FR3125048A1 - Bio-based polymer with improved biodegradability - Google Patents

Abstract

The present invention relates to a biobased polymer with improved biodegradability obtained by polymerization of at least one oligomer of acrylic acid or of one of its salts, said oligomer being at least partly of renewable and non-fossil origin, and n being between 1 and 10.

Description

Bio-based polymer with improved biodegradability

Field of invention

The present invention relates to a biobased polymer with improved biodegradability. The polymer according to the invention is made from at least one biosourced oligomer of acrylic acid or one of its salts. The invention also relates to a process for manufacturing the bio-based oligomer, and the use of the bio-based polymers of the invention in various technical fields.

Prior state of the art

The acrylic acid oligomer is made from acrylic acid (CH ₂ =CH-C(=O)-OH). Acrylic acid has fossil origins and comes from the propylene (propene) industry. Acrylic acid comes from the oxidation of propylene with air.

Propylene (CH ₂ =CH-CH ₃ ) is an olefin of fossil origin, and is currently produced by steam cracking of naphtha, itself coming from the refining of crude oil. More recently, and with the advent of shale gas production, various processes for the dehydrogenation of propane to produce propylene have been described.

Propylene of fossil origin contains various impurities, which remain or are transformed in the production process of acrylic acid.

Document US 8,415,498 describes, for example, the production of acrylic acid from propylene, in the presence of a catalyst, the whole being brought to a very high temperature in order to obtain acceptable conversions and selectivities. The hot gases must be cooled with water, therefore it is necessary to purify the acrylic acid thus obtained from the aqueous matrix, and to separate it from the reaction impurities. Many techniques have been described, the two preponderant being separation by vacuum distillation and fractional recrystallization, as described for example in document US 7,183,428.

Many alternative ways of producing acrylic acid have been described in the past, for example by fermentation of glucose, glycerol, as described in documents EP 1 874 720 and WO 2012/074818. These technologies have in common to obtain a synthesis intermediate, 3-hydroxypropionic acid (or 3-hydroxypropanoic acid) in the context of the fermentation of glucose, which must then undergo a reaction step at very high temperature. , thus generating many impurities. The resulting acrylic acid must also be purified.

Acrylic acid can be oligomerized, generally by Michael addition reaction, in the presence of acid or base, as for example described in document US 4,267,365.

The problem that the invention sets out to solve is to provide a new biobased polymer with improved biodegradability and offering improved application properties.

Quite surprisingly, the Applicant has observed that a polymer obtained by polymerization of at least one oligomer of acrylic acid at least partly of renewable and non-fossil origin makes it possible to improve the application performance of said polymer while by giving it a biosourced nature and an improved biodegradability property.

Without wishing to be bound by any theory, the Applicant puts forward the possibility that the different nature of the impurities between an acrylic acid of petrochemical origin and an acrylic acid of renewable and non-fossil origin is the cause of these unexpected technical effects ( improved performance and biodegradability).

Throughout the application, the terms "oligomer of acrylic acid" include the acid version of the oligomer, and also the corresponding salts of the oligomer of acrylic acid. The salts of these oligomers are, for example, alkali metal, alkaline-earth metal or ammonium salts. Preferred salts are sodium, potassium and ammonium salts.

Thus, throughout the application, formula (1) includes not only formula (1) as drawn, but it also includes the salts corresponding to formula (1), that is to say when the the hydrogen atom to the right of the molecule of formula (1) is replaced by an alkali metal cation, alkaline-earth metal cation, or by NH ₄ ⁺ ; then the adjacent oxygen atom becomes negatively charged and becomes O ^- .

The invention firstly relates to a biobased polymer with improved biodegradability obtained by polymerization of at least one oligomer of acrylic acid according to formula (1) or one of its salts, said oligomer being at least partly of of renewable and non-fossil origin, and n being between 1 and 10, preferably between 2 and 5.

In the present description, the expressions "between X and Y" and "from X to Y" include the terminals X and Y.

Generally and unless otherwise indicated, formula (1) designates an oligomer being at least partly of renewable and non-fossil origin.

The polymer according to the invention preferably has a biodegradability of between 20% and 100%, the biodegradability being measured according to the OECD 302B standard, known as the Zahn-Wellens standard. The value is expressed as a percentage of degradation relative to the control reference ethylene glycol (HO-CH ₂ -CH ₂ -OH).

The invention also relates to an oligomer of acrylic acid according to formula (1) or one of its salts, said oligomer being at least partly of renewable and non-fossil origin, and n being between 1 and 10, preferably between 2 and 5.

The invention also relates to a process for the manufacture of an oligomer of formula (1) or one of its salts comprising the reaction of acrylic acid with a source of Brønsted acid or a source of Brønsted base and in presence of at least 0.1% by weight of water, said acrylic acid being at least partly of renewable and non-fossil origin.

In a particularly preferred embodiment of the invention, the acrylic acid used to manufacture the oligomer according to the invention is preferably obtained by a biological process, said biological process comprising at least one step of bioconversion by enzymatic means in the presence of a biocatalyst comprising at least one enzyme.

A subject of the invention is also the reaction mixture obtained according to the process of the invention. This reaction mixture may comprise a mixture of at least two molecules of formula (1) having a different n value, n being between 0 and 10, preferably between 0 and 5. When n=0 then the molecule is the acid acrylic; this is particularly the case when all the acrylic acid or one of its salts has not reacted. This may well occur during the process according to the invention. “m” is the mean of the “n” values of the reaction mixture. The value “m” is then preferentially between 0.1 and 10, more preferentially between 0.2 and 5, even more preferentially between 0.5 and 4.

In other words, if the reaction mixture comprises 10% molar of acrylic acid (n=0), 30% molar of oligomer according to formula 1 with n=1, 30% molar of oligomer according to formula 1 with n=2 , and 30 molar % of oligomer according to formula 1 with n=3, then m=0.1*0+0.3*1+0.3*2+0.3*3, i.e. 1.8. If the mole percentages are 60%, 20%, 10%, and 10%, respectively, then m = 0.7.

The invention also relates to the use of the polymer according to the invention in various applications and processes using the polymer according to the invention.

Thanks to the present invention, it is possible to achieve environmental objectives inherent in new technical innovations. In the present case, the polymer obtained makes it possible to improve the application performance of said polymer while giving it a biosourced nature and improving its biodegradability.

Detailed disclosure of the invention

In the context of the invention, the term "of renewable and non-fossil origin" denotes the origin of a chemical compound derived from biomass or synthesis gas (syngas), i.e. say being the result of one or more chemical transformations carried out on one or more raw materials having a natural origin, and not fossil. The terms "bio-based" or "bio-based" can also be used to characterize the renewable and non-fossil origin of a chemical compound. The renewable and non-fossil origin of a compound includes renewable and non-fossil raw materials from the circular economy, and which have been previously recycled, one or more times, during a process of recycling material from biomass, such as, for example, materials resulting from the depolymerization of polymers or from the transformation of pyrolysis oil.

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

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

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

This standard mainly uses the technology of the AMS (Accelerator Mass Spectrometry) in English, mass spectrometry by accelerator. This technique is used to naturally measure the radionuclides present in a sample, in which the atoms are ionized, then accelerated to high energies, then separated, and individually counted in Faraday collectors. This high-energy separation is extremely effective at filtering out isobaric interference, so the AMS is able to accurately measure the abundance of carbon-14 relative to carbon-12 (14C ⁄ 12C) to an accuracy of 1.10 ^-15 .

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

The sample preparation method is described in the standard and does not require any particular comments as it corresponds to a commonly used procedure.

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

All pMC values obtained from radiocarbon analyzes should be corrected for isotopic fractionation using a given stable isotope. The correction should be made using the values of carbon-14 content compared to carbon-13 determined directly using the AMS when possible. If this is not possible, correction should be made using delta 13C (δ13C) measured by IRMS, CRDS (Cavity Ring Down Spectroscopy) or any other equivalent technology that can provide precision to plus or minus 0.3 per thousand.

