least one polymer according to the invention. The invention also relates to a textile fiber sizing agent, said agent comprising at least one polymer according to the invention. The invention also relates to a process for manufacturing superabsorbent from the monomer according to the invention, a superabsorbent obtained from at least one monomer according to the invention, said superabsorbent to be used for absorbing and retaining water in agricultural applications or for absorbing aqueous liquids in sanitary napkins. For example, the superabsorbent agent is a polymer according to the invention.

The invention also relates to a method for manufacturing sanitary napkins wherein a polymer according to the invention is used, for example as a superabsorbent agent.

The invention also relates to the use of the polymer according to the invention as a battery binder. The invention also relates to a battery binder composition 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 making a gel comprising at least one polymer according to the invention and filling same into said battery. Mention may be made of lithium ion batteries which are used in a variety of products, including medical devices, electric cars, aircraft and, most importantly, consumer products such as laptops, cell phones and cameras.

Generally, lithium ion batteries (LIBs) include 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 solvent to form a paste or sludge 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 stacked and wound before being housed in a pressurized case containing an electrolyte material, all of which together form a lithium-ion battery.

In a lithium battery, the binder plays several important roles in both mechanical and electrochemical performance. Firstly, it helps disperse the other components in the solvent during the manufacturing process (some also act as a thickener), thus allowing for even distribution. Secondly, it holds the various components together, including the active components, any conductive additives, and the current collector, ensuring that all of these parts stay 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 a material impact on electronic or ionic conductivity. Thirdly, 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 ion transfer across this interface. Another important point is that the binders must have a certain degree of flexibility so that they do not crack or develop defects. Brittleness can create problems during manufacturing or assembly of the battery.

Given all the roles it plays in an electrode (and in the battery as a whole), choosing a binder is critical in ensuring good battery performance.

The invention also relates to a method for manufacturing sanitary napkins wherein a polymer according to the invention is used, for example as a superabsorbent agent.

As previously described, the circular economy is an economic system devoted to efficiency and sustainability that minimizes waste by optimizing value generated by resources. It relies heavily on a variety of conservation and recycling practices in order to break away from the current more linear “take-make-dispose” approach.

Therefore, with material recycling being a major and growing concern, recycling processes are developing rapidly and enabling the production of materials that can be used to produce new compounds or objects. Recycling materials does not depend on the origin of the material and as long as it can be recycled, it is considered as a technical progress. Although the origin of the material to be recycled may be renewable and non-fossil, it may also be fossil.

Specific objects are described hereinafter.

A first specific object relates to a method for obtaining diallyldialkylammonium halide comprising the reaction between an allyl halide and dialkylamine characterized in that one of the two, preferentially both, is (are) derived at least partially, preferentially totally, from a recycling process of a renewable and non-fossil material, or from a fossil material

Preferentially, the allyl halide and the dialkylamine are totally renewable and non-fossil, then they are preferentially totally “segregated”, i.e. derived from a separate pipeline and processed separately. In an alternative embodiment, they are partially “segregated” and partially “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, or more preferably between 99:1 and 50:50. In an alternative embodiment, it is totally “segregated”.

A second specific object relates to a diallyldialkylammonium halide obtained by reaction between an allyl halide and dialkylamine, said allyl halide being derived at least partially, preferentially totally from a recycling process of a renewable and non-fossil material, or a fossil material, and/or preferentially and, said dialkylamine being derived at least partially, preferentially totally from a recycling process of a renewal and non-fossil material, or a fossil material.

A third specific object relates to a diallyldialkylammonium halide obtained by reaction between an allyl halide and dialkylamine, said allyl halide being derived at least partially, preferentially totally from a recycling process of a renewable and non-fossil material, or a fossil material, and/or preferentially and, said dialkylamine being derived at least partially, preferentially totally from a recycling process of a renewal and non-fossil material, or a fossil material.

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

A fifth specific object relates to the use of a polymer obtained by polymerization of at least one diallyldialkylammonium halide as just previously described, in the oil and/or gas recovery, in 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 circuits, in the treatment of fermentation slurry, treatment of sludge, in paper manufacturing, in construction, in wood processing, in hydraulic composition processing (concrete, cement, mortar and aggregates), in the mining industry, in the formulation of cosmetic products, in the formulation of detergents, in textile manufacturing, in battery component manufacturing; in geothermal energy; or in agriculture.

A sixth specific object relates to the use of a polymer obtained by polymerization of at least one diallyldialkylammonium halide as just previously described as a flocculant, coagulant, binding agent, fixing agent, viscosity reducing agent, thickening agent, absorbing agent, friction reducing agent, dewatering agent, draining agent, charge retention agent, dehydrating agent, conditioning agent, stabilizing agent, film forming agent, sizing agent, superplasticizing agent, clay inhibitor or dispersant.

