Process for obtaining bio-sourced monomers from renewable dimethylaminoethanol

Abstract

The present invention relates to a process for obtaining dimethylaminoethanol (meth)acrylate comprising reacting a (meth)acrylate with at least partially renewable and non-fossil dimethylaminoethanol.

Description

Technical Field

[0001] This invention relates to a method for obtaining monomers from at least partially renewable and non-fossilized dimethylaminoethanol, preferably dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, their salted forms, or their quaternized forms. In a preferred embodiment, the method is a biological method comprising enzymatic hydrolysis of the dimethylaminoethanol in the presence of a biocatalyst containing a hydrolytic enzyme (preferably a lipase).

[0002] This invention also relates to bio-sourced polymers obtained from the monomers of this invention, and the uses of said bio-sourced polymers in various technical fields. Background Technology

[0003] Dimethylaminoethyl acrylate and dimethylaminoethyl methacrylate, as well as their salted or quaternized forms, are monomers widely used in the manufacture of water-soluble polymers.

[0004] The reaction in the preparation of dimethylaminoethyl (meth)acrylate follows the reaction pattern described below, wherein the short alkyl chain acrylate, typically methyl, ethyl, or butyl acrylate, reacts with dimethylaminoethanol.

[0005] Those skilled in the art will know that dimethylaminoethyl (meth)acrylate cannot be obtained industrially and practically by direct esterification of acrylic acid (or acrylates) with dimethylaminoethanol in the absence of a catalyst. In fact, without a catalyst, dimethylaminoethanol tends to react at the double bond, forming an undesirable product, namely the Michael adduct.

[0006]

[0007] In this reaction, R1 is a straight-chain or branched alkyl chain with 1 to 4 carbon atoms.

[0008] Therefore, many patents describe the use of catalysts to improve the conversion and selectivity of the reaction in order to minimize the second-order Michael addition reaction of dimethylaminoethanol to the double bond of acrylic acid derivatives (esters or acids).

[0009] For example, US 6,437,173 describes the use of titanate catalysts. Other types of organometallic catalysts can be used, such as organotin, dibutyltin oxide, dilauryltin oxide, or tin dichloride. More specifically, EP2,435,180 describes the transesterification reaction between methyl acrylate and dimethylaminoethanol in the presence of dibutyltin oxide. EP 1,773,748 describes a complete method for obtaining acrylic acid by oxidizing propane or propylene.

[0010] These organometallic catalysts lose all their effectiveness in the presence of water, therefore acrylic acid cannot be used. To achieve this, those skilled in the art use short-chain acrylates, typically methyl, ethyl, or butyl acrylates.

[0011] Transesterification reactions between short-alkyl-chain acrylates and dimethylaminoethanol produce alcohol byproducts corresponding to the short-alkyl chains. For example, methanol is produced when methyl acrylate reacts with dimethylaminoethanol.

[0012] Reference JP 2000072725 describes a route for the reaction of ethylene oxide with dimethylamine to obtain dimethylaminoethanol. Ethylene oxide is obtained by the oxidation of ethylene.

[0013] Fossil-based ethylene contains various impurities that remain or transform during the production of dimethylaminoethanol. For example, the presence of 2-vinyloxyethanol can be mentioned. In the production of dimethylaminoethyl (meth)acrylate, this impurity reacts with alkyl acrylates to form vinyloxyethyl methacrylate. This impurity is undesirable during the polymerization of dimethylaminoethyl (meth)acrylate and severely affects the polymerization process and the final application performance.

[0014] Acrylates are obtained by esterification between acrylic acid and alcohol, usually catalyzed by acid, such as p-toluenesulfonic acid, Nafion resin, sulfuric acid, and methanesulfonic acid as described in document WO 2015 / 015100.

[0015] Numerous documents describe how to obtain bio-based acrylic acid, such as US2010 / 0168471, which claims to convert glycerol into acrylic acid, and WO 2012 / 074818, which calls for the protection of fermented biomass to obtain 3-hydroxypropionic acid intermediate, which is a chemical precursor of acrylic acid.

[0016] Dimethylaminoethyl (meth)acrylate can be quaternized with an alkylating agent, such as an alkyl halide, more specifically chloromethane. Chloromethane is obtained by the reaction of hydrochloric acid and methanol, as described in US 5,917,099. Methanol is obtained by the oxidation of methane with oxygen.

[0017] The problem to be solved by the present invention is to provide a new and improved method for producing olefinic unsaturated monomers (e.g., dimethylaminoethyl acrylate and dimethylaminoethyl methacrylate). Summary of the Invention

[0018] The applicant has very unexpectedly discovered that the use of at least partially renewable and non-fossilized dimethylaminoethanol, preferably a fully renewable source, in the method of obtaining monomers of formula (I), particularly dimethylaminoethyl acrylate (R2=H) or dimethylaminoethyl methacrylate (R2=CH3), helps to improve the quality (purity) of the obtained monomers, thereby improving their polymerization reaction and the application properties of the polymers.

[0019]

[0020] In particular, the applicant has discovered such improvements when the method is a biological method carried out in the presence of a biocatalyst containing hydrolytic enzymes, especially lipases. In this case, the consumption of the biocatalyst is also significantly reduced and the recovery rate of the biocatalyst is improved.

[0021] Without seeking to be bound by any particular theory, the applicant proposes the possibility that the different properties of impurities between fossil-based dimethylaminoethanol and renewable, non-fossil-based dimethylaminoethanol are the cause of these unexpected technical effects.

[0022] The present invention relates first to a method for obtaining a monomer of formula (I), comprising a reaction between a compound of formula (II) and dimethylaminoethanol, wherein R2 is a hydrogen atom or a CH3 group, and R3 is a hydrogen atom or an alkyl group containing 1 to 8 carbon atoms, characterized in that the dimethylaminoethanol is at least partially renewable and non-fossil.

[0023]

[0024] Preferably, R3 is an alkyl group containing 1 to 4 carbon atoms, more preferably 1 or 2 carbon atoms.

[0025] The bio-based carbon content of the dimethylaminoethanol is preferably 5 wt% to 100 wt% relative to the total carbon weight in the dimethylaminoethanol, and this bio-based carbon content is determined according to ASTM D6866-21 Method B.

[0026] In this specification, the terms "between X and Y" and "from X to Y" include endpoints X and Y.

[0027] Polymer or (co)polymer should be understood to refer to homopolymer of a monomer of formula (I) or copolymer of a monomer of formula (I) with at least one monomer other than a monomer of formula (I), such as a terpolymer.

[0028] The compound of formula (II) is an acrylate in which R3 is an alkyl group containing 1 to 8 carbon atoms, or an acrylic acid in which R3 is a hydrogen atom.

[0029] The present invention also relates to a monomer of formula (I) having a bio-source carbon content of 45 wt% to 100 wt% relative to the total carbon weight in the monomer, said bio-source carbon content being determined according to ASTM D6866-21 Method B.

[0030] The present invention also relates to polymers obtained by polymerizing monomers of at least one of the monomers of formula (I) as described above, obtained by the method according to the invention, and the use of said polymers in a number of technical fields.

[0031] Using this invention, the inherent environmental goals of new technological innovation can be achieved. In this case, the use of renewable raw materials (dimethylaminoethanol in this example) helps to significantly optimize the conversion process and the quality of the obtained monomers. Preferably, the use of renewable dimethylaminoethanol and acrylates or acrylic acid of formula (II), combined with biological methods, helps to further improve the quality of monomers of formula (I), which provides unexpectedly improved performance.

[0032] The applicant discovered that when dimethylaminoethanol is partially or wholly renewable and non-fossil-derived, the conversion rate of dimethylaminoethanol to compound (I) is improved. The purity of compound (I) is also improved.

[0033] The applicant also discovered that the formation of compound (I) is improved when compound (II) is partially or wholly renewable and non-fossil-derived. The purity of compound (I) is also improved.

[0034] The applicant has also discovered that the polymers of the present invention have improved biodegradability characteristics compared to polymers that do not contain bio-derived monomers.

[0035] The applicant also found that fully renewable and non-fossil-derived polymers have less insoluble matter.

[0036] The applicant has also discovered that the polymers of the present invention exhibit improved performance as retention aids for paper compared to polymers without bio-derived monomers. They can also improve drainage performance.

[0037] The applicant has also discovered that the polymers of the present invention provide improved drag reduction compared to polymers that do not contain bio-derived monomers. Detailed Implementation

[0038] In the context of this invention, the term "renewable and non-fossil" is used to indicate that the source of a chemical compound is derived from biomass or syngas, i.e., produced by one or more chemical transformations of one or more natural and non-fossil feedstocks. The terms "bio-derived" or "biologically sourced" can also be used to characterize a compound as having a renewable and non-fossil source. Renewable and non-fossil sources of compounds include renewable and non-fossil feedstocks derived from the circular economy that have previously been recycled once or multiple times in biomass recycling processes, such as materials from polymer depolymerization or cracked oil processing.

[0039] According to the present invention, the quality of a compound being "at least partially renewable and non-fossil" refers to a biogenic carbon content, preferably from 5 wt% to 100 wt%, relative to the total carbon weight of the compound.

[0040] In the context of this invention, ASTM D6866-21 Standard Method B is used to characterize the bio-origin properties of chemical compounds and determine the bio-origin carbon content of said compounds. This value is expressed as a weight percentage (wt%) of bio-origin carbon relative to the total carbon weight in said compound.

[0041] ASTM D6866-21 is a test method that teaches how to experimentally measure the biogenic carbon content of solid, liquid, and gaseous samples using radiocarbon analysis.

[0042] This standard primarily utilizes accelerator mass spectrometry (AMS). This technique is used to naturally measure the presence of radionuclides in a sample, where atoms are ionized, accelerated to high energies, separated, and counted individually in a Faraday cup. This high-energy separation is highly effective at filtering out isotopic interference, thus AMS can accurately measure the abundance of carbon-14 relative to carbon-12 (14C / 12C) with an accuracy of 1.10. -15 .

[0043] ASTM D6866-21 Standard Method B uses AMS and IRMS (Isotope Ratio Mass Spectroscopy). This test method can directly distinguish between contemporary carbon-based carbon atoms and fossil-based carbon atoms. The carbon-14 content of the product relative to carbon-12 or carbon-14 relative to carbon-13 is measured according to modern carbon-based reference materials recognized by the radiocarbon dating community (e.g., NIST Standard Reference Material (SRM) 4990C) (oxalic acid).

[0044] The standard describes the sample preparation method, which does not require any special annotations because it is a commonly used procedure.

[0045] The analysis, interpretation, and reporting are as follows. The isotopic ratio of carbon-14 to carbon-12 or carbon-14 to carbon-13 content is measured using AMS. This isotopic ratio is determined relative to a standard traceable to the modern reference standard NIST SRM 4990C. The “fraction of modern” (fM) represents the carbon-14 content in the tested product relative to a modern standard. It is often referred to as the modern carbon percentage (pMC), which is equivalent to fM (e.g., fM 1 = 100 pMC).

[0046] All pMC values ​​derived from radiocarbons must be corrected for isotopic fractionation using a given stable isotope. If possible, correction should be made using carbon-14 versus carbon-13 values ​​determined directly using AMS. If this is not possible, correction should be made using delta-13C (δ13C) measurements obtained using IRMS, CRDS (Cavity Ring Down Spectroscopy), or any other equivalent technique providing accuracy within ±0.3 parts per thousand.

[0047] "Zero pMC" indicates the complete absence of measurable 14C above the background signal in the material, thus suggesting a fossil (e.g., petroleum-based) carbon source. A pMC value of 100 indicates a completely "modern" carbon source. pMC values ​​between 0 and 100 represent the proportion of carbon from a fossil source relative to a "modern" source.

[0048] Due to the continuous but gradually diminishing effects of the atmospheric nuclear test protocol's injection of 14C into the atmosphere, the pMC may be higher than 100%. The pMC value needs to be adjusted using an atmospheric correction factor (REF) to obtain the actual biogenic content of the sample.