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

The pMC may be greater than 100% due to the continuing, but diminishing, effects of atmospheric 14C injection caused by atmospheric nuclear testing programs. pMC values should be adjusted by an atmospheric correction factor (REF) to obtain the true biobased content of the sample.

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

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

Table 1: Modern Percent Carbon (pMC) Reference

In the context of the invention, the term "segregated" is understood to mean a material flow that is distinctive and distinguishable from other material flows in a value chain (for example in a process for manufacturing a product), and this fact considered as part of a set of materials having an equivalent nature, so that we can follow and guarantee throughout this value chain the same origin of the material, or its manufacture according to the same standard or the same standard.

This corresponds, for example, to the purchase by a chemist of 100% biosourced acrylic acid exclusively from a single supplier who guarantees the 100% biosourced origin of the acrylic acid delivered, and the treatment separately from other potential sources of acid by said chemist transforming this 100% biobased acrylic acid to produce a chemical compound. If the chemical compound produced is only made from said 100% biobased acrylic acid, then the chemical compound is 100% biobased.

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

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

According to ADEME (Agence De l'Environnement et de la Maitrise de l'Energie), the circular economy can be defined as an economic system of exchange and production which, at all stages of the life cycle of products ( goods and services), aims to increase the efficiency of the use of resources and reduce the impact on the environment while developing the well-being of individuals. In other words, it is an economic system dedicated to efficiency and sustainability that minimizes waste by optimizing the value generated by resources. It relies heavily on various conservation and recycling methods to break away from the current, more linear approach of “grab, produce and throw away”.

In the field of chemistry, which is the science of transforming a substance into another substance, this results in the reuse of a material that has already been used to manufacture a product. Theoretically all chemicals can be isolated and therefore recycled separately from other chemicals. The industrial reality in particular is more complex and means that even isolated, the compound cannot very often be distinguished from the same compound coming from another origin, making the traceability of the recycled material complex.

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

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

One of these models is “segregation” which we have given a definition of previously. Some known examples for which this model applies are glass and certain metals for which it is possible to follow the flows of matter separately.

But the chemicals are often used in complex combinations, and the distinct cycles are very often difficult to set up, in particular for reasons of prohibitive costs and ultra-complex flow management, which means that the "segregation" model is not always applicable.

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

The mass or weight balance approach consists in carrying out precise accounting monitoring of the proportion of a category (for example "recycled") in relation to a whole in a production system in order to ensure, on the basis of of an auditable ledger, a proportionate and appropriate attribution of the content of said category in a finished product.

This may correspond, for example, to the purchase by a chemist of 50% biobased acrylic acid from a supplier guaranteeing, according to the mass or weight balance approach, that in the acrylic acid delivered, 50% of the acrylic acid has a bio-based origin, and de facto 50% does not have a bio-based origin, and the use by said chemist of this 50% bio-based acrylic acid with another stream of 0% bio-based acrylic acid, both streams that can no longer be distinguished at a certain point in the production, due to mixing for example. If the chemical compound produced is made from 50% by weight guaranteed 50% bio-based acrylic acid, and 50% by weight 0% bio-based acrylic acid, then the chemical compound is 25% bio-based.

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

In the context of the invention, the term “recycled” is understood to mean the origin of a chemical compound resulting from a process for recycling a material considered as waste, that is to say being the result of one or more transformations carried out during at least one recycling process on at least one material generally considered as waste.

The term “water-soluble polymer” means a polymer which gives a clear aqueous solution when it is dissolved with stirring at 25° C. and with a concentration of 20 gL ⁻¹ in water.

Polymer according to the invention

The invention relates to a biobased polymer with improved biodegradability obtained by polymerization of at least one oligomer of acrylic acid according to formula (1) or of one of its salts, said oligomer being at least partly of renewable origin and non-fossil, and n being between 1 and 10, preferably between 2 and 5.

The expression "with improved biodegradability" may be deleted if necessary in order to redefine the objects included in this application.

In the invention and in the various embodiments set out below, the oligomer according to formula (1) preferably has a biobased carbon content of between 5% by weight and 100% by weight relative to the total weight of carbon. in the oligomer, the biobased carbon content being measured according to standard ASTM D6866-21, method B.

The invention also relates to a biobased polymer with improved biodegradability obtained by polymerization of at least one oligomer of acrylic acid according to formula (1) or of one of its salts, said oligomer being obtained from acrylic acid being at least partly of renewable and non-fossil origin.

The invention also relates to a biobased polymer with improved biodegradability obtained by polymerization of at least one reaction mixture obtained according to a process for the manufacture of an oligomer of formula (1) or of one of its salts, comprising the reaction of acrylic acid with a source of Brønsted acid or a source of Brønsted base and in the presence of at least 0.1% by weight of water, said acrylic acid being at least partly of renewable and non-fossil origin. This method corresponds to the method according to the invention mentioned above in the summary of the invention, and detailed below.

In the invention and in the various embodiments set out below, the acrylic acid preferably has a biobased carbon content of between 5% by weight and 100% by weight relative to the total weight of carbon in said acrylic acid, the biobased carbon content being measured according to the ASTM D6866-21 standard, method B.

In the invention and in the various embodiments set out below, the acrylic acid is preferably partially or totally derived from bio-propylene. By bio-propylene is meant a bio-sourced propylene. Bio-propylene can be derived from a bacterial fermentation reaction of glucose, as described in example 8 of document WO 2014/086780. Bio-propylene can also be obtained by steam cracking of bio-naphtha, the latter being derived from vegetable oil as described in document WO 2014/111598. In a preferred mode, the bio-propylene comes from a recycling process. It is for example obtained by a recycling process comprising the depolymerization of polypropylene.

By polymer or (co)polymer is meant a homopolymer of the oligomer of formula (1) or a copolymer of the oligomer of formula (1) and of at least one monomer distinct from the oligomer of formula (1) , for example, but not limited to a terpolymer.

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

In a particularly preferred mode according to the invention, the acrylic acid is not only at least partly of renewable and non-fossil origin, but it is also preferentially obtained, partially, preferentially totally, by a biological process, said biological process comprising at least one enzymatic bioconversion step in the presence of a biocatalyst comprising at least one enzyme. Enzymes are able to transform one chemical function into another chemical function.

The combination of the biosourced nature of acrylic acid and its method of obtaining by a biological process of bioconversion makes it possible, unexpectedly, to obtain in the end a polymer with particularly advantageous application properties, and this, beyond its bio-sourced and bio-obtained character.

Throughout the invention, reference may be made to the which details, inter alia, in a general diagram, the various routes for obtaining the oligomer of formula (1) according to the invention.

In the invention and in the various embodiments set out below, the term “biological process” means a process comprising at least one enzymatic bioconversion step in the presence of a biocatalyst comprising at least one enzyme, preferably a process comprising at least one at least two bioconversion steps by enzymatic route, each step being carried out in the presence of a biocatalyst comprising at least one enzyme.

The acrylic acid, at least partly of renewable and non-fossil origin, can be obtained from an acrylate salt, itself obtained according to the various processes described below.

In a first embodiment, the acrylate salt is obtained directly from acrylonitrile at least partly of renewable and non-fossil origin. The acrylate bio-salt is obtained by bioconversion of acrylonitrile at least in part of renewable and non-fossil origin, said bioconversion comprising at least one step of enzymatic hydrolysis of said acrylonitrile in the presence of a biocatalyst comprising at least one enzyme nitrilase.

The enzyme contained in the biocatalyst making it possible to obtain the acrylate salt is a nitrilase preferentially synthesized by a microorganism of the Bacillus, Bacteridium, Micrococcus, Brevibacterium, Corynebacterium, Pseudomonas, Acinetobacter, Xanthobacter, Streptomyces, Rhizobium, Klebsiella, Enterobacter, Erwinia, Aeromonas, Citrobacter, Achromobacter, Agrobacterium, Pseudonocardia, Rhodococcus such as Rhodococcus rhodochrous, Comamonas, Saccharomyces, Dietzia, Clostridium, Lactobacillus, Escherichia, Agrobacterium, Mycobacterium, Methylophilus, Propionibacterium, Actinobacillus, Megasphaera, Aspergillus, Candida or Fusarium, preferably Rhodococcus rhodochrous.

