Oligonucleotide initiators and their use in generating water-soluble hybrid polymers

Abstract

This invention relates to an oligonucleotide initiator, a method for synthesizing the oligonucleotide initiator, and the use of the oligonucleotide initiator in generating a water-soluble hybrid polymer. The invention also relates to a water-soluble hybrid polymer obtained according to a synthetic method comprising functionalizing the biopolymer by reacting functional groups of the biopolymer with functional groups of the oligonucleotide initiator, thereby allowing the synthetic polymer chain to extend, thus forming the water-soluble hybrid polymer. The invention further relates to the use of the water-soluble hybrid polymer in various application areas.

Description

Technical Field

[0001] This invention relates to an oligonucleotide initiator and its use in generating water-soluble hybrid polymers. More specifically, the method for generating water-soluble hybrid polymers comprises functionalizing the biopolymer by reacting the functional groups of the biopolymer with the functional groups of the oligonucleotide initiator according to the invention; thus, it is possible to extend the synthetic polymer chain to form the water-soluble hybrid polymer. The invention also relates to the resulting water-soluble hybrid polymers and their use in various application areas. Background Technology

[0002] In recent years, the synthesis of hybrid polymers, namely polymer entities that combine at least two polymers with different properties, has become the subject of a great deal of research and development.

[0003] These hybrid polymers include those that combine biopolymers derived from natural and / or renewable resources with synthetic polymers derived from fossil resources. These hybrid polymers have attracted significant attention in the chemical industry due to their application properties, functional characteristics, and sustainability, which are very similar to those of synthetic polymers. These features make these hybrid polymers attractive in many applications, providing opportunities for innovation and the development of products that are more efficient and environmentally friendly than ever before.

[0004] There are three conventional methods for synthesizing such hybrid polymers.

[0005] The first method is named " Grafting through ( grafting through "( )," is composed of copolymers between monomers and biopolymers. This method allows for the heterogeneous or homogeneous addition of branches or side chains based on the reactivity ratio between the terminal functional groups of the biopolymer and the monomer. In this case, the side chains are biopolymer grafts. To avoid any steric hindrance, these biopolymer side chains are typically hydrolyzed to obtain low molecular weight grafts, as described in patent FR 2934268.

[0006] In the name " Grafting ( grafting from In the second method, the biopolymer backbone is chemically modified to introduce active sites that can initiate polymer chain growth. These initiation sites can be incorporated through copolymerization, during post-polymerization reactions, or may already be part of the biopolymer. The number of grafted chains can be controlled by the number of active sites.

[0007] The third method is named " grafting to ( grafting ontoThis method involves grafting a pre-formed polymer or polymer units onto a biopolymer substrate. This process involves covalent chemical bonds between the pre-existing polymer and the biopolymer substrate. In addition to supplementary treatments to enhance the stability of these covalent bonds, various chemical reagents are required to functionalize the substrate.

[0008] All three methods require stringent experimental conditions. Furthermore, when operating on a biopolymer substrate, it is difficult (if not impossible) to avoid side reactions, particularly the formation of ungrafted polymers, degradation of grafted chains or the final biopolymer, and / or crosslinking of grafted chains. Since most biopolymers are multifunctional, even the slightest modification can trigger a cascade reaction, leading to uncontrolled grafting onto the biopolymer backbone.

[0009] Furthermore, none of these methods can obtain well-defined polymers with controllable structures under mild copolymerization conditions, i.e., with a limited amount of reagents and polymerization reaction and without the use of harmful catalysts, in an aqueous medium and without requiring a large amount of energy input.

[0010] To solve this problem, the applicant developed a method that falls between " Grafting "Methods and" grafting to "The synthetic method between the methods uses mild copolymerization conditions to produce new water-soluble hybrid polymers. Specifically, the applicant has developed an oligonucleotide initiator that enables controlled polymerization under mild conditions, making it more environmentally friendly."

[0011] Furthermore, the present invention advantageously utilizes biologically derived materials (such as biomass) or recycled materials for implementation. The synthesis of the monomers used in the present invention is advantageously biosynthetic, for example by enzymatic catalysis or extraction from renewable feedstocks. The energy used to implement the method according to the invention is advantageously derived from heat pumps or renewable sources, such as photovoltaic or wind power generation, or, particularly for mobile devices, fuel cell units or lithium-ion battery types. Summary of the Invention

[0012] The present invention relates to an oligonucleotide initiator having the following formula (I), a method for obtaining said oligonucleotide initiator, and its use in generating water-soluble hybrid polymers.