[0049] The correction factor is based on the excess 14C activity in the atmosphere at the time of testing. The REF value for 2015 was determined to be 102 pMC based on measurements of CO2 in the air in rural Netherlands (Lugerwald, Groningen). The reference value in the first edition of this standard (ASTM D6866-04) in 2004 was 107.5 pMC, while the reference value in the later version, ASTM D6866-10 (2010), was 105 pMC. These data points represent a decrease of 0.5 pMC per year. Therefore, the values ​​in Table 1 below, dated January 2nd each year, were used as the REF values ​​prior to 2019, reflecting the same annual decrease of 0.5 pMC. Based on continuous measurements in the Netherlands (Lugerwald, Groningen) up to 2019, the REF values ​​(pMC) for 2020 and 2021 have been determined to be 100.0. References are provided below for reports on carbon isotope ratios for 14C and 13C: Roessler, N., Valenta, RJ, and van Cauter, S., “Time-Resolved Liquid Scintillation Counting and Organic Scintillator,” Ross, H., Noakes, JE, and Spaulding, JD, editors, Lewis Publishers, Chelsea, MI, 1991, pp. 501-511; Allison, CE, Francy, RJ, and Meijer, HAJ, “Reference and Comparison Materials for Stable Isotopes of Light Elements,” International Atomic Energy Agency, Vienna, Austria, IAEATECHDOC-825, 1995.

[0050] The percentage of bio-derived carbon content is calculated by dividing pMC by REF and multiplying the result by 100. For example, [10²(pMC) / 10²(REF)] × 100 = 100% bio-derived carbon. The result is expressed as the weight percentage (w%) of bio-derived carbon relative to the total carbon weight in the compound.

[0051] 2015 102，0 2016 101，5 2017 101，0 2018 100，5 2019 100，0 2020 100，0 2021 100，0

[0052] Table 1: Modern Carbon Percentage (pMC) Reference

[0053] In the context of this invention, the term "segregated" refers to a material stream that is distinct from and differentiated from other material streams in the value chain (e.g., in a product manufacturing process), and is therefore considered to belong to a group of materials with equivalent properties, such that the same source of the material, or its manufacture according to the same standards or specifications, can be traced and guaranteed throughout the value chain.

[0054] For example, this could be a scenario where a chemist purchases 100% bio-based dimethylaminoethanol from a single supplier who guarantees that the delivered dimethylaminoethanol is 100% bio-based, and the chemist processes this 100% bio-based dimethylaminoethanol separately from other potential sources of dimethylaminoethanol to produce a compound. If the resulting compound is made solely from the stated 100% bio-based dimethylaminoethanol, then the compound is 100% bio-based.

[0055] In the context of this invention, the term "non-segregated" is understood to mean a material flow that cannot be distinguished from other material flows in the value chain, as opposed to the term "segregated".

[0056] To better understand this concept of separation, it is helpful to review some basics of the circular economy and its practical applications in methods (especially chemical transformation).

[0057] According to the French Agency for Environment and Energy (ADEME), the circular economy can be defined as an economic system of trade and production that seeks to improve efficiency and reduce environmental impact in resource utilization at every stage of the product (goods and services) lifecycle, while simultaneously developing individual well-being. In other words, it is an economic system committed to efficiency and sustainability, minimizing waste by optimizing the value generated from resources. It relies heavily on various conservation and recycling applications to move away from the current more linear "get-make-dispose" approach.

[0058] In chemistry, this is the science of transforming one substance into another, which means reusing materials already used to manufacture products. Theoretically, all chemicals can be separated and therefore recycled separately from other chemicals. The reality is more complex, especially in industry, meaning that even after separation, the compound is often indistinguishable from the same compound from other sources, complicating the traceability of recycled materials.

[0059] To address this industrial reality, various traceability models have been developed, enabling users in the chemical industry to manage their material flows with full knowledge of the facts, and allowing end customers to easily understand and know the source of the materials used to produce objects or goods.

[0060] These models are developed to establish transparency and trust throughout the value chain. Ultimately, this allows end users or customers to choose more sustainable solutions by understanding the proportions of desired ingredients (such as bio-based properties) in an object or product, without having to autonomously control every aspect of the approach.

[0061] One such model is the "separation" model we defined earlier. Some known examples of applying this model are glass and some metals, where the material flow can be tracked separately.

[0062] However, chemicals are often used in complex combinations, and individual cycles are often difficult to implement, especially due to high costs and highly complex flow management, making the “separate” model not always applicable.

[0063] Therefore, when material flows cannot be distinguished, other models are applied. These models are grouped together under the term "non-separated" and take into account factors such as the proportion of a particular flow relative to other flows, without physically separating the flows. One example is the Mass Balance Approach.

[0064] The quality balance approach involves accurately tracking the proportion of a category (e.g., “recycling”) relative to the whole in a production system in order to ensure that the content of that category is allocated proportionally and appropriately in the finished product, based on auditable ledgers.

[0065] For example, a chemist purchases 50% bio-based dimethylaminoethanol from a supplier who guarantees, based on mass or weight balance methods, that 50% of the delivered dimethylaminoethanol is bio-based, while in fact 50% is not. The chemist then uses this 50% bio-based dimethylaminoethanol with another stream of 0% bio-based dimethylaminoethanol. These two streams are not identifiable at some point during production, for example, due to mixing. If the resulting compound is made from 50 wt% of the 50% bio-based guaranteed dimethylaminoethanol and 50 wt% of the 0% bio-based dimethylaminoethanol, then the compound is 25% bio-based.

[0066] For example, to ensure the claimed "bio-based" figures and to encourage the use of recycled raw materials in the production of new products, a set of globally shared standardized rules (ISCC+, ISO 14020) have been developed to reliably manage material flows.

[0067] In the context of this invention, the term "recycled" should be understood as referring to a source of compounds derived from methods of recycling materials considered as waste, i.e., one or more transformations of at least one material generally considered as waste using at least one recycling method.

[0068] The term "water-soluble polymer" is understood to refer to a polymer that dissolves in water at a concentration of 20 g / L when stirred at 25°C. -1 Polymers that produce clear aqueous solutions.

[0069] The method of the present invention

[0070] Therefore, the present invention relates to a method for obtaining a monomer of formula (I), comprising a reaction between a compound of formula (II) and dimethylaminoethanol, wherein R2 is a hydrogen atom or a CH3 group, and R3 is a hydrogen atom or an alkyl group containing 1 to 8 carbon atoms, characterized in that the dimethylaminoethanol is at least partially renewable and non-fossil.

[0071]

[0072] R3 is preferably an alkyl group containing 1 to 4 carbon atoms, and more preferably an alkyl group containing 1 or 2 carbon atoms.

[0073] The bio-based carbon content of dimethylaminoethanol is preferably 5 wt% to 100 wt% relative to the total carbon weight in dimethylaminoethanol, and this bio-based carbon content is determined according to ASTM D6866-21 Method B.

[0074] Throughout the invention, the bio-based carbon content of a compound that is at least partially renewable and non-fossil is specified, or the bio-based carbon content of the compound is specified as 5 wt% to 100 wt%, preferably 10 wt% to 100 wt%, preferably 15 wt% to 100 wt%, preferably 20 wt% to 100 wt%, preferably 25 wt% to 100 wt%, preferably 30 wt% to 100 wt%, preferably 35 wt% to 100 wt%, preferably 40 wt% to 100 wt%, preferably 45 wt% to 100 wt%, preferably 50 wt%. The bio-derived carbon content is determined according to ASTM D6866-21 Method B, up to 100 wt%, preferably 55 wt% to 100 wt%, preferably 60 wt% to 100 wt%, preferably 65 wt% to 100 wt%, preferably 70 wt% to 100 wt%, preferably 75 wt% to 100 wt%, preferably 80 wt% to 100 wt%, preferably 85 wt% to 100 wt%, preferably 90 wt% to 100 wt%, preferably from 95 wt% to 100 wt%, preferably 97 wt% to 100 wt%, preferably 99 wt% to 100 wt%.

[0075] Regarding the monomer of formula (I) of the present invention, the bio-based carbon content relative to the total carbon weight in the monomer is preferably 45 wt% to 100 wt%, preferably 50 wt% to 100 wt%, preferably 55 wt% to 100 wt%, preferably 60 wt% to 100 wt%, preferably 65 wt% to 100 wt%, preferably 70 wt% to 100 wt%, preferably 75 wt% to 100 wt%, preferably 80 wt% to 100 wt%, preferably 85 wt% to 100 wt%, preferably 90 wt% to 100 wt%, preferably 95 wt% to 100 wt%, preferably 97 wt% to 100 wt%, preferably 99 wt% to 100 wt%, and the bio-based carbon content is determined according to standard ASTM D6866-21 Method B.

[0076] Preferably, the compound of formula (II) is at least renewable and non-fossil. Preferably, based on the total carbon weight of the acrylate or acrylic acid of formula (II), the bio-based carbon content of the compound of formula (II) is 25 wt% to 100 wt%, preferably 50 wt% to 100 wt%, more preferably 75 wt% to 100 wt%, and the bio-based carbon content is determined according to ASTM D6866-21 Method B.

[0077] Preferably, dimethylaminoethanol is fully renewable and non-fossilized. Preferably, the monomer of formula (I) is fully renewable and non-fossilized. Preferably, both dimethylaminoethanol and the monomer of formula (I) are fully renewable and non-fossilized.

[0078] The monomer of formula (I) is dimethylaminoethyl acrylate or dimethylaminoethyl methacrylate.

[0079] In one specific embodiment, the monomer of formula (I) is salted or quaternized with an alkylating agent, preferably an alkyl halide, such as chloromethane, or a dialkyl sulfate, such as dimethyl sulfate, diethyl sulfate, or benzyl chloride. Chloromethane is a preferred alkylating agent.

[0080] Preferably, the bio-based carbon content of the alkylating agent is 50 wt% to 100 wt%, more preferably 70 wt% to 100 wt%, and even more preferably 100 wt%, relative to the total carbon weight in the alkylating agent, and the bio-based carbon content is determined according to ASTM D6866-21 Method B.

[0081] Preferably, dimethylaminoethanol, the monomer of formula (I), and the alkylating agent are fully renewable and non-fossil.

[0082] In a particularly preferred embodiment, the method is a biological method carried out in the presence of a biocatalyst comprising a hydrolytic enzyme selected from the group consisting of lipases, esterases, glycosylation enzymes, and proteases, either in free form or immobilized on a substrate. Preferably, the biocatalyst is a lipase or esterase.

[0083] Preferably, the enzyme is a lipase synthesized by microorganisms preferably selected from the group consisting of: Alcaligenes, Aspergillus, Mucor, Penicillium, Geotrichum, Rhizopus, Burkholderia, Candida, Pseudomonas, thermophilic fungi, and Candida antarcticis. Preferably, the lipase is derived from Candida antarcticis-type microorganisms.

[0084] Dimethylaminoethanol, and / or compounds of formula (II), and / or alkylating agents may be non-separated, partially separated, or completely separated.

[0085] When dimethylaminoethanol, and / or compounds of formula (II), and / or alkylating agents are fully renewable and non-fossilized, they can be:

[0086] a) A fully recyclable source and

[0087] a) 1) or completely separated;

[0088] a)2) or partially separated;

[0089] a)3) or non-separable;

[0090] b) or a partial recycling source and

[0091] b) 1) or completely separated;

[0092] b)2) or partially separated;

[0093] b)3) or non-separable;

[0094] c) or a completely non-recyclable source and

[0095] c)1) or completely separated;

[0096] c)2) or partially separated;

[0097] c)3) or non-separable.

[0098] In these different embodiments, when the dimethylaminoethanol, and / or the compound of formula (II), and / or the alkylating agent are partially separated, the weight ratio between the "separated" portion and the "non-separated" portion is preferably 99:1 to 10:90, more preferably 99:1 to 30:70, or even more preferably 99:1 to 50:50.