According to the first embodiment, the invention relates to a biobased polymer with improved biodegradability obtained by polymerization of at least one oligomer of acrylic acid according to formula (1) in which n is between 1 and 10, preferably between 2 and 5, said oligomer being obtained from acrylic acid, itself obtained from ammonium acrylate, said ammonium acrylate being obtained by bioconversion of acrylonitrile at least partly of renewable and non-fossil origin, said bioconversion comprising at least one step of enzymatic hydrolysis of said acrylonitrile in the presence of a biocatalyst comprising at least one nitrilase enzyme.

In the invention and in the various embodiments set out below, the bio-acrylonitrile can be obtained either from bio-propylene or from bio-3-hydroxypropionitrile.

In a second embodiment, the acrylate salt is obtained from acrylamide at least partly of renewable and non-fossil origin, itself obtained from acrylonitrile at least partly of renewable origin and not fossil. The acrylate bio-salt is obtained by bioconversion of acrylamide at least in part of renewable and non-fossil origin, said bioconversion comprising at least one step of enzymatic hydrolysis of said acrylamide in the presence of a biocatalyst comprising at least one enzyme amidase, said acrylamide being obtained by bioconversion of acrylonitrile at least partly of renewable and non-fossil origin, said bioconversion comprising at least one step of enzymatic hydrolysis of said acrylonitrile in the presence of a biocatalyst comprising at least one nitrile hydratase enzyme.

The enzyme nitrile hydratase is preferentially synthesized by a microorganism of the Bacillus, Bacteridium, Micrococcus, Brevibacterium, Corynebacterium, Pseudomonas, Acinetobacter, Xanthobacter, Streptomyces, Rhizobium, Klebsiella, Enterobacter, Erwinia, Aeromonas, Citrobacter, Achromobacter, Agrobacterium, Pseudonocardia type microorganisms. , Rhodococcus such as Rhodococcus rhodochrous, Comamonas, Saccharomyces, Dietzia, Clostridium, Lactobacillus, Escherichia, Agrobacterium, Mycobacterium, Methylophilus, Propionibacterium, Actinobacillus, Megasphaera, Aspergillus, Candida or Fusarium, preferably Rhodococcus rhodochrous, and more preferably Rhodococcus rhodochrous J1.

The amidase enzyme is preferentially synthesized by the following microorganisms: Rhodococcus Erythropolis, Pseudomonas methylotropha, Rhodococcus rhodochrous or Comamonas testosteroni, and more preferentially Rhodococcus rhodochrous.

According to the second embodiment, the invention relates to a biobased polymer with improved biodegradability obtained by polymerization of at least one oligomer of acrylic acid according to formula (1) in which n is between 1 and 10, preferably between 2 and 5, said oligomer being obtained from acrylic acid, itself obtained from ammonium acrylate, said ammonium acrylate being obtained by bioconversion of acrylamide at least partly of renewable and non-fossil origin , said bioconversion comprising at least one step of enzymatic hydrolysis of said acrylamide in the presence of a biocatalyst comprising at least one amidase enzyme, said acrylamide being obtained by bioconversion of acrylonitrile at least in part of renewable and non-fossil origin, said bioconversion comprising at least one enzymatic hydrolysis step of said acrylonitrile in the presence of a biocatalyst comprising at least one nitrile hydratase enzyme.

In a third embodiment, the acrylate salt is obtained from 3-hydroxypropionitrile.

The invention also relates to a biobased polymer with improved biodegradability obtained by polymerization of at least one oligomer of acrylic acid according to formula (1) in which n is between 1 and 10, preferably between 2 and 5, said oligomer being obtained from acrylic acid, itself obtained from 3-hydroxypropionitrile at least partly of renewable and non-fossil origin, said biological process comprising at least one step of bioconversion by enzymatic means in the presence of a biocatalyst comprising at least one enzyme.

In a first variant of the third embodiment, the 3-hydroxypropionitrile, at least partly of renewable and non-fossil origin, is converted into 3-hydroxypropionamide by enzymatic bioconversion in the presence of a biocatalyst comprising at least one nitrile hydratase enzyme, said 3-hydroxypropionamide then being transformed into 3-hydroxypropionic acid salt by enzymatic bioconversion in the presence of a biocatalyst comprising at least one amidase enzyme, said 3-hydroxypropionic acid salt being transformed into 3-hydroxypropionic acid, said 3-hydroxypropionic acid being finally transformed into acrylic acid.

In a second variant, third embodiment, the 3-hydroxypropionitrile, at least in part of renewable and non-fossil origin, is transformed into the 3-hydroxypropionic acid salt by enzymatic bioconversion in the presence of a biocatalyst comprising at least one enzyme nitrilase, said 3-hydroxypropionic acid salt being transformed into 3-hydroxypropionic acid, said 3-hydroxypropionic acid finally being transformed into acrylic acid.

In a third variant of the third embodiment, the 3-hydroxypropionitrile, at least partly of renewable and non-fossil origin, is converted into 3-hydroxypropionamide by enzymatic bioconversion in the presence of a biocatalyst comprising at least one nitrile hydratase enzyme, said 3-hydroxypropionamide then being converted into a 3-hydroxypropionic acid salt by enzymatic bioconversion in the presence of a biocatalyst comprising at least one amidase enzyme, said 3-hydroxypropionic acid salt being converted into an acrylate salt, said acrylate salt being finally transformed into acrylic acid.

In a fourth variant of the third embodiment, the 3-hydroxypropionitrile, at least in part of renewable and non-fossil origin, is transformed into a 3-hydroxypropionic acid salt by enzymatic bioconversion in the presence of a biocatalyst comprising at least one nitrilase enzyme, said 3-hydroxypropionic acid salt being transformed into acrylate salt, said acrylate salt finally being transformed into acrylic acid.

The second embodiment is more particularly preferred.

The biobased polymer with improved biodegradability according to the invention preferably has a biodegradability of between 20 and 100%, the biodegradability being measured according to the OECD 302B standard, known as the Zahn-Wellens standard. The biodegradability of the polymer according to the invention is preferentially between 30% and 100%, more preferentially greater than 40%, even more preferentially greater than 50%, even more preferentially greater than 60%, even more preferentially greater than 70%, even more preferably greater than 80%, even more preferably greater than 90%.

The polymer according to the invention offers the advantage of being partially or totally biobased. It can also, in a preferred mode, be obtained from bio-obtained monomers, that is to say obtained according to a biological process involving a biocatalyst comprising at least one enzyme. In English we speak of “soft chemistry”, or soft chemistry. The acrylic acid raw material can also, in a preferred mode, come from a recycling process. Finally, the polymer according to the invention has biodegradable properties. Then the polymer according to the invention can claim to participate in the virtuous circle of the circular economy.

The acrylic acid or the acrylate salt used to obtain the oligomer according to the invention can be non-segregated, partially segregated, or totally segregated.

When the acrylic acid or acrylate salt is totally of renewable and non-fossil origin, then it can be:
a) Either entirely of recycled origin and
a)1) Is completely segregated;
a)2) Is partially segregated;
a)3) Is non-segregated;
b) Either partially of recycled origin and
b)1) Is completely segregated;
b)2) Is partially segregated;
b)3) Is non-segregated;
c) Either totally of non-recycled origin and
c)1) Is totally segregated;
c)2) Is partially segregated;
c)3) Is non-segregated.

In these different modes, when the acrylic acid or the acrylate salt is partially segregated, then the ratio by weight between the "segregated" part and the "non-segregated" part is preferably between 99:1 and 10:90, preferably between 99:1 and 30:70, more preferably between 99:1 and 50:50.