A seventh specific object relates to a polymer obtained according to a method comprising the following steps:

- Recycling at least one material that is at least partially renewable and non-fossil, or a fossil material, to obtain the allyl halide and/or dialkylamine;

- Reacting the allyl halide and the dialkylamine thus obtained in order to obtain diallyldialkylammonium halide; - Polymerize said diallyldialkylammonium halide thus obtained, optionally with at least one second monomer comprising at least an ethylenic unsaturation to obtain a polymer.

Said allyl halide and/or dialkylamine being preferentially totally “segregated”, i.e. derived from a separate pipeline and treated separately.

In an alternative embodiment, they are partially “segregated” and partially “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, or more preferably between 99:1 and 50:50. In an alternative embodiment, it is totally “segregated”

Examples:

Abbreviations list:

- DMA: Dimethylamine;

- AC: Allyl chloride;

- DADMAC: Diallyldimethylammonium chloride;

- AOH: Allyl alcohol.

The purity of diallyldimethylammonium chloride is indicated by the amounts of dimethylamine and allyl alcohol present in the product.

Description of the method for the detection of dimethylamine in gas chromatography

The measurement of the amount of dimethylamine is carried out by gas chromatography with a flame ionization detector.

The different compounds present in the sample are identified by their retention time in the capillary column, they are represented by peaks. Their concentration is calculated from the peak area ratios using a calibration made from external standard calibrators.

The retention time of dimethylamine is 1.35 minutes.

The sample of diallyldimethylammonium chloride undergoes a preliminary treatment with 1,4 dioxane in a 1 : 1 mixture by weight, previously treated with sodium hydroxide in order to obtain a solution with a pH>7. The supernatant organic phase is then injected into the equipment.

The capillary column has a length of 20 meters, a diameter of 0.18mm and a stationary phase thickness of 0.18pm (Agilent reference DB-5).

The analysis conditions are as follows:

- Temperature of injector: 180° C - Oven temperature: 40°C for 2 minutes, followed by a ramp of 15°C per minute to 110°C, then a ramp of 25°C per minute to 190°C

- Temperature of detector: 225°C

- Detection gas flow: 40ml/min of hydrogen and 390ml/min of air

- Carrier gas flow: 0.6 ml/min of helium

- Injection volume: 1 mΐ in split ratio 1 ml/min (injected product flow rate: 100 ml/min (capillary column flow rate)

- Analysis time: 10 min

Description ot the method ot analysis ot allyl alcohol in liquid chromatography

The measurement of the amount of allyl alcohol is carried out by liquid phase chromatography. The different products are identified by their retention time in the column represented by peaks.

The HPLC column used to perform the analyzes is filled with Cl 8 silica with a carbon content of 16%. It has a diameter of 4.6mm, a length of 250mm, and contains particles having a size of lOpm.

The analysis conditions are as follows:

- Mobile phase: 20wt% water + 80wt% methanol.

- Injection volume: 50 pL.

- Injection flow rate: lml/min.

- Detection wavelength: 200nm.

- Analysis time: 45 minutes.

The retention time of allyl alcohol is 5.08 minutes.

The quantification of the amount of allyl alcohol is carried out with a calibration made from external standard standards.

Preparation of DADMAC monomers

• Example 1:

1066g of demineralized water and 480g of anhydrous dimethylamine are added to a 5L Parr- type pressure reactor equipped with a double jacket, a stirrer and a pH meter.

The reaction medium is heated by a heating unit supplying the reactor jacket until a temperature of 80°C is reached. The reactor pressure naturally rises to a value of 4.1 bar absolute. 1587g of allyl chloride is added to the Parr reactor over 90 minutes. Simultaneously, 830g of 50% soda is added for the same duration. The reaction is exothermic, the reactor is cooled by the jacket, so as to maintain a temperature of 80° C in the reaction medium.

At the end of the 90 minutes of addition of allyl chloride and 50% soda, the reactor is de-gassed until atmospheric pressure is reached. The reactor is then maintained at 50° C, and placed under a vacuum of 100 mbar. Water is evaporated until a distillate weight of 944g is reached.

The reaction medium is then cooled to 30° C and returned to atmospheric pressure. Sodium chloride is present in the reaction medium, and the latter is filtered through a Nutsch filter maintained under vacuum. 600g of salt are thus filtered, and 2405g of filtrate is recovered, the latter containing approximately 67wt% of diallyl dimethylammonium chloride.

• Example 2-7

The protocol of example 1 is reproduced by adjusting the origin of the dimethylamine and its percentage of carbon 14 in order to carry out examples 2-7 (Inv2 to Inv 7) which are summarized in table 2. Dimethylamine of non-fossil origin can be derived from bio-sourced-methanol produced from the treatment of municipal waste, biomass, by fermentation or from the recycling of carbon dioxide.