[0099] Among these different implementations, three implementations a), three implementations b), and implementation c)1) are preferred. Among these implementations, implementations a)1), a)2), b)1), b)2), and c)1) are more preferred. The two most preferred implementations are a)1) and b)1).

[0100] In industrial reality, it is not always possible to obtain industrial quantities of fully recycled and / or isolated or highly recycled and isolated dimethylaminoethanol and / or compounds of formula (II) and / or alkylating agents from biological sources. Therefore, the aforementioned preferred embodiments may currently be more difficult to achieve. From a practical standpoint, embodiments a), b), and c) are currently easier and more readily implemented on a large scale. With the rapid development of circular economy technologies, there is no doubt that the already applicable preferred models will soon be widely adopted.

[0101] If the dimethylaminoethanol and / or the compound of formula (II) and / or the alkylating agent portion is renewable and non-fossilized, then there is a distinction between the renewable (bio-based) and non-bio-based portions. Clearly, each of these portions can be derived according to the same embodiments a), b), and c) described above.

[0102] Regarding partially bio-derived dimethylaminoethanol, and / or the bio-derived portion of compounds of formula (II) and / or alkylating agents, the same preference is given to compounds that are entirely bio-derived.

[0103] However, for the non-biological portion of a partially bio-based compound, a circular economy approach is more preferably one that has the largest possible recoverable component. Therefore, in this case, preferred embodiments a)1), a)2), b)1), b)2), and especially a)1) and b)1)).

[0104] Compound (II) can be obtained by reacting acrylic acid with an alcohol having an alkyl chain containing 1 to 8 carbons. The reaction can be carried out in a batch, semi-batch, or continuous manner. The molar ratio between the alcohol and acrylic acid ranges from 1 to 10, preferably from 1 to 5, and even more preferably from 1 to 2.

[0105] When the reaction (acrylic acid / acrylate-alcohol) is an enzymatic reaction, it is usually carried out at a temperature between 5°C and 35°C, typically at room temperature. When the reaction is not enzymatic, it is usually carried out at a temperature between 30°C and 150°C, preferably between 50°C and 120°C.

[0106] The reaction time (acrylic acid / acrylate-alcohol) is generally between 1 minute and 24 hours.

[0107] The reaction (acrylic acid / acrylate-alcohol) can be carried out in the presence of an acid or base catalyst. It can be homogeneous or heterogeneous.

[0108] Dimethylaminoethanol can be prepared by reacting dimethylamine with ethylene oxide. This reaction can be carried out in a batch, semi-batch, or continuous manner. Preferably, dimethylamine is first added to the synthesis reactor, followed by the addition of ethylene oxide. The molar ratio of dimethylamine to ethylene oxide is typically 1 to 10, preferably 1 to 5.

[0109] The reaction (dimethylamine-ethylene oxide) is typically carried out at temperatures ranging from 50 to 200°C, preferably from 70 to 180°C. The reaction time is generally from 1 minute to 24 hours.

[0110] Alkylating agents can be produced by alcohols and Brønsted acids ( It is obtained by reacting alcohol (e.g., methanol and hydrochloric acid) to form chloromethane. This reaction can be carried out in a batch, semi-batch, or continuous manner. The molar ratio of alcohol to Brønsted acid is typically 1 to 10, preferably 1 to 5. Brønsted acid, such as hydrochloric acid, can be in liquid or gaseous form. Preferably, it is in gaseous form. It can also be in anhydrous or aqueous solution form. Preferably, it is in anhydrous form.

[0111] The reaction (formation of the alkylating agent) is typically carried out at temperatures between 30°C and 150°C, preferably between 50°C and 120°C. The reaction time is generally from 1 minute to 24 hours. The reaction can be carried out in the presence of an acid or base catalyst or a metal salt. It can be homogeneous or heterogeneous.

[0112] Alkylating agents can also be obtained by halogenation of alkanes, for example by chlorinating methane with chlorine, typically at temperatures between 400°C and 500°C.

[0113] In specific embodiments applicable to the various methods described in this invention, dimethylaminoethanol and / or compound (II) and / or alkylating agent are partially or entirely derived from the recycling process.

[0114] Recycling methods can include polymer depolymerization or synthesis from pyrolysis oil, the latter typically produced by the high-temperature, anaerobic combustion of waste plastics. Therefore, materials considered waste can be used as a source for producing recycled compounds, which in turn can be used as raw materials for manufacturing the monomers of this invention. Since the monomers of this invention are derived using recycling methods, the polymers of this invention described below are suitable for a virtuous cycle within a circular economy.

[0115] In this particular embodiment of the invention, the method for preparing the compound of formula (I) of the invention includes the following steps:

[0116] -Recycle at least one at least partially renewable and non-fossil material to obtain dimethylaminoethanol, and / or compounds of formula (II);

[0117] - The dimethylaminoethanol is reacted with the compound of formula (II) to obtain the compound of formula (I), preferably by a biological method in the presence of a biocatalyst containing a hydrolytic enzyme.

[0118] -Optionally, the compound of formula (I) is reacted with an alkylating agent.

[0119] In another specific embodiment of the present invention, the method for preparing the compound of formula (I) of the present invention includes the following steps:

[0120] - The dimethylaminoethanol is reacted with a compound of formula (II) to obtain a compound of formula (I), preferably by a biological method in the presence of a biocatalyst containing a hydrolytic enzyme; wherein the dimethylaminoethanol and / or the compound of formula (II) can be independently derived from at least partially renewable and non-fossil materials.

[0121] - React the compound of formula (I) with an alkylating agent derived from at least partially renewable and non-fossil materials.

[0122] Recovery rate refers to the weight ratio of recovered materials to total materials.

[0123] In a particular embodiment, the portion obtained from the recycling is preferably completely “separate,” i.e., obtained from a separate pipeline and processed in a separate manner. In another embodiment, it is partially “separate” and partially “non-separate.” In this case, the weight ratio between the “separate” portion and the “non-separate” portion is preferably 99:1 to 10:90, more preferably 99:1 to 30:70, or more preferably 99:1 to 50:50.

[0124] In another specific preferred embodiment, the biological method for bioconverting compound (II) and dimethylaminoethanol to obtain monomer of formula (I) includes enzymatic hydrolysis in the presence of a biocatalyst containing an enzyme. The bioconversion can be carried out in an aqueous medium, in which case water is used as both a solvent and a reagent. Those skilled in the art can refer to common knowledge regarding the steps and conditions of this method.

[0125] The monomer of the present invention

[0126] The present invention also relates to a monomer of formula (I) having a bio-based carbon content of 45 wt% to 100 wt%, preferably 70 wt% to 100 wt%, relative to the total carbon weight in the monomer, the bio-based carbon content being determined according to ASTM D6866-21 Method B.

[0127]

[0128] The preferred options in the Methods section apply to this section which describes monomers.

[0129] The present invention also relates to a monomer of formula (I) obtained by reacting a compound of formula (II) with dimethylaminoethanol, wherein R2 is a hydrogen atom or a CH3 group, R3 is a hydrogen atom or an alkyl group containing 1 to 8 carbon atoms, preferably by a biological method in the presence of a biocatalyst containing a hydrolytic enzyme, wherein the bio-source carbon content of the dimethylaminoethanol is 5 wt% to 100 wt% based on the total weight of carbon in the dimethylaminoethanol, and / or, preferably, the bio-source carbon content of the compound of formula (II) is 5 wt% to 100 wt% based on the total weight of carbon in the compound of formula (II), the bio-source carbon content being determined according to ASTM D6866-21 Method B.

[0130] Preferably, dimethylaminoethanol is fully renewable and non-fossil. Preferably, the compound of formula (II) is fully renewable and non-fossil. Preferably, the monomer of formula (I) is partially, preferably fully renewable and non-fossil. Preferably, dimethylaminoethanol, the compound of formula (II), and the monomer of formula (I) are fully renewable and non-fossil.

[0131] The present invention also relates to a bio-based dimethylaminoethyl methacrylate having a bio-based carbon content of 45 wt% to 100 wt% relative to the total carbon weight in the bio-based dimethylaminoethyl methacrylate, wherein the bio-based carbon content is determined according to ASTM D6866-21 Method B.

[0132] The term "(meth)acrylate" refers to methacrylate or acrylate.

[0133] Bio-derived dimethylaminoethyl methacrylate should be understood as (meth)acrylate acrylamide that is at least partially, preferably entirely, derived from biomass, i.e., the result of one or more chemical transformations of one or more raw materials of natural origin (rather than fossils). Bio-derived dimethylaminoethyl methacrylate may also be referred to as bio-based or biologically derived dimethylaminoethyl methacrylate.

[0134] This invention relates to bio-derived dimethylaminoethyl methacrylate, obtained by reacting methyl methacrylate with dimethylaminoethanol, preferably by a biological method in the presence of a biocatalyst containing a hydrolytic enzyme. In this reaction, the bio-derived carbon content of the dimethylaminoethanol and / or the methyl methacrylate is from 45 wt% to 100 wt%, based on the total carbon weight in the dimethylaminoethanol and / or the methyl methacrylate, and is determined according to ASTM D6866-21 Method B.

[0135] The present invention also relates to the salted or quaternized form of bio-derived (meth)acrylate dimethylaminoethyl acrylate. It can be quaternized with an alkylating agent, preferably an alkyl halide such as chloromethane, or a dialkyl sulfate such as dimethyl sulfate, diethyl sulfate, or benzyl chloride. Chloromethane is a preferred alkylating agent.

[0136] Preferably, the alkylating agent has a bio-based carbon content of 50 wt% to 100 wt%, preferably 70 wt% to 100 wt%, and even more preferably 100 wt%, relative to the total carbon weight in the alkylating agent, the bio-based carbon content being determined according to ASTM D6866-21 Method B.

[0137] Preferably, the dimethylaminoethanol, the monomer of formula (I), and the alkylating agent are fully renewable and non-fossil.

[0138] Dimethylaminoethanol and / or compounds of formula (II) and / or alkylating agents may be non-separated, partially separated, or completely separated. The preferred cases described in the Methods section apply to this section describing the monomers.

[0139] In one specific embodiment, the dimethylaminoethanol, and / or the compound of formula (II), and / or the alkylating agent may be partially or completely recycled. The preferred embodiments described in the Methods section apply to this section describing the monomers.

[0140] The polymer of the present invention

[0141] The present invention also relates to polymers obtained by polymerizing at least one monomer obtained according to the method of the invention. It further relates to polymers obtained by polymerizing at least one monomer as described above. The preferred embodiments described in the Methods section apply to this section describing the polymers.

[0142] The polymer of the present invention is preferably water-soluble or water-swellable. The polymer can also be a superabsorbent.

[0143] The polymers of the present invention may be homopolymers or copolymers with at least one first monomer obtained by the method according to the present invention, or with at least one previously described first monomer and at least one different second monomer, the latter preferably selected 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 containing a hydrophobic group.

[0144] Therefore, the copolymer may contain at least one second monomer different from the first monomer, the second monomer being selected from nonionic monomers, anionic monomers, cationic monomers, zwitterionic monomers, monomers containing hydrophobic groups, and mixtures thereof.

[0145] The nonionic monomer is preferably selected from the group consisting of: acrylamide, methacrylamide, N-isopropylacrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, N-hydroxymethylacrylamide, N-vinylformamide (NVF), N-vinylacetamide, N-vinylpyridine and N-vinylpyrrolidone (NVP), N-vinylimazole, N-vinylsuccinimide, acrylmorpholine (ACMO), acryloyl chloride, glycidyl methacrylate, glyceryl methacrylate and diacetone acrylamide.

[0146] The anionic monomers are preferably selected from the group consisting of: acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, acryloylaminoundecanoic acid, 3-acrylamido-3-methylbutyric acid, maleic anhydride, 2-acrylamido-2-methylpropanesulfonic acid (ATBS), vinyl sulfonic acid, vinyl phosphonic acid, allyl sulfonic acid, methyl allyl sulfonic acid, 2-sulfoethyl methacrylate, sulfopropyl methacrylate, sulfopropyl acrylate, allyl phosphonic acid, styrene sulfonic acid, 2-acrylamido-2-methylpropane disulfonic acid, and water-soluble salts of these monomers, such as their alkali metal salts, alkaline earth metal salts, or ammonium salts. Acrylic acid (and / or its salts), and / or ATBS (and / or its salts) are preferred.