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

Industrial reality means that it is not always possible to obtain industrial quantities of acrylic acid or bio-based acrylate salt that is totally recycled and/or segregated or with a high degree of recycling and/or segregation. This is why the aforementioned preferences are perhaps more difficult to implement at present. From a practical point of view, modes a)3), b)3), and modes c) are implemented more easily and on a larger scale today. As techniques are rapidly evolving in the direction of the circular economy, there is no doubt that the preferred modes, which can already be applied, will be able to be applied on a very large scale quickly.

When the acrylic acid or acrylate salt is partially of renewable and non-fossil origin, then a distinction is made between the part of renewable origin (bio-based) and the non-bio-based part. Each of these parts can of course be according to the same modes a) b) and c) previously described.

With regard to the bio-based part of the partially bio-based compound, the same preferences as in the case where the compound is totally bio-based apply.

But when it comes to the non-biobased part of the partially biobased compound, then it is even more preferable to have as much recycled component as possible for a circular economy approach. This is why, in this case, modes a)1), a)2), b)1), b)2) are preferred, and particularly a)1) and b)1).

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

The polymer according to the invention can be a homopolymer or a copolymer of at least one oligomer according to the invention, and of at least one different additional monomer. The polymer according to the invention is preferably obtained by polymerization of at least one oligomer of formula (I) or of one of its salts, and of at least one different additional monomer, the latter being advantageously chosen from at least one monomer nonionic, and/or at least one anionic monomer, and/or at least one cationic monomer, and/or at least one zwitterionic monomer and/or at least one monomer comprising a hydrophobic group.

Thus, the copolymer can comprise at least one second monomer different from the first monomer, this second monomer being chosen from nonionic monomers, anionic monomers, cationic monomers, zwitterionic monomers, monomers comprising a hydrophobic group, and mixtures thereof.

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

The anionic monomer is preferably chosen from acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, acrylamido undecanoic acid, 3-acrylamido 3 acid -methylbutanoic acid, maleic anhydride, 2-acrylamido-2-methylpropane sulfonic acid (ATBS), vinylsulfonic acid, vinylphosphonic acid, allylsulfonic acid, methallylsulfonic acid, 2-sulfoethylmethacrylate, sulfopropylmethacrylate , sulfopropylacrylate, allylphosphonic acid, styrenesulfonic acid, 2-acrylamido-2-methylpropane disulfonic acid, and the water-soluble salts of these monomers such as their alkali metal, alkaline earth metal, or ammonium. It is preferably acrylic acid (and/or one of its salts), and/or ATBS (and/or one of its salts).

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

The zwitterionic monomer can be a derivative of a unit of the vinyl type, in particular acrylamide, acrylic, allylic or maleic, this monomer having an amine or ammonium function (advantageously quaternary) and an acid function of the carboxylic (or carboxylate), sulphonic ( or sulfonate) or phosphoric (or phosphate).

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

Each of these monomers can also be biosourced.

According to the invention, the polymer can have a linear, branched, star (star-shaped), comb (comb-shaped), dendritic or block structure. These structures can be obtained by selection of the choice of the initiator, the transfer agent, the polymerization technique such as the controlled radical polymerization called RAFT (reversible chain transfer by addition-fragmentation, from the English "reversible -addition fragmentation chain transfer"), NMP (polymerization in the presence of nitroxides, from the English "Nitroxide Mediated Polymerization") or ATRP (radical polymerization by transfer of atoms, from the English "Atom Transfer Radical Polymerization"), of the incorporation of structural monomers, concentration...

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

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

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

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

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

The invention also relates to a composition comprising at least one polymer according to the invention and at least one natural polymer, said natural polymer being preferably chosen from the natural polymers described above. The ratio by weight between the synthetic polymer and the natural polymer is generally between 90:10 and 10:90. The composition can be in liquid form, invert emulsion or in powder form.

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

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

The polymer according to the invention can be modified after it has been obtained by polymerization. We then speak of post modification of the polymer. All known post-modifications can be applied to the polymer according to the invention, and the invention also relates to the polymers obtained after said post-modifications. Among the possible post modifications developed below are post hydrolysis, post modification by Mannich reaction, post modification by Hoffman reaction and post modification by glyoxalation reaction.

The polymer according to the invention can be obtained by carrying out a post-hydrolysis reaction on a polymer obtained by polymerization of at least one oligomer obtained by the process according to the invention or of at least one oligomer as previously described in the part “oligomer”. Before post-hydrolysis, the polymer comprises, for example, monomeric units of acrylamide or methacrylamide. The polymer may also further comprise monomeric units of N-vinylformamide, more precisely the post-hydrolysis consists of the reaction of hydrolyzable functional groups of advantageously nonionic monomeric units, more advantageously amide or ester functions, with an agent of hydrolysis. This hydrolysis agent can be an enzyme, an ion exchange resin, an alkali metal, or an appropriate acidic compound. Preferably, the hydrolysis agent is a Brønsted base. When the polymer comprises amide and/or ester monomeric units, then the post-hydrolysis reaction produces carboxylate groups. When the polymer comprises vinylformamide monomeric units, then the post-hydrolysis reaction produces amine groups.

The polymer according to the invention can be obtained by carrying out a Mannich reaction on a polymer obtained by polymerization of at least one oligomer obtained by the process according to the invention or of at least one oligomer as previously described in the part "oligomer ". More specifically, before the Mannich reaction, the polymer advantageously comprises monomeric units of acrylamide and/or methacrylamide. The Mannich reaction is carried out in aqueous solution in the presence of a dialkyl amine and a formaldehyde precursor. More preferably the dialkyl amine is dimethylamine and the formaldehyde precursor is formaldehyde itself. After this reaction, the polymer contains tertiary amines.

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

This reaction, discovered by Hofmann at the end of the nineteenth century, makes it possible to convert an amide function into a primary amine function with one less carbon atom. The reaction mechanism is detailed below.

In the presence of a Brønsted base (e.g. sodium hydroxide), a proton is stripped from the amide.

The amidate ion formed then reacts with the active chlorine (Cl ₂ ) of the hypochlorite (eg: NaClO which is in equilibrium: 2 NaOH + Cl ₂ NaClO + NaCl + H ₂ O) to give an N-chloramide. The Brønsted base (e.g. NaOH) strips a proton from the chloramide to form an anion. The anion loses a chloride ion to form a nitrene which undergoes rearrangement to isocyanate.

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

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

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

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

According to the invention, the polymer can be in liquid, gel or solid form when its preparation includes a drying step such as “spray drying” (drying by spraying), drying on a drum, drying by radiation such as microwave drying, or fluidized bed drying.

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

These aqueous liquid absorption properties are particularly appreciated in fields such as agriculture or sanitary diapers. These super absorbent polymers are generally in the form of solid particles which, when brought into contact with water or an aqueous liquid, swell absorbing said liquid to form a structured gel. Once inflated, the particles are able to return the absorbed liquid; this property is used in particular in agriculture, a field in which the particles then act as mini water reservoirs capable of restoring water in times of water stress. The tests on these polymers consist, for example, in evaluating their absorbent capacity, their capacity to retain or release water, and their resistance to mechanical or physical stresses such as temperature.

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

The polymer according to the invention is preferably obtained by polymerization of at least one oligomer of formula (1) or of one of its salts, and of at least one monomer, the latter being a nonionic monomer, and/or a anionic monomer, and/or a cationic monomer, and/or a zwitterionic monomer, and/or a monomer comprising a hydrophobic group.

Said monomer polymerized with the oligomer according to the invention is preferably also at least partly, preferably totally of renewable and non-fossil origin.

Thus, in a preferred embodiment, the invention relates to a polymer comprising:
- at least 5% molar, preferably at least 10% molar, preferably between 20% and 99% molar, more preferably between 30% and 90% of an oligomer of formula (1) according to the invention, and
- at least 1% molar, preferably between 5% and 90% molar, more preferably between 10% and 80% molar of at least one second monomer (the first monomer relating to the monomeric unit of the oligomer of formula ( 1)) comprising ethylenic unsaturation, said second monomer being at least partly of renewable and non-fossil origin.