Alternatively, the amino moiety of dimethylamine can also be derived from green ammonia.

The carbon 14 level in the different dimethylamines is measured according to ASTM D6866- 21 method B.

Diallyldimethylammonium chloride is analyzed for the amount of allyl alcohol and residual dimethylamine.

Table 2

From Table 2, it can be seen that when the DMA is of bio-sourced origin, the amount of residual DMA in DADMAC is greatly reduced. A second unexpected advantage is a better reactivity of the DMA with the allyl chloride making it possible to have a residual quantity of the latter which is also lower.

The higher the weight of carbon-14 in the DMA, the lower the amount of impurity.

• Examples 8 to 14

The example 1 protocol is reproduced by adjusting the origin of the allyl chloride and its percentage of carbon 14 in order to carry out examples 8-14 (Inv 8 to Inv 14) which are summarized in Table 3.

The allyl chloride of non-fossil origin can come from the treatment of residues from the paper pulp industry (“tall oil”) in order to form the bio-sourced-propylene precursor before the chlorination process. Alternatively, it may come from processing of vegetable oil according to patent WO 2014/111598 or recycling cooking oil.

The carbon 14 level in the various allyl chlorides is measured according to ASTM D6866-21 method B.

Table 3

From Table 3, it can be seen that when the allyl chloride is of bio-sourced origin, the amount of residual allyl alcohol in the DADMAC is greatly reduced. A second unexpected advantage is better reactivity with dimethylamine, making it possible to have a residual quantity of the latter which is also lower.

The higher the weight of carbon-14 in the allyl chloride, the lower the amount of impurity.

• Examples 15 to 21

The example 1 protocol is reproduced by adjusting the origin of the allyl chloride and the dimethylamine and their percentage of carbon 14 to carry out examples 15-21 (Inv 15 to Inv 21) which are summarized in Table 4.

Table 4

From table 4, it can be seen that when the DMA and the AC are of bio-sourced origins there is a synergistic effect which makes it possible to more significantly reduce the quantities of residual DMA and allyl alcohol in the DADMAC.

Preparation of polymers

• Examples 22 to 27

Thirty g of demineralized water and 316 g of DADMAC are added to a 1000 mL jacketed reactor, equipped with a stirrer and a condenser, according to Table 5. The solution thus obtained is heated to a temperature of 90°C. A persulfate solution is prepared by dissolving 2.5g of sodium persulfate in 250g of water. The persulfate solution thus prepared is added to the polymerization reactor at a flow rate of 50 ml/hour for 60 minutes, followed by a flow rate of 100 g/h for 120 minutes.

The polymerization reaction is carried out under reflux. After the addition of the sodium persulfate solution, the reaction medium is maintained at 90° C for 30 minutes. The viscous solution obtained is then cooled to room temperature The molecular weight of the polymers thus obtained are measured. The weight-average molecular weight of the polymer according to the invention is advantageously determined by the intrinsic viscosity of the 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 polymer concentrations by a graphical method consisting of noting the reduced viscosity values (ordinate axis) on the concentration (x-axis) and of extrapolating the curve to zero concentration. The intrinsic viscosity value is plotted on the ordinate axis or using the least squares method.

The molecular weight can then be determined by the Mark-Houwink equation: [h] = K Ma in which

[h] represents the intrinsic viscosity of the polymer determined by the solution viscosity measurement method,

K represents an empirical constant, M represents the molecular weight of the polymer, a represents the Mark-Houwink coefficient,

K and a depend on the particular polymer-solvent system.

Table 5 From Table 5, it can be seen that, when polymerizing DADMAC monomers obtained from DMA and/or AC, at least one of which is of renewable and non-fossil origin, polymers are obtained with a higher molecular weight than if the DMA and AC are of fossil origin.

Application testing

• Example 28 Polymers (Inv 22 to Inv 27), as well as that from counter-example 4, are respectively dissolved in tap water in order to obtain aqueous solutions 1 to 7, having a concentration of 0.1 wt% of the polymer relative to the total weight of the solution.

The solutions are stirred mechanically at 200 rev/min until the complete solubilization of the polymers and the obtaining of clear and homogeneous solutions.

A series of coagulation tests is carried out on an aqueous effluent containing 1 g/L of Kaolin, 1 g/L of calcium chloride and 10 g/L of crushed ores.

The tests are carried out in Jar Manual test according to the following protocol:

- Filling of the tubes with the effluent; - Injection of a polymeric solution at different dosages;

- Performing 5 reversals of the Jar Test for mixing the aqueous polymer solution in the suspension of the effluent.

The results are summarized in Table 6 and recapitulate the turbidity of the supernatant according to the dosage of polymer implemented with respect to the quantity of effluent.

Table 6

From Table 6, it can be seen that the polymers obtained according to the invention offer better coagulation performance.