[0147] The cationic monomer is preferably selected from the group consisting of: quaternized dimethylaminoethyl acrylate (ADAME), quaternized dimethylaminoethyl methacrylate (MADAME), dimethyl diallyl ammonium chloride (DADMAC), acrylamidopropyltrimethylammonium chloride (APTAC), and methacrylamidopropyltrimethylammonium chloride (MAPTAC).

[0148] The zwitterionic monomer can be a derivative of a vinyl unit, particularly acrylamide, acrylic acid, allyl or maleic acid, having an amine or ammonium functional group (preferably quaternary ammonium) and an acid functional group of a carboxylic acid (or carboxylic ester), sulfonic acid (or sulfonate) or phosphoric acid (or phosphate) type.

[0149] Monomers with hydrophobic properties can also be used to prepare polymers. Preferably, they are selected from the group consisting of: esters of (meth)acrylic acid having alkyl, arylalkyl, propoxylated, ethoxylated, or ethoxylated and propoxylated chains; derivatives of (meth)acrylamide having alkyl, arylalkyl, propoxylated, ethoxylated, ethoxylated and propoxylated chains, or dialkyl chains; alkylaryl sulfonates, or monosubstituted or disubstituted amides of (meth)acrylamide having propoxylated, ethoxylated, or ethoxylated and propoxylated alkyl, arylalkyl chains; derivatives of (meth)acrylamide having propoxylated, ethoxylated, ethoxylated and propoxylated alkyl, arylalkyl, or dialkyl chains; alkylaryl sulfonates.

[0150] Each of these monomers can also be of biological origin.

[0151] According to the present invention, the polymer can have straight-chain, branched, star-shaped, comb-shaped, dendritic, or block structures. These structures can be obtained by selecting initiators, transfer agents, polymerization techniques such as controlled radical polymerization known as RAFT (reversible addition-fragmentation chain transfer), NMP (nitrogen oxide-mediated polymerization), or ATRP (atom transfer radical polymerization), incorporation of structural monomers, concentration, etc.

[0152] According to the present invention, the polymer is preferably linear and structured. A structured polymer refers to a nonlinear polymer with side chains so that when the polymer is dissolved in water, it acquires a significant entanglement state, resulting in a very low gradient viscosity. The polymer of the present invention can also be crosslinked.

[0153] Furthermore, the polymer of the present invention can be structured:

[0154] - By means of at least one structuring agent, which may be selected from the group consisting of polyene-bonded unsaturated monomers (having at least two unsaturated functional groups), such as vinyl functional groups, particularly allyl, acrylic, and epoxy functional groups, and may also be mentioned such as methylene bisacrylamide (MBA), triallylamine, or tetraallyl ammonium chloride, or 1,2-dihydroxyethylene bis-(N-acrylamide), and / or

[0155] - Through macromolecular initiators, such as polyperoxides, polyazo compounds, and polytransfer agents, such as polymers (co)polymers and polyols, and / or

[0156] - Functionalized polysaccharides.

[0157] The amount of branching / crosslinking agent in the monomer mixture is preferably less than 4 wt%, more preferably less than 1%, and even more preferably less than 0.5% relative to the monomer content (by weight). According to a specific embodiment, it can be at least equal to 0.00001 wt% relative to the monomer content.

[0158] In specific embodiments, the polymers of the present invention may be semi-synthetic and therefore semi-natural polymers. In this embodiment, the polymers can be synthesized by copolymerization of at least one monomer of the present invention and at least one natural compound, which is preferably selected from the group consisting of starch and its derivatives, polysaccharides and their derivatives, fibers, plant gums, animal gums or alginates and their modified forms. For example, plant gums may include guar gum, gum arabic, locust bean gum, tragacanth gum, guanidine gum, anthocyanin gum, tara gum, cinnamon gum, xanthan gum, solanum gum, guilarin gum, gellan gum, cyanobacteria gum, guar bean gum, soybean gum, β-glucan or dammar gum. Natural compounds may also be gelatin, casein or chitosan. For example, alginates may include sodium alginate or its acid, agar or carrageenan.

[0159] Polymerization is typically carried out through copolymerization or grafting, but is not limited to these methods. Those skilled in the art can refer to existing common knowledge in the field of semi-natural polymers.

[0160] The present invention also relates to compositions comprising at least one polymer of the present invention and at least one natural polymer, wherein the natural polymer is preferably selected from the previously described natural polymers. The weight ratio of the synthetic polymer to the natural polymer is generally from 90:10 to 10:90. The composition may be in liquid, reverse emulsion, or powder form.

[0161] Generally, polymers do not require the development of specific polymerization methods. In fact, they can be obtained using all polymerization techniques well known to those skilled in the art. Specifically, this can be solution polymerization; gel polymerization; precipitation polymerization; emulsion polymerization (aqueous phase polymerization or reverse phase polymerization); suspension polymerization; reactive extrusion polymerization; water-in-water polymerization; or micellar polymerization.

[0162] Polymerization is typically free radical polymerization, preferably via reverse 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) or matrix polymerization techniques.

[0163] The polymers of the present invention can be modified after being obtained by polymerization. This is referred to as post-modification of the polymer. All known post-modifications can be applied to the polymers of the present invention, and the present invention also relates to polymers obtained after said post-modification. Among the possible post-modifications developed below, post-hydrolysis, post-modification by the Mannich reaction, post-modification by the Hoffmann reaction and post-modification by glyoxalization may be mentioned.

[0164] The polymers of the present invention can be obtained by post-hydrolysis of polymers obtained by polymerizing at least one monomer obtained by the method of the present invention or at least one monomer as previously described in the "Monomers" section. Prior to post-hydrolysis, the polymer contains, for example, acrylamide or methacrylamide monomer units. The polymer may further contain N-vinylformamide monomer units. More specifically, post-hydrolysis involves the reaction of a preferably nonionic monomer unit, more preferably a hydrolyzable functional group of an amide or ester functional group, with a hydrolyzing agent. The hydrolyzing agent can be an enzyme, an ion exchange resin, an alkali metal, or a suitable acid compound. Preferably, the hydrolyzing agent is a Brønsted base. When the polymer contains amide and / or ester monomer units, the post-hydrolysis reaction produces carboxylate groups. When the polymer contains vinylformamide monomer units, the post-hydrolysis reaction produces amine groups.

[0165] The polymers of the present invention can be obtained by performing a Mannich reaction on a polymer obtained by polymerizing at least one monomer obtained by the method of the present invention or a polymer obtained by polymerizing at least one monomer as previously described in the "Monomers" section. More specifically, prior to the Mannich reaction, the polymer preferably contains acrylamide and / or methacrylamide monomer units. The Mannich reaction is carried out in an aqueous solution in the presence of a dialkylamine and a formaldehyde precursor. More preferably, the dialkylamine is dimethylamine and the formaldehyde precursor is formaldehyde itself. After the reaction, the polymer contains a tertiary amine.

[0166] The polymers of the present invention can be obtained by performing a Hoffmann reaction on a polymer obtained by polymerizing at least one monomer obtained by the method of the present invention or a polymer obtained by polymerizing at least one monomer as previously described in the "Monomers" section. Prior to the Hoffmann reaction, the polymer preferably contains acrylamide and / or methacrylamide monomer units. The so-called Hoffmann degradation reaction is carried out in an aqueous solution in the presence of alkaline earth metals and / or alkali metal hydroxides and alkaline earth metals and / or alkali metal hypohalides.

[0167] This reaction, discovered by Hoffmann in the late 19th century, is used to convert amide functional groups into primary amine functional groups with one less carbon atom. The detailed reaction mechanism is as follows.

[0168] Protons are extracted from amides in the presence of Brønsted bases (e.g., soda ash).

[0169]

[0170] The amidate is formed and then reacts with the active chlorine (Cl2) of the chlorate (e.g., NaClO in equilibrium). The chloroamide is generated. A Brønsted base (e.g., NaOH) extracts a proton from the chloroamide to form an anion. The anion loses a chloride ion to form a nitroene, which undergoes an isocyanate rearrangement.

[0171]

[0172] Carbamates are formed through the reaction between hydroxide ions and isocyanates.

[0173]

[0174] After decarboxylation (removal of CO2) of urethane esters, primary amines are obtained.

[0175]

[0176] To convert all or part of the amide functional groups in a (co)polymer containing amide groups into amine functional groups, two main factors (expressed as molar ratios) are involved. They are:

[0177] -Alpha = (alkali metal and / or alkaline earth metal hypohalides / amide groups) and

[0178] -Beta = (alkali metal and / or alkaline earth metal hydroxides / alkali metal and / or alkaline earth metal hypohalides).

[0179] The polymers of the present invention can also be obtained by glyoxalization of a polymer obtained by polymerization of at least one monomer obtained by the method of the present invention or a polymer obtained by polymerization of at least one monomer as previously described in the "Monomers" section, wherein the polymer comprises at least one monomer unit (preferably acrylamide or methacrylamide) by the glyoxalization reaction. More specifically, the glyoxalization reaction involves the reaction of at least one aldehyde on the polymer, thereby functionalizing the polymer. Preferably, the aldehyde is selected from glyoxal, glutaraldehyde, furanyl dialdehyde, 2-hydroxyhexanedialdehyde, succinal, starch dialdehyde, 2,2-dimethoxyacetaldehyde, diepoxides, and combinations thereof. Preferably, the aldehyde compound is glyoxal.

[0180] According to the present invention, the polymer may be in liquid, gel or solid form, and the preparation includes a drying step, such as spray drying, drum drying, radiation drying (e.g. microwave drying) or fluidized bed drying.

[0181] According to the present invention, the water-soluble polymer preferably has a molecular weight of 1,000 to 40 million g / mol. The polymer can be a dispersant, in which case its molecular weight is preferably 1,000 to 50,000 g / mol. The polymer can have a higher molecular weight, typically between 1 and 30 million g / mol. Molecular weight is understood as weight-average molecular weight. The polymer of the present invention can also be a superabsorbent capable of absorbing 10 to 500 times its weight in water.

[0182] Molecular weight is preferably determined by the intrinsic viscosity of the (co)polymer. Intrinsic viscosity can be measured by methods known to those skilled in the art, and can be calculated from the specific viscosity values ​​at different (co)polymer concentrations (x-axis) by plotting the specific viscosity values ​​(y-axis) against concentration graphically, and extrapolating the curve to zero concentration. The intrinsic viscosity values ​​can be plotted on the y-axis or using the least squares method. The molecular weight can then be determined using the Mark-Houwink equation:

[0183] [η]=KM α

[0184] [η] represents the intrinsic viscosity of the (co)polymer as determined by solution viscosity measurement methods.

[0185] K represents an empirical constant.

[0186] M represents the molecular weight of the (co)polymer.

[0187] α represents the Mark-Houwink coefficient.

[0188] K and α depend on the specific (co)polymer-solvent system.

[0189] The comonomers used in combination with the monomers of the present invention to obtain the polymers of the present invention are preferably at least partially or more fully renewable and non-fossilized.

[0190] Therefore, in a preferred embodiment, the present invention relates to a polymer comprising:

[0191] - At least 5 mol%, preferably at least 10 mol%, preferably 20 mol% to 99 mol%, more preferably 30 mol% to 90 mol% of the first monomer, said monomer being the monomer of the present invention, and

[0192] - At least 1 mol%, preferably 5 mol% to 90 mol%, more preferably 10 mol% to 80 mol% of at least one second monomer containing olefinic unsaturation, the second monomer being different from the first monomer and being at least partially renewable and non-fossil.