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

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

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

In this preferred embodiment, the second monomer and the optional other monomers are preferably chosen from acrylamide, acrylic acid and/or one of its salts, 2-acrylamido-2-methylpropane sulphonic acid (ATBS) and / or one of its salts, N-vinylformamide (NVF), N-vinylpyrrolidone (NVP), dimethyldiallylammonium chloride (DADMAC), quaternized dimethylaminoethyl acrylate (ADAME), quaternized dimethylaminoethyl methacrylate (MADAME), a substituted acrylamide of formula CH ₂ =CHCO-NR ¹ R ² , R ¹ and R ² being, independently of each other, a linear or branched carbon chain C _n H _2n+1 , in which n is between 1 and 10. The second monomer and the optional other monomers are very preferably chosen from biobased acrylamide, acrylic acid and/or one of its biobased salts, 2-acrylamido-2-methylpropane sulphonic acid (ATBS) and /or its biosourced salts.

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

In a particular mode applicable to the various polymers, oligomers and processes described in the invention, the acrylic acid or one of its salts used to obtain the oligomer and the polymer according to the invention is preferentially at least partially, preferentially totally derived from a recycling process.

In this particular mode, the bio-based polymer with improved biodegradability is obtained according to a process comprising the following steps:
- Recycle at least one raw material of renewable and non-fossil origin to obtain acrylic acid or one of its recycled salts;
- Reacting acrylic acid or one of its recycled salts with a source of Brønsted acid or a source of Brønsted base and in the presence of at least 0.1% by weight of water to obtain an oligomer according to Formula 1) ;
- Polymerizing said oligomer, optionally with an ethylenically unsaturated monomer as described above, to produce a polymer.

Recycled acrylic acid can be obtained from various previously defined methods.

The recycling rate corresponds to the ratio by weight of the recycled material to the total material.

In this particular mode, the part resulting from recycling is preferentially completely "segregated", that is to say from a separate sector and treated separately. In an alternative mode, it is partly "segregated", and partly "non-segregated". In this case, the ratio by weight between the “segregated” part and the “non-segregated” part is preferably between 99:1 and 10:90, preferably between 99:1 and 30:70, more preferably between 99:1 and 50:50.

Throughout the invention, it will be understood that the molar percentage of the monomers of the polymer is equal to 100%.

The invention also relates to a biobased polymer with improved biodegradability, characterized in that the polymer comprises a biobased carbon content of between 5% by weight and 100% by weight relative to the total weight of carbon in said polymer, the biobased carbon content being measured according to ASTM D6866-21, method B.

The invention also relates to the use of at least one oligomer according to formula (1) according to the invention for synthesizing a polymer.

Oligomer according to the invention

The invention relates to an oligomer of acrylic acid according to formula (1) or one of its salts, said oligomer being at least partly of renewable and non-fossil origin, and n being between 1 and 10, preferentially between 2 and 5

All the modes and preferences mentioned in the “Polymer” part apply in this part concerning the oligomer.

Throughout the application, the terms "oligomer of acrylic acid" include the acid version of the oligomer, and also the corresponding salts of the oligomer of acrylic acid. The salts of these oligomers are, for example, alkali metal, alkaline-earth metal or ammonium salts. Preferred salts are sodium, potassium and ammonium salts.

Thus, throughout the application, formula (1) includes not only formula (1) as drawn, but it also includes the salts corresponding to formula (1), that is to say when the the hydrogen atom to the right of the molecule of formula (1) is replaced by a cation of alkali metals, alkaline-earth metals, or by NH4+; then the adjacent oxygen atom becomes negatively charged and becomes O ^- .

In the invention and in the various embodiments set out below, the oligomer according to formula (1) preferably has a biobased carbon content of between 5% by weight and 100% by weight relative to the total weight of carbon. in the oligomer, the biobased carbon content being measured according to standard ASTM D6866-21, method B.

The invention relates to an oligomer obtained from acrylic acid, characterized in that the acrylic acid used to manufacture said oligomer is at least partly of renewable and non-fossil origin.

In the invention and in the various embodiments set out below, the acrylic acid preferably has a biobased carbon content of between 5% by weight and 100% by weight relative to the total weight of carbon in said acrylic acid, the biobased carbon content being measured according to the ASTM D6866-21 standard, method B.

In a particularly preferred mode according to the invention, the acrylic acid is not only partially or preferentially totally biobased, but it is also preferentially obtained by a bioconversion process implementing a biocatalyst comprising enzymes. The latter are capable of transforming a chemical function into another chemical function.

A preferred bioconversion process is the hydrolysis of acrylonitrile to acrylic acid and/or its salts such as ammonium acrylate with a biocatalyst comprising nitrilase-type enzymes. Another particularly preferred bioconversion process is the hydrolysis of acrylamide to acrylic acid and/or its salts such as ammonium acrylate with a biocatalyst comprising amidase type enzymes. The latter method is more particularly preferred. The other processes described in the “Polymer” section also apply in the “Oligomer” section.

The invention therefore relates to an oligomer of acrylic acid according to formula (1) in which n is between 1 and 10, preferably between 2 and 5, said oligomer being obtained from acrylic acid, itself obtained from from ammonium acrylate, said ammonium acrylate being obtained by bioconversion of acrylonitrile at least in part of renewable and non-fossil origin, said bioconversion comprising at least one step of enzymatic hydrolysis of said acrylonitrile in the presence of a biocatalyst comprising at least one nitrilase enzyme.

The invention therefore also relates to an oligomer of acrylic acid according to formula (1) in which n is between 1 and 10, preferably between 2 and 5, said oligomer being obtained from acrylic acid, itself obtained from ammonium acrylate, said ammonium acrylate being obtained by bioconversion of acrylamide at least in part of renewable and non-fossil origin, said bioconversion comprising at least one step of enzymatic hydrolysis of said acrylamide in the presence of a biocatalyst comprising at least one amidase enzyme, said acrylamide being obtained by bioconversion of acrylonitrile at least in part of renewable and non-fossil origin, said bioconversion comprising at least one step of enzymatic hydrolysis of said acrylonitrile in the presence of a biocatalyst comprising at least one nitrile hydratase enzyme.

The enzyme contained in the biocatalyst making it possible to obtain acrylic acid, or its salts, is generally a nitrilase or an amidase synthesized by a microorganism advantageously of the Bacillus, Bacteridium, Micrococcus, Brevibacterium, Corynebacterium, Pseudomonas, Acinetobacter, Xanthobacter, Streptomyces, Rhizobium, Klebsiella, Enterobacter, Erwinia, Aeromonas, Citrobacter, Achromobacter, Agrobacterium, Pseudonocardia, Rhodococcus, Comamonas, Saccharomyces, Dietzia, Clostridium, Lactobacillus, Escherichia, Agrobacterium, Mycobacterium, Methylophilus, Propionibacterium, Actinobacillus, Megasphaera, Aspergillus Candida, or Fusarium. For the amidases, the preferred microorganisms are Rhodococcus Erythropolis, Pseudomonas methylotropha, Rhodococcus rhodochrous or Comamonas testosteroni, and more preferentially Rhodococcus rhodochrous. For the nitrilases, the preferred microorganisms are Acidovorax facilis, Arabidopsis thaliana, Nicotiana tabacum, Rhodococcus rhodocrous J1, Rhodococcus rhodocrous PA34, Rhodococcus rhodocrous K22, Klebsiella ozaenae or Comamonas testosteroni.

The bioconversion of acrylamide to acrylic acid and/or its salts is generally carried out by bringing acrylamide in aqueous solution into contact with an enzyme of the amidase type. In this case, water plays both the role of reactant and solvent. Preferably, the aqueous acrylamide solution is poured continuously or semi-contained in a solution containing the enzyme. The temperature is generally regulated between 5 and 60°C. The reaction time is adjusted according to the desired degree of conversion, and is generally between 30 minutes and 30 days. A buffer solution can be added to the reaction medium, in order to maintain a pH advantageously between 6 and 8. The same type of bioprocess can be used for the bioconversion of acrylonitrile into acrylic acid with enzymes of the nitrilase type. The person skilled in the art will be able to refer to his technical knowledge to carry out the bioconversion.

The invention also relates to an oligomer of formula (1) in which n is between 1 and 10, preferably between 2 and 5, said oligomer being obtained by reaction of acrylic acid with a source of Brønsted acid or a source of Brønsted base and in the presence of at least 0.1% by weight of water, characterized in that the said acrylic acid is at least partly of renewable and non-fossil origin.

The acrylic acid or the acrylate salt used to obtain the oligomer according to the invention can be non-segregated, partially segregated, or totally segregated. The same modes and preferences set out in the “Polymer” section apply for the oligomer according to the invention.

In a particular mode, the acrylic acid or one of its salts used to obtain the oligomer and the polymer according to the invention is at least partially, preferentially completely resulting from a recycling process. The same modes and preferences set out in the “Polymer” section apply for the oligomer according to the invention.

Recycled acrylic acid can be obtained from various sources, some of which are set out below.

One source is to obtain recycled acrylic acid from recycled propylene.

Another source is to obtain recycled acrylic acid from recycled acrylonitrile which is transformed:
- Either in ammonium acrylate by bioconversion with at least one nitrilase enzyme, said ammonium acrylate being transformed into recycled acrylic acid,
- Either to acrylamide by bioconversion with at least one nitrile hydratase enzyme, said acrylamide being able to be transformed into ammonium acrylate by bioconversion with at least one amidase enzyme, said ammonium acrylate being transformed into recycled acrylic acid.

Another source consists in obtaining a recycled acrylic acid from recycled acrylamide, which can then be transformed into ammonium acrylate by bioconversion with at least one amidase enzyme, said ammonium acrylate being transformed into recycled acrylic acid.

Another source is to obtain recycled acrylic acid from recycled 3-hydroxypropionitrile. Reference can then be made to the various modes and variants mentioned in the “Process” section.

A subject of the invention is also the reaction mixture obtained according to the process of the invention. This reaction mixture may comprise a mixture of at least two molecules of formula (1) having a different n value, n being between 0 and 10, preferably between 0 and 5. When n=0 then the molecule is the acid acrylic; this is particularly the case when all the acrylic acid or one of its salts has not reacted. This may well occur during the process according to the invention. “m” is the mean of the “n” values of the reaction mixture. The value “m” is then preferentially between 0.1 and 10, more preferentially between 0.2 and 5, even more preferentially between 0.5 and 4.

In other words, if the reaction mixture comprises 10% molar of acrylic acid (n=0), 30% molar of oligomer according to formula 1 with n=1, 30% molar of oligomer according to formula 1 with n=2 , and 30 molar % of oligomer according to formula 1 with n=3, then m=0.1*0+0.3*1+0.3*2+0.3*3, i.e. 1.8. If the mole percentages are 60%, 20%, 10%, and 10%, respectively, then m = 0.7.

Process for manufacturing the oligomer according to the invention

The invention also relates to a process for manufacturing an oligomer of formula (1) or one of its salts in which n is between 1 and 10, preferably between 2 and 5, said process comprising a reaction of acrylic acid with a source of Brønsted acid or a source of Brønsted base and in the presence of at least 0.1% by weight of water, characterized in that the said acrylic acid is at least partly of renewable origin and not fossil.

The same modes and preferences set out in the “Polymer” section apply for the process for manufacturing the oligomer according to the invention.

The oligomer of formula (1) is generally obtained by heating acrylic acid comprising at least 0.1% by weight of water, at a temperature of 30 to 200°C. The reaction time depends on the desired degree of oligomerization, and is generally between 60 minutes and 60 days.

The oligomerization catalyst can be homogeneous or heterogeneous. In the case of a homogeneous form of the catalyst, a solution of sodium hydroxide or an alkaline carbonate salt is preferred. Sodium hydroxide, sodium carbonate and potassium carbonate are preferred.

As part of a heterogeneous form of the catalyst, an ion exchange resin can be used, more particularly a basic ion exchange resin.

In the process according to the invention, the acrylic acid is preferably obtained by a process comprising at least one bioconversion step, said bioconversion comprising at least one enzymatic hydrolysis step in the presence of a biocatalyst comprising at least one enzyme.

In the process according to the invention, the acrylic acid is preferably obtained from a recycling process.

The methods and preferences previously mentioned in the parts relating to the polymer and the oligomer according to the invention, and particularly those relating to the method of obtaining acrylic acid by bioconversion, and those relating to the recycled origin of the acid acrylic, apply to the process according to the invention.

Use of the polymer according to the invention

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

The invention also relates to the use of the polymer according to the invention as a flocculant, coagulant, binding agent, fixing agent, viscosity-reducing agent, thickening agent, absorbing agent, friction-reducing agent, dripping agent, drainage agent, filler retention agent, dehydrating agent, conditioning agent, stabilizing agent, fixing agent, film-forming agent, sizing agent, superplasticizer, clay inhibitor or dispersant.

Process using the polymer according to the invention

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

The invention also relates to a method for enhanced recovery of oil or gas by sweeping an underground formation comprising the following steps:
To. Prepare an injection fluid from a polymer according to the invention, with water or brine,
b. Inject the injection fluid into a subterranean formation,
vs. Sweep the underground formation using the injected fluid,
d. Recover an aqueous mixture of oil and/or gas.

The invention also relates to a process for the hydraulic fracturing of an underground oil and/or gas reservoir comprising the following steps:
To. Prepare an injection fluid from a polymer according to the invention, with water or brine, and with at least one propping agent,
b. Injecting said fluid into the underground reservoir and fracturing at least a portion thereof to recover oil and/or gas.

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

The invention also relates to a method for stimulating an underground formation comprising the following steps:
To. Prepare an injection fluid from a polymer according to the invention, with water or brine,
b. Inject the injection fluid into a subterranean formation,
vs. partially or totally blocking a part of the underground formation using the injected fluid, said blocking being temporary or permanent.

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

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

In the drilling and cementing of a well, the polymer according to the invention can be used as a fluid loss additive control agent in well cement compositions to reduce the loss flow of the cement compositions to permeable formations or areas into or through which the cement compositions are pumped. In primary cementing, the loss of fluid, i.e., water, to permeable subterranean formations or areas can lead to premature gelation of the cement composition, such that bridging of the annular space between the formation or permeable zone and the drill string cemented therein prevents the cement composition from being placed along the entire length of the annulus.

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

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

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

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

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

The process can be used successfully for the manufacture of packaging paper and cardboard, coating support paper, sanitary and household paper, all types of paper, cardboard or the like.

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

By retention properties, we mean the ability to retain the materials in suspension of the paper pulp (fibers, fines, fillers (calcium carbonate, titanium oxide), etc. on the forming fabric, therefore in the fibrous mat which will constitute the final sheet. The mode of action of retention agents is based on the flocculation of these materials in suspension in water. Indeed, the flocs formed are more easily retained on the forming fabric.

Retention of fillers consists of specifically retaining fillers (small mineral species with little affinity with cellulose). The significant improvement in filler retention leads to clarification of white water by retaining fillers in the sheet and increasing its weight. This also gives the possibility of substituting part of the fibers (the most expensive species in the composition of paper, cardboard or the like) by fillers (lower costs) to reduce manufacturing costs.

With regard to the drainage properties (or drainage), this is the ability of the fibrous mat to evacuate or drain as much water as possible so that the sheet dries as quickly as possible, in particular during the manufacture of the sheet.

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

By fibrous suspension, we mean the thick paste or the thin paste which is based on water and cellulosic fibers. The thick stock, having a mass concentration of dry matter greater than 1%, or even greater than 3%, is upstream of the mixing pump (fan-pump). The thin stock (“Thin Stock”), having a mass concentration of dry matter generally less than 1%, is located downstream of the mixing pump.