[0193] Therefore, in a preferred embodiment, the present invention relates to a polymer comprising:

[0194] - at least 5 mol%, preferably at least 10 mol%, preferably 20 mol% to 99 mol%, more preferably 30 mol% to 90 mol%, of the first monomer, said monomer being the monomer of the present invention; and

[0195] - At least 1 mol%, preferably 5 mol% to 90 mol%, more preferably 10 mol% to 80 mol% of at least one second monomer containing olefinic unsaturation, the second monomer being different from the first monomer and being at least partially renewable and non-fossil;

[0196] - At least 1 mol%, preferably 5 mol% to 90 mol%, more preferably 10 mol% to 80 mol% of at least one third monomer containing olefinic unsaturation, said third monomer being different from the first and second monomers and being at least partially renewable and non-fossil.

[0197] The polymer of the present invention may contain four or more different monomers.

[0198] In a preferred embodiment, the bio-source carbon content of the second monomer and possibly other monomers is 5 wt% to 100 wt%, preferably 10 wt% to 100 wt%, relative to the total carbon weight in the relevant monomers, and the bio-source carbon content is determined according to ASTM D6866-21 Method B.

[0199] In this preferred embodiment, the second monomer and possible other monomers are preferably selected from the group consisting of: acrylamide, methacrylamide, (meth)acrylic acid and / or its salts, acrylic acid oligomers, 2-acrylamide-2-methylpropanesulfonic acid (ATBS) and / or its salts, N-vinylformamide (NVF), N-vinylpyrrolidone (NVP), dimethyl diallyl ammonium chloride (DADMAC), and monomers having the formula CH2=CHCO-NR. 1 R 2 The substitution of acrylamide, R 1 and R 2 Each is an independent straight-chain or branched carbon chain (C). n H 2n+1 , where n is from 1 to 10.

[0200] Throughout the invention, it should be understood that the molar percentage of the monomers (excluding any crosslinking agents) of the polymer is equal to 100%.

[0201] Preferably, the bio-based carbon content of the polymer is 5 wt% and 100 wt% relative to the total carbon weight in the polymer of the present invention, and the bio-based carbon content is determined according to ASTM D6866-21 Method B.

[0202] The dimethylaminoethanol and / or the compound of formula (II) and / or the alkylating agent may be non-separated, partially separated, or completely separated. The preferred cases described in the Methods section apply to this section describing the polymer.

[0203] In one specific embodiment, the dimethylaminoethanol, and / or the compound of formula (II), and / or the alkylating agent may be partially or wholly recycled. The preferred embodiments described in the Methods section apply to this section describing the polymer.

[0204] The present invention also relates to polymers obtained according to a method comprising the following steps:

[0205] -Recycle at least one at least partially renewable and non-fossil material to obtain dimethylaminoethanol and / or compounds of formula (II);

[0206] - React the dimethylaminoethanol thus obtained with the compound of formula (II) to obtain the compound of formula (I), preferably by a biological method in the presence of a biocatalyst containing a hydrolytic enzyme;

[0207] The monomer of formula (I) obtained therefrom is optionally polymerized with at least one second monomer containing at least one degree of olefinic unsaturation to obtain a polymer.

[0208] The present invention also relates to the use of at least one monomer obtained according to the method of the present invention for the synthesis of polymers.

[0209] Using the polymer of the present invention

[0210] This invention also relates to the use of the polymers of this invention in: hydrocarbon (oil and / or gas) recovery; drilling and cementing; hydrocarbon well (oil and / or natural gas) production enhancement; for example, hydraulic fracturing, construction, diversion; water treatment in open, closed, or semi-closed loops; fermentation slurry treatment, sludge treatment; papermaking; construction; wood processing; hydraulic composition processing (concrete, cement, mortar, and aggregates); mining; cosmetic formulation; detergent formulation; textile manufacturing; battery module manufacturing; geothermal energy; sanitary napkin manufacturing; or agriculture.

[0211] The present invention also relates to the use of the polymers of the present invention as flocculants, coagulants, adhesives, fixatives, viscosity reducers, thickeners, absorbents, drag reducers, dehydrating agents, drainage agents, charge retaining agents, dehydrating agents, conditioning agents, stabilizers, film-forming agents, sizing agents, superplasticizers, clay inhibitors, or dispersants.

[0212] Method using the polymer of the present invention

[0213] This invention also relates to various methods described below, wherein the polymers of this invention are used to improve application performance.

[0214] The present invention also relates to a method for improving oil and / or gas recovery by clearing underground formations, comprising the following steps:

[0215] a. An injection fluid is prepared from the polymer of the present invention with water or brine.

[0216] b. Inject the fluid into the underground formation.

[0217] c. Clean the underground strata with the injected fluid.

[0218] d. Recovering aqueous mixtures of oil and / or gas.

[0219] The present invention also relates to a method for hydraulic fracturing of underground oil and / or gas reservoirs, comprising the following steps:

[0220] a. An injection fluid is prepared from the polymer of the present invention with water or brine and with at least one proppant.

[0221] b. Inject the fluid into the underground reservoir and fracture at least a portion of it to recover oil and / or gas.

[0222] 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 a powder, a reverse emulsion, a partially dehydrated reverse emulsion, or a "transparent" form, i.e., a dispersion of solid polymer particles in an aqueous or oily fluid. The powder form is preferably obtained by gelling or spray drying of the reverse emulsion. It also relates to compositions comprising a reverse emulsion of the polymer of the present invention and solid particles of the polymer of the present invention.

[0223] This invention also relates to a method for increasing the production of underground strata, comprising the following steps:

[0224] a. An injection fluid is prepared from the polymer of the present invention with water or brine.

[0225] b. Inject the fluid into the underground formation.

[0226] c. To partially or completely block the underground formation with injected fluid, the blockage being temporary or permanent.

[0227] The present invention also relates to a method for drilling and / or cementing wells in underground formations, comprising the following steps:

[0228] a. An injection fluid is prepared from the polymer of the present invention with water or brine.

[0229] b. Injecting drilling and / or cementing fluids into the underground formation via the drill bit in at least one step of drilling or cementing.

[0230] Drilling and cementing are two consecutive steps in drilling a well in underground formations. The first step is drilling with drilling fluid, and the second step is cementing with cementing fluid. This invention also relates to a method of injecting an intermediate fluid (“spacer fluid”) between the drilling fluid and the cementing fluid, the intermediate fluid comprising at least one polymer of this invention. This intermediate fluid prevents contamination between the cementing fluid and the drilling fluid.

[0231] During drilling and cementing, the polymers of this invention can be used as fluid loss additives in well cement compositions to reduce fluid loss from the cement composition to the permeable formation or area being pumped in or passed through. During initial cementing, fluid (i.e., water) loss to the permeable formation or subsurface area can cause premature gelation of the cement composition, creating a bridge between the permeable formation or area and the annular space where the drill string is cemented, preventing the cement composition from settling along the entire length of the annulus.

[0232] The present invention also relates to a method for clay inertization in a hydraulic composition for use in construction purposes, the method comprising the step of adding at least one clay inertizing agent to the hydraulic composition or one of its components, characterized in that the clay inertizing agent is a polymer of the present invention.

[0233] Clay absorbs moisture and causes a deterioration in the performance of building materials. When the polymer of this invention is used as a clay inhibitor, it particularly allows for the prevention of clay swelling, which can lead to cracking and thus weaken any building.

[0234] The hydraulic composition may be concrete, cement, mortar, or aggregate. Preferably, the polymer is added to the hydraulic composition or one of its components at a dosage of 2 to 200 ppm of inert agent relative to the weight of the aggregate.

[0235] In methods of inertizing clay, the clay includes, but is not limited to, 2:1 expanded clay (e.g., montmorillonite), 1:1 expanded clay (e.g., kaolinite), or 2:1:1 expanded clay (e.g., chlorite). The term "clay" generally refers to magnesium silicate and / or aluminum silicate, including layered silicates having a layered structure. However, in this invention, the term "clay" also includes clays that do not have such a structure, such as amorphous clay.

[0236] This invention also relates to a method for manufacturing paper, paperboard, etc., wherein, prior to paper formation, the following step is performed: adding at least one polymer of the invention to a fiber suspension at one or more injection points. The polymer can provide dry strength or retention properties or wet strength. It can also improve paper smoothness, drainage, and dewatering capabilities.

[0237] This method can be successfully used to manufacture packaging paper and paperboard, coated paper, sanitary and household paper, any type of paper, paperboard, etc.

[0238] The post-modified polymers described in the "Polymers" section, especially those modified by the Hoffmann reaction or by glyoxalization, are particularly advantageous in methods for manufacturing paper, paperboard, etc.

[0239] Retention properties are understood as the ability to retain suspended materials from pulp (fibers, fine powders, fillers (calcium carbonate, titanium dioxide, etc.)) on the formed fabric, and thus in the fibers that will make up the final paper. Retention aids work by flocculating these suspended substances in water. In fact, the flocs formed are more likely to be retained on the formed sheet.

[0240] Filler retention involves specifically retaining fillers (small mineral species with little affinity for cellulose). Significant improvements in filler retention, achieved by retaining fillers within the sheet and increasing its basis weight, result in clearer white water. It can also reduce manufacturing costs by replacing some fibers (the most expensive type in compositions of paper, paperboard, or similar materials) with fillers (which are less expensive).

[0241] Regarding dehydration (or drainage) performance, it is the ability of the fiber pad to empty or drain the maximum amount of water to allow the sheet to dry as quickly as possible, especially during the sheet manufacturing process.

[0242] These two properties (retention and drainage) are intricately linked, one depending on the other; therefore, the challenge is to find the optimal compromise between retention and drainage. Those skilled in the art often refer to retention aids and drainage agents because they are the same type of products used to improve both properties.

[0243] Fiber suspension should be understood as a thick or thin slurry composed of water and cellulose fibers. Thick slurries with a dry matter concentration exceeding 1% or even 3% are located upstream of the blower pump. Thin slurries with a dry matter concentration generally less than 1% are located downstream of the blower pump.

[0244] The polymer can be added to either thick or thin slurry. It can be added at the level of the blower pump or headbox. Preferably, the polymer is added before the headbox.

[0245] In methods for preparing paper, paperboard, etc., the polymer of the present invention can be used alone or in combination with a second retention aid. Preferably, the second retention aid, selected from organic polymers and / or inorganic microparticles, is added to the fiber suspension.

[0246] The second retention aid added to the fiber suspension is preferably selected from anionic polymers in the broad sense, and therefore can be (but is not limited to) linear, branched, crosslinked, hydrophobic, associative and / or inorganic microparticles (e.g., bentonite, colloidal silica).

[0247] The present invention also relates to a method for treating a suspension of solid particles in water generated from mining or oil sands operations, comprising contacting the suspension with at least one polymer of the present invention. This method can be carried out in a thickener, which is a holding zone, typically in the form of a pipe section several meters in diameter with a conical bottom, in which the particles can settle. According to one specific embodiment, the aqueous suspension is conveyed to the thickener through a pipe, and the polymer is added to the pipe.

[0248] According to another embodiment, a polymer is added to a thickener that already contains a suspension to be treated. In typical mineral processing operations, the suspension is typically concentrated in a thickener. This results in a high-density sludge being discharged from the bottom of the thickener, and an aqueous fluid released from the treated suspension (referred to as the liquid) being discharged from the top of the thickener via an overflow. Generally, the addition of the polymer increases the concentration of the sludge and increases the clarity of the liquid.

[0249] According to another embodiment, a polymer is added to the particulate suspension during the transport of the suspension to the deposition zone. Preferably, the polymer is added to the conduit that transports the suspension to the deposition zone. The treated suspension is then dispersed in the deposition zone in preparation for dehydration and solidification. The deposition zone can be open (e.g., an unrestricted soil area) or closed, such as a tank or chamber.

[0250] An example of such treatment during suspension transport is spreading a suspension treated with the polymer of the present invention onto soil in preparation for dehydration and solidification, followed by spreading a second layer of treated suspension on top of the solidified first layer. Another example is the continuous dispersal of a suspension treated with the polymer of the present invention, such that the treated suspension continuously falls onto a suspension previously discharged into a deposition area, thereby forming a large quantity of treated material from which water has been extracted.

[0251] According to another embodiment, a water-soluble polymer is added to a suspension and mechanically treated, such as by centrifugation, pressing, or filtration.

[0252] Water-soluble polymers can be added simultaneously at different stages of suspension treatment, i.e., for example, in the pipes that transport the suspension to the thickener and in the sludge leaving the thickener, which will be transported to the sedimentation area or to a mechanical treatment device.

[0253] The present invention also relates to a method for treating municipal or industrial water, comprising adding at least one polymer of the present invention to the water to be treated. Effective water treatment requires the removal of dissolved compounds as well as dispersed and suspended solids from the water. This treatment is typically enhanced by chemicals such as coagulants and flocculants. These are usually added to the water stream prior to separation units such as flotation and sedimentation.

[0254] The polymers of the present invention can be preferably used to coagulate or flocculate suspended particles in urban or industrial wastewater. Generally, they are used in combination with inorganic coagulants such as alum.

[0255] They can also be effectively used to treat the sludge generated from the treatment of this wastewater. Sewage sludge (whether municipal or industrial) is a major waste generated by treatment plants from liquid wastewater. Generally, sludge treatment includes dewatering. This dewatering can be carried out by centrifugation, filter presses, belt presses, electrostatic dewatering, sludge drying on reed beds, or solar drying. It is used to reduce the concentration of the sludge water.

[0256] In this urban or industrial water treatment method, the polymer of the present invention is preferably linear or branched. It is preferably in the form of a powder, a reverse emulsion, or a partially dehydrated reverse emulsion. The powder form is preferably obtained from the reverse emulsion by gel or spray drying.

[0257] This invention also relates to additives for use in cosmetic, dermatological, or pharmaceutical compositions, said additives comprising at least one polymer of this invention. This invention further relates to the use of the polymers of this invention in the manufacture of said compositions as thickeners, modifiers, stabilizers, emulsifiers, fixatives, or film-forming agents. This invention also relates to cosmetic, dermatological, or pharmaceutical compositions comprising at least one polymer of this invention.

[0258] In particular, reference can be made to the description of the manufacture of such compositions and other components of such compositions in application FR2979821 representing L'Oréal. The compositions may be in the form of lotions, lotions, gels, creams, gel-creams, soaps, bubble baths, balms, shampoos, or conditioners. The use of the compositions for cosmetic or dermatological treatment of keratin materials such as skin, scalp, eyelashes, eyebrows, nails, hair, and / or mucous membranes is also part of this invention. Such use includes applying the composition to keratin materials, possibly followed by rinsing with water.

[0259] This invention also relates to additives for detergent compositions, said additives comprising at least one polymer of the present invention. The invention further relates to the use of the polymers of the present invention in the manufacture of said compositions as thickeners, modifiers, stabilizers, emulsifiers, fixatives, or film-forming agents. The invention also relates to detergent compositions for domestic or industrial use comprising at least one polymer of the present invention. In particular, reference can be made to applicant's application WO2016020622 for the manufacture of such compositions and for the description of other components of such compositions.

[0260] "Detergent compositions for household or industrial use" should be understood as compositions for cleaning a variety of surfaces, particularly textile fibers, any kind of hard surface (e.g., tableware, floors, windows, wood, metal, or composite surfaces). Such compositions include, for example, detergents for washing clothes by hand or in a washing machine, products for cleaning dishes by hand or in a dishwasher, detergent products for cleaning interiors of the home (e.g., kitchen components, bathrooms, furniture, floors, windows), and other cleaning products for general use.

[0261] Polymers used as additives, such as thickeners, in cosmetic, dermatological, pharmaceutical, or detergent compositions are preferably cross-linked. They are preferably in the form of powder, reverse emulsion, or partially dehydrated reverse emulsion. The powder form is preferably obtained from a reverse emulsion by spray drying.

[0262] The present invention also relates to thickeners for pigment compositions used in textile printing, the thickener comprising at least one polymer of the present invention. The present invention further relates to textile fiber sizing agents comprising at least one polymer of the present invention.

[0263] The present invention also relates to a method for manufacturing superabsorbents from monomers of the present invention, wherein the superabsorbent is obtained from at least one monomer of the present invention, the superabsorbent being used to absorb and retain water in agricultural applications or to absorb aqueous liquids in sanitary napkins. For example, the superabsorbent is a polymer of the present invention.

[0264] The present invention also relates to a method of manufacturing sanitary napkins, wherein the polymer of the present invention is used, for example, as a superabsorbent agent.

[0265] This invention also relates to the use of the polymers of this invention as battery adhesives. This invention also relates to a battery adhesive composition comprising the polymers of this invention, electrode materials, and a solvent. This invention further relates to a method of manufacturing a battery, comprising preparing a gel comprising at least one polymer of this invention and filling it into the battery. For example, lithium-ion batteries are used in a variety of products, including medical devices, electric vehicles, aircraft, and most importantly, consumer products such as laptops, mobile phones, and cameras.

[0266] Typically, a lithium-ion battery (LIB) comprises an anode, a cathode, and an electrolyte material (such as an organic solvent containing lithium salts). More specifically, the anode and cathode (collectively referred to as "electrodes") are formed by mixing the electrode active material (anode or cathode) with a binder and solvent to form a paste or slurry, which is then applied to a current collector (such as aluminum or copper) and dried to form a film on the current collector. The anode and cathode are then stacked and wound, and then packaged into a pressurized casing containing the electrolyte material; all of these together form a lithium-ion battery.

[0267] In lithium-ion batteries, binders play a crucial role in mechanical and electrochemical performance. First, they help disperse other components in a solvent during manufacturing (some also act as thickeners), achieving a uniform distribution. Second, they hold various components together, including active components, any conductive additives, and current collectors, ensuring all these parts remain in contact. Through chemical or physical interactions, binders connect these individual components, fixing them together and ensuring the mechanical integrity of the electrodes without affecting the electronic or ionic conductivity. Third, they typically act as the interface between the electrodes and the electrolyte. In this role, they protect the electrodes from corrosion or the electrolyte from depletion, while facilitating ion transport across the interface.

[0268] Another important point is that the adhesives must have a certain degree of flexibility so that they do not break or develop defects. Brittleness can cause problems during the manufacturing or assembly of batteries.

[0269] Given all the roles it plays in the electrodes (and the entire battery), choosing the right binder is crucial to ensuring good battery performance.

[0270] The present invention also relates to a method of manufacturing sanitary napkins, wherein the polymer of the present invention is used, for example, as a superabsorbent agent.

[0271] As mentioned earlier, the circular economy is an economic system committed to efficiency and sustainability, minimizing waste by optimizing the value generated from resources. It relies heavily on various conservation and recycling practices to move away from the current more linear "take-make-dispose" path.

[0272] Therefore, as material recycling becomes a major concern, recycling processes are rapidly developing and are capable of producing materials that can be used to create new compounds or substances. The recycling of materials is not dependent on their origin; anything that can be recycled is considered a technological advancement. While the source of the material to be recycled may be renewable and non-fossil, it may also be fossil.

[0273] The specific objectives are as follows.

[0274] The first specific object relates to a method for obtaining a monomer of formula (I), the method comprising a reaction between a compound of formula (II) and dimethylaminoethanol, wherein R2 is a hydrogen atom or a CH3 group, and R3 is a hydrogen atom or an alkyl group containing 1 to 8 carbon atoms, characterized in that the dimethylaminoethanol is obtained at least partially, preferably entirely, from renewable and non-fossil materials or from the recycling process of fossil materials. The method may include the steps of salting or quaternizing (using an alkylating agent) the monomer of formula (I).

[0275] The dimethylaminoethanol and / or the compound of formula (II) and / or the alkylating agent may be non-separated, partially separated, or completely separated. The same preferred embodiments described in the Methods section apply to this section of the specification.

[0276] In one specific embodiment, the dimethylaminoethanol, and / or the compound of formula (II), and / or the alkylating agent may be partially or wholly recovered. The same preferred embodiments described in the Methods section apply to this section of the specification.

[0277] The second specific objective relates to a monomer of formula (I) obtained by reacting a compound of formula (II) with dimethylaminoethanol, wherein R2 is a hydrogen atom or a CH3 group, R3 is a hydrogen atom or an alkyl group containing 1 to 8 carbon atoms, preferably by a biological method in the presence of a biocatalyst containing a hydrolytic enzyme, wherein the dimethylaminoethanol is obtained at least partially, preferably entirely, from a process of recycling renewable and non-fossil materials or fossil materials, and / or, preferably, the compound of formula (II) is obtained at least partially, preferably entirely, from a process of recycling renewable non-fossil materials or fossil materials.

[0278]

[0279] The third specific objective relates to dimethylaminoethyl (meth)acrylate, which is obtained by reacting methyl (meth)acrylate with dimethylaminoethanol, preferably by a biological method in the presence of a biocatalyst containing a hydrolytic enzyme, wherein the dimethylaminoethanol and / or methyl (meth)acrylate are at least partially, preferably entirely, obtained from renewable and non-fossil materials or from fossil material recycling methods.

[0280] The present invention also relates to the salted or quaternized form of dimethylaminoethyl (meth)acrylate. It can be quaternized using an alkylating agent, preferably an alkyl halide (e.g., chloromethane), or a dialkyl sulfate (e.g., dimethyl sulfate, diethyl sulfate, or benzyl chloride). Chloromethane is a preferred alkylating agent.

[0281] The fourth specific objective relates to polymers obtained by polymerizing at least one monomer of formula (I) as described above.

[0282] The fifth specific purpose relates to the use of polymers obtained by polymerizing at least one monomer of formula (I) as described above in the following: oil and / or gas recovery, drilling and cementing; oil and / or gas well enhancement (e.g., hydraulic fracturing, construction, diversion), water treatment in open, closed or semi-closed loops, fermentation slurry treatment, sludge treatment, papermaking, construction, wood processing, hydraulic composition processing (concrete, cement, mortar and aggregate), mining, cosmetic formulation, detergent formulation, textile manufacturing, battery component manufacturing; geothermal energy; sanitary napkin manufacturing; or agriculture.

[0283] The sixth specific objective relates to the use of polymers obtained by polymerizing at least one monomer of formula (I) as flocculants, coagulants, adhesives, fixatives, viscosity reducers, thickeners, absorbents, drag reducers, dehydrating agents, drainage agents, charge-retaining agents, dehydrating agents, regulators, stabilizers, film-forming agents, sizing agents, superplasticizers, clay inhibitors, or dispersants.

[0284] The seventh specific objective relates to polymers obtained according to a method comprising the following steps:

[0285] -Recycle at least one at least partially renewable non-fossil material or fossil material to obtain dimethylaminoethanol, and / or compounds of formula (II);

[0286]

[0287] - React the dimethylaminoethanol obtained therefrom with a compound of formula (II) to obtain a compound of formula (I), preferably by a biological method in the presence of a biocatalyst containing a hydrolytic enzyme;

[0288] - The monomer of formula (I) obtained therefrom is optionally polymerized with at least one second monomer containing at least one degree of olefinic unsaturation to obtain a polymer.

[0289] The dimethylaminoethanol and / or the compound of formula (II) are preferably completely “separate”, i.e. derived from separate pipelines and processed separately.

[0290] In another embodiment, they are partially "separate" and partially "non-separate". In this case, the weight ratio between the "separate" and "non-separate" portions is preferably 99:1 to 25:75, more preferably 99:1 to 50:50. In another embodiment, they are completely "separate". Attached Figure Description

[0291] Figures 1 to 4 It is a graph showing the relationship between the drag reduction percentage of each polymer and time.

[0292] Example

[0293] The following examples relate to the synthesis of compound (I) of the present invention. This is to illustrate the advantages of the invention in a clear and non-limiting manner.

[0294] In the following embodiment:

[0295] - Compound (I) is dimethylaminoethyl acrylate, labeled ADAME.