The polymer can be introduced into the thick paste (thick stock) or into the diluted paste (thin stock). It can be added at the fan pump or at the headbox. Preferably, the polymer is introduced before the headbox.

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

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

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

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

According to another embodiment, the polymer is added to the suspension of particles during the transport of said suspension to a deposit zone. Preferably, the polymer is added in the pipe which transports said suspension towards a zone of deposit. It is on this deposit zone that the treated suspension is spread with a view to its dehydration and solidification. The deposit zones can be non-closed, such as for example an undelimited expanse of ground, or closed, such as for example a basin, a cell.

An example of these treatments during transport of the suspension is the spreading of the suspension treated with the polymer according to the invention on the ground with a view to its dehydration and its solidification, then the spreading of a second layer of suspension treated on the first solidified layer. Another example is the continuous spreading of the suspension treated with the polymer according to the invention in such a way that the treated suspension falls continuously on the suspension previously discharged into the deposit zone, thus forming a mass of treated materials whose water is extracted.

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

The water-soluble polymer can be added simultaneously in different stages of the treatment of the suspension, i.e. for example in the pipe transporting the suspension to a thickener and in the sludge leaving the thickener which will be conducted either to a deposit area or to a mechanical treatment device.

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

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

They can also advantageously be used to treat the sludge resulting from the treatment of this waste water. Sewage sludge (urban or industrial) is the main waste produced by a wastewater treatment plant from liquid effluents. Sludge treatment generally consists of dewatering it. This dehydration can be carried out by centrifugation, filter press, belt filter press, electro-dehydration, drying bed planted with reeds, solar drying. It reduces the water concentration of the sludge.

In this municipal or industrial water treatment process, the polymer according to the invention is preferably linear or branched. It is preferably in the form of powder, inverse emulsion, partially dehydrated inverse emulsion. The powder form is preferably obtained by gel or by "spray drying" from an inverse emulsion.

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

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

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

The term "detergent compositions for household or industrial use" means compositions for cleaning various surfaces, in particular textile fibers, hard surfaces of any kind such as dishes, floors, windows, wooden surfaces, metal or composite. Such compositions correspond, for example, to detergents for washing linen manually or in a washing machine, products for cleaning dishes manually or for dishwashers, detergent products for washing home interiors such as kitchen units , toilets, furniture, floors, windows, and other general-purpose cleaning products.

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

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

The invention also relates to a process for the manufacture of superabsorbent from the monomer according to the invention, a superabsorbent obtained from at least one oligomer according to the invention, the use of said superabsorbent for absorbing and retaining water in agricultural applications or for absorbing aqueous liquids in sanitary diapers.

The superabsorbent agent is for example a polymer according to the invention. Thus, the invention also relates to the use of at least one polymer according to the invention as a superabsorbent agent for absorbing and retaining water in agricultural applications or for absorbing aqueous liquids in sanitary diapers.

The invention also relates to a process for manufacturing sanitary diapers in which a polymer according to the invention is used, for example as a superabsorbent agent.

The invention also relates to the use of the polymer according to the invention as a binder for a battery. The invention also relates to a binding composition for a battery comprising the polymer according to the invention, an electrode material and a solvent. The invention also relates to a method for manufacturing a battery comprising the manufacture of a gel comprising at least one polymer according to the invention and its introduction into said battery. Examples include lithium-ion batteries which are used in a range of products including medical devices, electric cars, airplanes and, most importantly, consumer products such as laptops, cell phones and cameras. .

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

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

Another important point is that the binders must have a certain degree of flexibility so that they do not crack or develop defects. Weakness can create problems when manufacturing or assembling the battery.

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

The invention also relates to a process for manufacturing a sanitary diaper in which a polymer according to the invention is used, for example as a superabsorbent agent.

As previously explained, the circular economy is an economic system dedicated to efficiency and sustainability that minimizes waste by optimizing the value generated by resources. It relies heavily on various conservation and recycling methods to break away from the current, more linear approach of “grab, produce and throw away”.

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

Specific objects are described below.

Bio-based polymer with improved biodegradability obtained by polymerization of at least one oligomer of acrylic acid according to formula (1) or of one of its salts in which n is between 1 and 10, preferably between 2 and 5, said oligomer being either derived at least in part from a process of recycling a raw material of renewable and non-fossil origin, or of fossil origin, or manufactured from acrylic acid at least partly derived from a process of recycling of a raw material of renewable and non-fossil origin, or of fossil origin.

Oligomer according to formula (1) or one of its salts in which n is between 1 and 10, preferably between 2 and 5, produced from acrylic acid at least partly resulting from a process of recycling a material first of renewable and non-fossil origin, or of fossil origin.

Process for the manufacture of an oligomer of formula (1) or of one of its salts in which n is between 1 and 10, preferably between 2 and 5, comprising the reaction of acrylic acid with a source of Brønsted or a source of Brønsted base and in the presence of at least 0.1% by weight of water, said acrylic acid being at least partly derived from a recycling process of a raw material of renewable origin and non-fossil, or of fossil origin.

Bio-based polymer with improved biodegradability obtained according to a process comprising the following steps:
- Recycle at least one raw material of renewable and non-fossil origin, or of fossil origin to obtain recycled acrylic acid;
- Reacting the recycled acrylic acid with a source of Brønsted acid or a source of Brønsted base and in the presence of at least 0.1% by weight of water to obtain an oligomer according to formula (1);
- Polymerize said oligomer with optionally an ethylenically unsaturated monomer as described above, to manufacture a polymer.

Recycled acrylic acid can be obtained from various sources, some of which are set out below.

One source is to obtain recycled acrylic acid from recycled propylene.

Another source is to obtain recycled acrylic acid from recycled acrylonitrile which is transformed:
- Either in ammonium acrylate by bioconversion with at least one nitrilase enzyme, said ammonium acrylate being transformed into recycled acrylic acid,
- Either to acrylamide by bioconversion with at least one nitrile hydratase enzyme, said acrylamide being able to be transformed into ammonium acrylate by bioconversion with at least one amidase enzyme, said ammonium acrylate being transformed into recycled acrylic acid.

Another source consists in obtaining a recycled acrylic acid from recycled acrylamide, which can then be transformed into ammonium acrylate by bioconversion with at least one amidase enzyme, said ammonium acrylate being transformed into recycled acrylic acid.

Another source is to obtain recycled acrylic acid from recycled 3-hydroxypropionitrile.

There details, inter alia, in a general diagram, the various routes for obtaining the oligomer of formula (1) according to the invention.

Claims (32)