[0296] - Compound (II) is methyl acrylate.

[0297] - Dimethylaminoethanol is annotated as DMOH.

[0298] Purity Test Instructions

[0299] The purity of dimethylaminoethyl acrylate (or ADAME) was determined by gas chromatography under the following conditions:

[0300] -DB-WAXUI column, 60m x 0.32mm ID, 50μm thin film

[0301] -Injector temperature: 250℃

[0302] - Oven: 80℃ for 5 minutes, then increase the temperature to 125℃ at a rate of 4℃ / min and hold for 2 minutes, then increase the temperature to 240℃ at a rate of 35℃ / min.

[0303] - Detector temperature: 250℃

[0304] -Injection volume: 2 μL, split ratio 1:200, protective gas flow rate 20 m / min, after 5 minutes

[0305] - Detector: FID (PerkinElmer AUTOSYSTEM XL type)

[0306] - Detection gases: H2 at 30 mL / min, air at 400 mL / min

[0307] -Carrier gas (He): 1.5 mL / min

[0308] The purity of ADAME can be calculated by using external standards and measuring the area of ​​various impurity peaks.

[0309] I. Synthesis of bio-based ADAME using DBTO catalysts:

[0310]

[0311] Example 1: Synthesis of ADAME using fossil-derived compound (II)

[0312] In this embodiment, compound (II) is fossil-derived methyl acrylate.

[0313] The source of DMOH will be 100% fossil or semi-fossil, or 100% renewable and non-fossil source.

[0314] To form DMOH, two precursors are required: an ethanol precursor and a methanol precursor.

[0315] Renewable and non-fossil-derived DMOH can be derived from the treatment of pulp industry residues ("tall oil") or agricultural waste to form bioethanol precursors (which in turn form bio-oxides of ethylene). Methanol, on the other hand, can be derived from municipal waste treatment, biomass, through fermentation, or carbon dioxide recovery. Alternatively, the amino moiety of DMOH can also be derived from green ammonia.

[0316] As described in the following examples, renewable and non-fossil-derived DMOH has precursors that are entirely renewable and non-fossil-derived.

[0317] As described in the following examples, the semi-fossil-derived DMOH comes from at least one of these precursors being renewable and non-fossil-derived, while the other is of fossil origin. It will be the precursor. Bioethanol +Methanol (Source 1), or precursor ethanol+ born Methanol + Green Ammonia (Source 2)

[0318] The fossil source of DMOH is fossil ethylene.

[0319] 14 The C level is measured according to ASTM D6866-21 standard, Method B. This standard allows for the characterization of the biogenic nature of compounds by determining their biogenic carbon level.

[0320] 890g of methyl acrylate (compound II), 460g of DMOH, 130g of hexane, 18g of dibutyltin oxide (DBTO) and 1g of phenothiazine were added to a 2000mL jacketed reactor under stirring.

[0321] Then add 90g of hexane to the mixture.

[0322] The mixture is heated using the heating unit supplied with the reactor jacket until it reaches a temperature of 80°C.

[0323] The temperature of the mixture was maintained at 80°C for 7 hours.

[0324] Once the hexane and methanol vapors are condensed and collected, the synthesis reaction begins; hexane is continuously added to the reaction medium to compensate for the amount distilled.

[0325] Seven hours after the reaction, the reaction medium was sampled for analysis by gas chromatography to determine the degree of DMOH conversion.

[0326] The reaction medium was distilled at 95°C under reduced pressure using a vacuum pump.

[0327] Three fractions were collected under different pressures: the first fraction was collected under reduced pressure of 80 mbar absolute pressure; the second fraction was collected under reduced pressure of 6 mbar absolute pressure; and finally, the final fraction was collected under reduced pressure of 4 mbar absolute pressure.

[0328] By adjusting the source of DMOH and its... 14 The percentage in C is based on the test set according to the previous scheme (see Table 2).

[0329] 14 The wt% of C indicates the properties of carbon. "Zero pMC" means that there is absolutely no measurable carbon present in the material. 14 C indicates that it is a fossil carbon source.

[0330] Vinyl ethanol (VOE) level is an indicator of the level of impurities converted during DMOH production. The higher the ratio, the more difficult the polymerization becomes, and the final application performance will be affected.

[0331] To verify the conversion test from DMOH to ADAME, the DMOH conversion rate must be greater than or equal to 93%, and the ADAME purity must be greater than or equal to 99.8% (see Table 2).

[0332]

[0333] Table 2 (CEx = Counterexample; Inv = Embodiment of the Invention)

[0334] The applicant observed that some or all of the DMOH was renewable and of non-fossil origin, which could validate the conversion test.

[0335] Example 2: Synthesis of ADAME using a renewable and non-fossil-derived compound (II)

[0336] In this embodiment, compound II is a non-fossil-derived methyl acrylate containing 100% 14 C.

[0337] Reproduce the scheme previously described in Example 1.

[0338] The conditions for verifying the conversion of DMOH to ADAME were the same as in Example 1.

[0339]

[0340] Table 3 (CEx = Counterexample; Inv = Embodiment of the Invention)

[0341] The applicant observed that the properties of compound (II) affected the effectiveness of the conversion test.

[0342] II. Synthesis of ADAME using lipase-type biocatalysts:

[0343]

[0344] Example 3: Synthesis of fully renewable and non-fossil-derived ADAME:

[0345] 2500g methyl acrylate, 300g DMOH, 650g hexane, 250g lipase CalB (Novozyme) and 5g MEHQ were added to a 5000mL reactor with a double jacket under stirring.

[0346] Add 450g of hexane to the mixture above.

[0347] The mixture is heated by a heating unit supplied to the reactor jacket until it reaches a temperature of 40°C. Once this temperature is reached, the mixture is maintained at 40°C for 30 hours.

[0348] The synthesis reaction begins once the hexane and methanol vapors are condensed and collected. Hexane is continuously added to the reaction medium to compensate for the amount distilled.

[0349] After 30 hours at 40°C, samples of the reaction medium were taken to determine the degree of DMOH conversion.

[0350] The reaction medium was distilled at 95°C under reduced pressure using a vacuum pump.

[0351] Three fractions were collected under different pressures: the first fraction was collected under reduced pressure of 80 mbar absolute pressure; the second fraction was collected under reduced pressure of 6 mbar absolute pressure; and finally, the final distillate was collected under reduced pressure of 4 mbar absolute pressure.

[0352] As with the previous examples, DMOH from different sources was tested.

[0353] To verify the conversion test from DMOH to ADAME, the conversion rate must be greater than or equal to 80%, and the purity of ADAME must be greater than or equal to 99.8%.

[0354] (See Table 4.)

[0355]

[0356] Table 4 (CEx = Counterexample; Inv = Embodiment according to the present invention)

[0357] The biological origin of the precursor affects the transformation test as described above.

[0358] Example 4: Quaternized monomers of the present invention

[0359] In a 1000L stainless steel reactor with a pressure-resistant jacket, 300g of monomer from the aforementioned embodiment was added with stirring. The reactor was then sealed and pressurized with 1 bar of air.

[0360] The reaction medium is heated by the heating unit supplying the reactor jacket until it reaches a temperature of 40°C. Chloromethane is added at a flow rate of 111 g / h. Once 10% of the stoichiometric amount of chloromethane has been reached, water is simultaneously added at a flow rate of 42 g / h. When all the water has been added (i.e., 100 g), the addition of chloromethane is stopped, and the reactor is restored to atmospheric pressure.

[0361] Then air is introduced for 30 minutes to remove excess chloromethane.

[0362] This yields an aqueous solution of ADAME quaternized with chloromethane. The concentration of this salt in water is 80%.

[0363] According to the aforementioned scheme, by adjusting the source of ADAME and the source of chloromethane, and 14 The percentage of C is used for the test set (see Table 5).

[0364] Non-fossil-derived chloromethane can come from pulp industry residues ("tall oil"), agricultural or municipal waste treatment, biomass, through fermentation or carbon dioxide recovery. Alternatively, the chlorinated portion of chloromethane can also be derived from chlorine or green hydrogen chloride, i.e., produced from renewable energy sources.

[0365] Different products 14 The C ratio was determined according to ASTM D6866-21 Method B.

[0366]

[0367] Table 5 (CEx = Counterexample; Inv = Embodiment of the Invention)

[0368] III. Polymers of the Invention

[0369] Example 5: Biodegradability test of polymers P1 to P5.

[0370] Add deionized water and monomer (from Table 5) to a 2000 mL beaker.

[0371] The resulting solution was cooled to 5-10°C and transferred to an adiabatic polymerization reactor.

[0372] Perform nitrogen bubbling for 30 minutes to eliminate all trace amounts of dissolved oxygen.

[0373] Then the following substances are added to the reactor:

[0374] -0.45g 2,2′-azobisisobutyronitrile,

[0375] -1.5 mL 2.5 g / L 2,2′-azobis[2-(2-imidazolin-2-yl)propane aqueous solution] dihydrochloride,

[0376] -1.5 mL of 1 g / L sodium hypophosphite aqueous solution,

[0377] -1.5 mL of 1 g / L tert-butyl hydrogen peroxide aqueous solution,

[0378] -1.5 mL of 1 g / L ammonium sulfate aqueous solution and ferric(II) hexahydrate (Mohr's salt).

[0379] A few minutes later, the nitrogen bubbling was stopped. The polymerization reaction then proceeded for 4 hours to reach the peak temperature. Finally, the resulting polymer gel was chopped and dried, then crushed again and sieved to obtain polymer in powder form.

[0380] The biodegradability of the obtained polymer was assessed according to OECD 302B standards (after 28 days).

[0381] Mass (g) of quaternized ADAME 202.5 202.5 202.5 202.5 202.5 202.5 202.5 202.5 202.5 monomer M1 M2 M3 M4 M4 Cex7 CEx8 CEx9 CEx9 <![CDATA[of the 14 monomer, weight %]]> 87.5 97.5 82.5 100 100 0 0 0 0 Mass of acrylamide (g) 276 276 276 276 276 276 276 276 276 <![CDATA[Acrylamide 14 wt%]]> 0 0 0 0 100 0 0 0 100 Mass of water (g) 522 522 522 522 522 522 522 522 522 Biodegradability % 35 40 33 40 50 12 15 14 17

[0382] Table 6 (CEx = Counterexample)

[0383] The applicant observed that the biodegradability curve of the polymer of the present invention is 60% higher than that of the polymer without bio-derived monomers described in the present invention.

[0384] Example 6: Measurement of insolubility in polymer solution.

[0385] UL viscosity (Brookfield viscosity), insolubility, and insolubility point were measured on a polymer consisting of 70 mol% acrylamide and 30 mol% quaternized ADAME, prepared by conventional bulk polymerization.

[0386] UL viscosity was measured using a Brookfield viscometer with a UL adapter, which was rotated at 60 rpm between 23 and 25°C (0.1 wt% polymer in 1M sodium chloride solution).

[0387] The insolubility was determined by transferring 1 g of polymer solution to 200 mL of water at 20 °C, stirring for 2 h, and then filtering the dissolved solution through a filter with a diameter of 4 cm and a porosity of 200 μm. After completely draining the filtered solution, the filter paper was pressed down. For solutions that could not be filtered, the filter was placed at 105 °C for 4 hours. The residual mass was used to determine the insolubility, and the insolubility was related to the initial mass of the polymer. Vinyl acrylate impurities formed covalent bonds between 2-dimethylaminoethyl acrylate monomers, preventing the aggregates from passing through the filter.

[0388] Insoluble point refers to the number and size of aggregates on the filter. Use the following scale: small spots (pt) between 1 and 3 mm; large spots (bp) exceeding 3 mm (visual count).

[0389]

[0390] Table 7 (CEx = Counterexample)

[0391] The applicant observed that fully renewable and non-fossil-derived polymers have less insoluble matter.

[0392] IV. Uses of the polymers of the present invention

[0393] Example 7: Use of polymers as additives in papermaking processes.