Bio-based polymer with improved biodegradability obtained by polymerization of at least one oligomer of acrylic acid according to formula (1) or of one of its salts, said oligomer being at least partly of renewable and non-fossil origin, and n being between 1 and 10.
Bio-based polymer with improved biodegradability according to claim 1, characterized in that the oligomer according to formula (1) has a bio-based carbon content of between 5% by weight and 100% by weight relative to the total weight of carbon in the oligomer, the biobased carbon content being measured according to the ASTM D6866-21 standard, method B. Bio-based polymer with improved biodegradability according to claim 1 or 2, said oligomer being obtained from acrylic acid at least partly of renewable and non-fossil origin. Bio-based polymer with improved biodegradability according to claim 3, characterized in that the acrylic acid has a bio-based carbon content of between 5% by weight and 100% by weight relative to the total weight of carbon in the acrylic acid, the content in bio-based carbon being measured according to ASTM D6866-21, method B. Bio-based polymer with improved biodegradability according to Claim 3 or 4, characterized in that the acrylic acid used to produce the oligomer of formula (1) is obtained by a biological process, the said biological process comprising at least one step of bioconversion by enzymatic in the presence of a biocatalyst comprising at least one enzyme. Bio-based polymer with improved biodegradability according to one of Claims 3 to 5, characterized in that the acrylic acid used to produce the oligomer of formula (1) is obtained from ammonium acrylate, the said ammonium acrylate being obtained by bioconversion of acrylonitrile at least partly of renewable and non-fossil origin, said bioconversion comprising at least one step of enzymatic hydrolysis of said acrylonitrile in the presence of a biocatalyst comprising at least one nitrilase enzyme. Bio-based polymer with improved biodegradability according to one of Claims 3 to 5, characterized in that the acrylic acid used to produce the oligomer of formula (1) is obtained from ammonium acrylate, the said ammonium acrylate being obtained by bioconversion of acrylamide at least in part of renewable and non-fossil origin, said bioconversion comprising at least one step of enzymatic hydrolysis of said acrylamide in the presence of a biocatalyst comprising at least one amidase enzyme, said acrylamide being obtained by bioconversion of acrylonitrile at least partly of renewable and non-fossil origin, said bioconversion comprising at least one step of enzymatic hydrolysis of said acrylonitrile in the presence of a biocatalyst comprising at least one nitrile hydratase enzyme. Bio-based polymer with improved biodegradability according to one of Claims 3 to 7, characterized in that the polymer has a biodegradability of between 20 and 100%, the biodegradability being measured according to the OECD 302B standard, known as the Zahn-Wellens standard. Bio-based polymer with improved biodegradability according to one of Claims 3 to 8, characterized in that the acrylic acid used to produce the oligomer of formula (1) is partially segregated, or totally segregated. Bio-based polymer with improved biodegradability according to one of claims 1 to 9,characterized in that the acrylic acid used to produce the oligomer of formula (1) comes at least partially from a recycling process. Biosourced polymer with improved biodegradability according to one of Claims 1 to 10, characterized in that the polymer is obtained by polymerization of the said oligomer and of at least one second monomer different from the oligomer, this second monomer being chosen from monomers not ionic monomers, anionic monomers, cationic monomers, zwitterionic monomers, monomers comprising a hydrophobic group, and mixtures thereof. Bio-based polymer with improved biodegradability according to Claim 11, characterized in that the said monomer is at least partly of renewable and non-fossil origin, and preferably comprises a bio-based carbon content of between 5% by weight and 100% by weight with respect to to the total weight of carbon in the monomer, the biobased carbon content being measured according to the ASTM D6866-21 standard, method B. Bio-based polymer with improved biodegradability according to one of Claims 1 to 12, characterized in that the polymer is a polymer comprising:
- at least 5% molar, preferably at least 10% molar, preferably between 20% and 99% molar, more preferably between 30% and 90% of an oligomer of formula (1), and
- at least 1% molar, preferably between 5% and 90% molar, more preferably between 10% and 80% molar of at least one second monomer comprising ethylenic unsaturation, said second monomer being at least partly of renewable origin and not fossil. Bio-based polymer with improved biodegradability according to Claim 13, characterized in that the at least second monomer is chosen from acrylamide, acrylic acid and/or one of its salts, 2-acrylamido-2-methylpropane sulphonic acid ( ATBS) and/or one of its salts, N-vinylformamide (NVF), N-vinylpyrrolidone (NVP), dimethyldiallylammonium chloride (DADMAC), quaternized dimethylaminoethyl acrylate (ADAME), dimethylaminoethyl methacrylate (MADAME ) quaternized, a substituted acrylamide of formula CH ₂ =CHCO-NR ¹ R ² , R ¹ and R ² being, independently of one another, a linear or branched carbon chain C _n H _2n+1 , in which n is between 1 and 10. Oligomer of acrylic acid according to formula (1) or one of its salts, said oligomer being at least partly of renewable and non-fossil origin, and n being between 1 and 10.
Oligomer of acrylic acid according to Claim 15, characterized in that the said oligomer has a biobased carbon content of between 5% by weight and 100% by weight relative to the total weight of carbon in the oligomer, the carbon content biobased being measured according to ASTM D6866-21, method B. Oligomer of acrylic acid according to formula (1) according to one of Claims 15 or 16, characterized in that the acrylic acid used to manufacture the said oligomer is at least partly of renewable and non-fossil origin, and has a biobased carbon content of between 5% by weight and 100% by weight relative to the total weight of carbon in said acrylic acid, the biobased carbon content being measured according to standard ASTM D6866-21, method B. Oligomer of acrylic acid according to formula (1) according to one of Claims 15 to 17, characterized in that the acrylic acid used to produce the oligomer of formula (1) is obtained by a biological process, the said process biological comprising at least one enzymatic bioconversion step in the presence of a biocatalyst comprising at least one enzyme. Process for the manufacture of an oligomer of formula (1) or of one of its salts comprising the reaction of acrylic acid with a source of Brønsted acid or a source of Brønsted base and in the presence of at least 0 ,1% by weight of water, said acrylic acid is at least partly of renewable and non-fossil origin, and has a bio-based carbon content of between 5% by weight and 100% by weight relative to the total weight of carbon in said acrylic acid, the biobased carbon content being measured according to standard ASTM D6866-21, method B. Process for the manufacture of an oligomer of formula (1) according to one of Claims 18 or 19, characterized in that the acrylic acid used to produce the oligomer of formula (1) is obtained by a biological process, the said process biological comprising at least one enzymatic bioconversion step in the presence of a biocatalyst comprising at least one enzyme. Use of at least one oligomer of formula (1) according to one of Claims 15 to 18 for synthesizing a polymer. Use of a polymer according to one of Claims 1 to 14 in a field chosen from the recovery of hydrocarbons; in the drilling and cementing of wells; in the stimulation of hydrocarbon wells; in water treatment; in the treatment of fermentation musts; in sludge treatment; in the manufacture of paper; in the construction ; in the treatment of wood; in the treatment of hydraulic composition; in the mining industry; in the formulation of cosmetic products; in the formulation of detergents; in the manufacture of textiles; in the manufacture of battery components; in geothermal energy; in the manufacture of sanitary diapers; or in agriculture. Use of the polymer according to one of Claims 1 to 14 as a flocculant, coagulant, binding agent, fixing agent, viscosity-reducing agent, thickening agent, absorbing agent, friction-reducing agent, draining agent, drainage agent, filler retention, dehydrating agent, conditioning agent, stabilizing agent, fixing agent, film-forming agent, sizing agent, superplasticizer, clay inhibitor or dispersant. A method of enhanced oil and/or gas recovery by sweeping an underground formation, comprising the following steps:
- Prepare an injection fluid from a polymer according to one of claims 1 to 14, with water or brine,
b. Inject the injection fluid into a subterranean formation,
vs. Sweep the underground formation using the injected fluid,
d. Recover an aqueous mixture of oil and/or gas. Process for the hydraulic fracturing of an underground oil and/or gas reservoir, comprising the following steps:
- Prepare an injection fluid from a polymer according to one of claims 1 to 14, with water or brine, and with at least one propping agent,
b. injecting said fluid into the underground reservoir and fracturing at least a portion thereof to recover oil and/or gas. Method for drilling and/or cementing a well in an underground formation, comprising the following steps:
- Prepare a fluid from a polymer according to one of claims 1 to 14, with water or brine,
b. Injecting said drilling and/or cementing fluid into the subterranean formation via the drill head in at least one step of drilling or cementing a well. Process for manufacturing a sheet of paper, cardboard or the like, according to which, before forming said sheet, a suspension of fibers is added, at one or more injection points, to at least one polymer according to one of Claims 1 at 14. Municipal or industrial water treatment process comprising the introduction into said municipal or industrial water of at least one polymer according to one of claims 1 to 14. Thickener for cosmetic, dermatological, pharmaceutical or detergent composition, said thickener comprises at least one polymer according to one of Claims 1 to 14. Thickener for pigment composition used in textile printing, said thickener comprises at least one polymer according to one of Claims 1 to 14. Process for treating a suspension of solid particles in water resulting from mining or oil sands exploitation, comprising bringing said suspension into contact with at least one polymer according to one of Claims 1 to 14. Use of at least one polymer according to one of Claims 1 to 14 as a superabsorbent agent for absorbing and retaining water in agricultural applications or for absorbing aqueous liquids in sanitary diapers.