[0394] Retention aids are polymers added to cellulose fiber pulp before papermaking to improve the paper's retention efficiency.

[0395] Pulp type used: Virgin fiber pulp:

[0396] Wet pulp is obtained by breaking down dry pulp to achieve a final water concentration of 1 wt%. It is a neutral pH pulp composed of 90% bleached virgin grown fiber, 10% bleached virgin short fiber, and 30% wt% additional GCC (ground calcium carbonate) (from Omya). 55) Composition.

[0397] Evaluation of total retention rate and filler retention rate

[0398] For all the following tests, the polymer solution was prepared at 0.5 wt%. After 45 minutes of preparation, the polymer solution was diluted 10-fold before injection.

[0399] Different results were obtained using a BrittJar apparatus with a stirring speed of 1000 rpm.

[0400] The process sequence is as follows:

[0401] -T = 0 seconds: Stir 500 mL of pulp with a concentration of 0.5 wt%.

[0402] -T = 10 seconds: Add retention aid (300g dry polymer / ton of dry pulp).

[0403] -T = 20 seconds: Remove the first 20 mL representing the dead volume under the cloth, then collect 100 mL of white water.

[0404] The first pass retention percentage (%FPR) corresponds to the total retention rate and is calculated using the following formula:

[0405] The percentage of ash retained in the first pass (%FPAR) is calculated using the following formula: in:

[0406] -CHB: Headbox consistency

[0407] -CWW: White Water Consistency

[0408] -AHB: Headbox ash consistency

[0409] For each analysis, the highest value represents the best performance.

[0410] Evaluation of gravity drainage performance using the Canadian Standard Degrees of Freedom (CSF)

[0411] The pulp was treated in a beaker with stirring at 1,000 rpm.

[0412] The process sequence is as follows:

[0413] -T = 0 seconds: Stir 500 mL of pulp with a concentration of 0.6 wt%.

[0414] -T = 10 seconds: Add retention aid (300g dry polymer / ton of dry pulp).

[0415] -T=20 seconds: Stop stirring and add the necessary amount of water to obtain 1 liter.

[0416] The pulp was transferred to a Canadian standard degrees of freedom tester and the TAPPI procedure T227om-99 was applied.

[0417] The volume (expressed as m1) provides a measure of free gravity. The higher the value, the better the gravity-driven displacement.

[0418] This performance can also be expressed as a percentage improvement relative to the blank (%CSF). The highest value represents the best performance.

[0419] The same polymer as described above was tested, and the results are as follows.

[0420] %FPAR 31.5 33.2 30.1 32.3 34.6 20.3 20.7 20.8 21 %FPR 72.3 74 75.6 77 78.5 64.2 64.8 65 65.4 %CSF 7.3 12.3 17.5 18.2 19.7 1.5 2 3.4 4.9

[0421] Table 8 (CEx = Counterexample)

[0422] The applicant observed that the polymers of the present invention provide better performance as retention aids for paper. Regarding water filtration, the polymers prepared using only the monomers of the present invention show an improvement of more than 25%.

[0423] Example 8: Measurement of drag reduction

[0424] Polymers P1 to P5 and CEx10 to 13 were dissolved in brine at a concentration of 10,000 ppm with stirring. Each liter of brine consisted of water, 85 g of sodium chloride (NaCl), and 33.1 g of calcium chloride (CaCl2, 2H2O).

[0425] The resulting polymer salt solution was then injected into the circulating brine at a concentration of 0.5 pptg (parts per kilogram) for flow loop testing.

[0426] In fact, in order to evaluate the drag reduction of each polymer and the polymers from Counterexamples 1 to 4, the reservoir of the flow loop (calibration tube length (loop): 6 mm, tube inner diameter: 4 mm) was filled with 20 L of brine as described above.

[0427] The brine was then circulated through the flow loop at a rate of 24 gallons per minute. A polymer was added to the circulating brine at a concentration of 0.5 pptg. The percentage of drag reduction was determined by measuring the pressure change within the flow loop.

[0428] Figures 1 to 4 These are graphs showing the percentage drag reduction for each polymer as a function of time. These graphs demonstrate that the injected fluid of the present invention can improve drag reduction.

Claims

1. A method for obtaining a monomer of formula (I), comprising a reaction between a compound of formula (II) and dimethylaminoethanol, wherein, R2 is a hydrogen atom or a CH3 group. R3 is a hydrogen atom or an alkyl group containing 1 to 8 carbon atoms, characterized in that the dimethylaminoethanol is at least partially renewable and non-fossil. The bio-based carbon content of the dimethylaminoethanol is 40 wt% to 100 wt% relative to the total carbon weight in the dimethylaminoethanol, and the bio-based carbon content is determined according to standard ASTM D6866-21 Method B. 。 2. The method according to claim 1, characterized in that, The bio-based carbon content of the compound of formula (II) is 25 wt% to 100 wt% relative to the total carbon weight in the compound, and the bio-based carbon content is determined according to standard ASTM D6866-21 Method B.

3. The method according to any one of claims 1 or 2, characterized in that, The bio-based carbon content of the monomer of formula (I) is 45 wt% to 100 wt% relative to the total carbon weight in the monomer, and the bio-based carbon content is determined according to standard ASTM D6866-21 Method B.

4. The method according to claim 1, characterized in that, The method is a biological method performed in the presence of a biocatalyst comprising a hydrolytic enzyme selected from the group consisting of lipases, esterases, glycosylation enzymes, and proteases; the hydrolytic enzyme is in free form or immobilized on a substrate.

5. The method according to claim 4, characterized in that, The enzyme is a lipase synthesized by microorganisms selected from the following group: Alcaligenes, Aspergillus, Mucor, Penicillium, Geotrichum, Rhizopus, Burkholderia, Candida, Pseudomonas, Thermophilic Fungi, and Candida antarcticis.

6. The method according to any one of claims 1 to 5, characterized in that, The dimethylaminoethanol and / or compound (II) are obtained, in part or entirely, from the recovery method.

7. A monomer of formula (I), wherein the bio-based carbon content of the monomer is from 45 wt% to 100 wt% relative to the total carbon weight in the monomer, the bio-based carbon content being determined according to ASTM D6866-21 Method B. R2 is a hydrogen atom or a CH3 group. 。 8. The monomer of formula (I), characterized in that, The monomer is obtained by reacting a compound of formula (II) with dimethylaminoethanol via a biological method in the presence of a biocatalyst containing a hydrolytic enzyme, wherein R2 is a hydrogen atom or a CH3 group, and R3 is a hydrogen atom or an alkyl group containing 1 to 8 carbon atoms. Furthermore, based on the total weight of carbon in the dimethylaminoethanol, the bio-based carbon content of the dimethylaminoethanol is 40 wt% to 100 wt%, and the bio-based carbon content is determined according to ASTM D6866-21 Method B. 。 9. The salting or quaternization form of the monomer of formula (I) obtained by the method according to claim 7 or 8, or according to claim 1 or 2.

10. A polymer obtained by polymerizing at least one monomer obtained by the method according to claim 1, or at least one monomer according to any one of claims 7 to 8, or a salted or quaternized form of the monomer according to claim 9.

11. The polymer according to claim 10, characterized in that, The polymer is a copolymer of the following: - at least one first monomer obtained by the method according to claim 1, or at least one first monomer according to claim 7 or 8, and - At least one second monomer different from the first monomer, the second monomer being selected from the group consisting of: nonionic monomers, anionic monomers, cationic monomers, zwitterionic monomers, monomers containing a hydrophobic portion, and mixtures thereof.

12. The polymer according to claim 10, characterized in that, The polymer is a copolymer of the following: - At least 5 mol% of the first monomer, said monomer being obtained by the method according to claim 1, or being the monomer according to any one of claims 7 to 8, or the salted or quaternized form of the monomer according to claim 9, and - At least 1 mol% of at least one second monomer containing olefin unsaturation, the second monomer being different from the first monomer, and the second monomer having a bio-source carbon content of 5 wt% to 100 wt% relative to the total carbon weight in the second monomer, said bio-source carbon content being determined according to standard ASTM D6866-21 Method B.

13. The polymer according to claim 10, characterized in that, The polymer is a copolymer of the following group: - 20 mol% to 90 mol% of a first monomer, said monomer being obtained by the method according to claim 1, or being a monomer according to any one of claims 7 to 8, or a salted or quaternized form of the monomer according to claim 9, and At least one second monomer containing olefin unsaturation of -5 mol% to 95 mol%, the second monomer being different from the first monomer, and having a bio-source carbon content of 5 wt% to 100 wt% relative to the total carbon weight in the second monomer, said bio-source carbon content being determined according to standard ASTM D6866-21 Method B.

14. The polymer according to claim 12, characterized in that, The second monomer is selected from the group consisting of: acrylamide, acrylic acid and / or its salts, methacrylic acid and / or its salts, acrylic acid oligomers, 2-acrylamido-2-methylpropanesulfonic acid and / or its salts, N-vinylformamide, N-vinylpyrrolidone, dimethyldiallylammonium chloride, or the formula CH2=CHCO-NR. 1 R 2 The substitution of acrylamide, R 1 and R 2 Each is an independent straight-chain or branched carbon chain (C). n H 2n+1 , where n is from 1 to 10.

15. The polymer of claim 10, wherein the bio-based carbon content of the polymer is from 5 wt% to 100 wt% relative to the total carbon weight in the polymer, the bio-based carbon content being determined according to ASTM D6866-21 Method B.

16. Use of at least one monomer obtained by the method according to claim 1, or at least one monomer according to any one of claims 7 to 8, or a salted or quaternized form of the monomer according to claim 9, for the synthesis of polymers.

17. Use of the polymer according to any one of claims 10 to 15 in the fields selected from the group consisting of: hydrocarbon recovery; drilling and cementing; hydrocarbon well enhancement; water treatment; fermentation slurry treatment; sludge treatment; papermaking; construction; wood processing; hydraulic composition processing; mining; cosmetic formulation; detergent formulation; textile manufacturing; battery component manufacturing; geothermal energy; sanitary napkin manufacturing; or agriculture.

18. Use of the polymer according to any one of claims 10 to 15 as a flocculant, coagulant, adhesive, fixative, viscosity reducer, thickener, absorbent, drag reducer, dehydrating agent, drainage agent, charge retainer, dehydrating agent, conditioning agent, stabilizer, film-forming agent, sizing agent, superplasticizer, clay inhibitor, or dispersant.

19. A method for enhancing oil and / or gas recovery by clearing underground formations, comprising the following steps: a. An injection fluid is prepared from the polymer according to any one of claims 10 to 15 with water or brine. b. Inject the fluid into the underground formation. c. Clean the underground strata with the injected fluid. d. Recovering aqueous mixtures of oil and / or gas.

20. A method for hydraulic fracturing of underground oil and / or gas reservoirs, comprising the following steps: a. An injection fluid is prepared from the polymer according to any one of claims 10 to 15 with water or brine and with at least one proppant. b. Inject the fluid into the underground reservoir and fracture at least a portion of it to recover oil and / or gas.

21. A method for drilling and / or cementing wells in underground formations, comprising the following steps: a. A fluid prepared from the polymer according to any one of claims 10 to 15 with water or brine. b. In at least one step of drilling or cementing, the drilling and / or cementing fluids are injected into the underground formation via a drill bit.

22. A method for manufacturing paper and paperboard, wherein, Before the paper is formed, at least one polymer according to any one of claims 10 to 15 is added to the fiber suspension at one or more injection points.

23. A method for treating municipal water and industrial water, comprising adding at least one polymer according to any one of claims 10 to 15 to the municipal water or industrial water.

24. A thickener for use in cosmetic, dermatological, pharmaceutical, or detergent compositions, said thickener comprising at least one polymer according to any one of claims 10 to 15.

25. A thickener for a pigment composition used in textile printing, said thickener comprising at least one polymer according to any one of claims 10 to 15.

26. A method for treating a suspension of solid particles in water generated from mining or oil sands operations, comprising contacting the suspension with at least one polymer according to any one of claims 10 to 15.

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