[0013] According to the present invention, the oligonucleotide initiator has the following formula (I): [Chemical Formula 1]

[0014] (I) in: W= R 1 Or W = ZR 3Where Z = O, S, or NR 4 , R 1 R 2 R 3 and R 4 They can be the same or different and represent: Optionally substituted alkyl, acyl, aryl, olefinic, or alkyne groups (i), or Optionally substituted or aromatic saturated or unsaturated carbonyl rings (ii), or Optionally substituted saturated or unsaturated heterocycles (ii). These groups, as well as rings (i), (ii), and (iii), may be substituted with substituted phenyl groups, substituted aromatic groups, or the following groups: alkoxycarbonyl or aryloxycarbonyl (-COOR), carboxyl (-COOH), acyloxy (-O2CR), carbamoyl (-CON(R)2), cyano (-CN), alkylcarbonyl, alkylarylcarbonyl, arylcarbonyl, arylalkylcarbonyl, phthalimide, maleimide, succinimide, amidoyl, guanidinyl, hydroxyl (-OH), amino (-N(R)2), halogen, allyl, epoxy, alkoxy (-OR), S-alkyl, S-aryl, groups with hydrophilic or ionic properties, such as alkali metal salts of carboxylic acids, alkali metal salts of sulfonic acids, polyepoxide (PEO, PPO) chains, cationic substituents, quaternary ammonium salts. (R) represents C1-C 20 Alkyl or aryl, especially C2-C 20 Alkyl or aryl.

[0015] (R)2 functional group, the two R groups can be the same or different from each other. R 4 It can also represent a hydrogen atom; G includes A and / or Q.

[0016] A is a single unit or includes n A A linear or structured polymer chain of identical or different hydrophilic monomers, wherein the hydrophilic monomers contain at least one olefinic unsaturated functional group, wherein n A It is an integer between 0 and 500. Q is a single unit or a component. n Q A linear or structured polymer chain of monomers, wherein the monomers are selected from monomers having at least one reactive functional group (frQ), wherein the at least one reactive functional group is an epoxide and / or anhydride and / or hydroxyl and / or isocyanate and / or acetal and / or aldehyde and / or carboxylic acid and / or ester and / or vinyl type, wherein nQ It is an integer between 1 and 1000. A and Q can be statistically, gradient-wise, or block-wise copolymerized to form G.

[0017] The present invention also relates to a water-soluble hybrid polymer obtained using an oligonucleotide initiator according to the invention according to a specific synthetic method.

[0018] This invention relates to a water-soluble hybrid polymer HP obtained according to a method comprising at least the following sequential steps: 1-Biopolymer B1 is functionalized by reacting at least one reactive functional group (frB) of biopolymer B1 with at least one reactive functional group (frQ) of the oligonucleotide initiator to obtain functionalized biopolymer B2. 2- A hydrophilic monomer containing at least one olefinic unsaturation is polymerized on at least one oligonucleotide initiator of the functionalized biopolymer B2 to form at least one side chain L, and thus obtain the hybrid polymer HP. Its features The oligonucleotide initiator has formula (I). [Chemical Formula 1]

[0019] (I) in: W= R 1 Or W = ZR 3 Where Z = O, S, or NR 4 , R 1 R 2 R 3 and R 4 They can be the same or different and represent: Optionally substituted alkyl, acyl, aryl, olefinic, or alkyne groups (i), or Optionally substituted or aromatic saturated or unsaturated carbonyl rings (ii), or Optionally substituted saturated or unsaturated heterocycles (ii). These groups, as well as rings (i), (ii), and (iii), may be substituted with substituted phenyl groups, substituted aromatic groups, or the following groups: alkoxycarbonyl or aryloxycarbonyl (-COOR), carboxyl (-COOH), acyloxy (-O2CR), carbamoyl (-CON(R)2), cyano (-CN), alkylcarbonyl, alkylarylcarbonyl, arylcarbonyl, arylalkylcarbonyl, phthalimide, maleimide, succinimide, amidoyl, guanidinyl, hydroxyl (-OH), amino (-N(R)2), halogen, allyl, epoxy, alkoxy (-OR), S-alkyl, S-aryl, groups with hydrophilic or ionic properties, such as alkali metal salts of carboxylic acids, alkali metal salts of sulfonic acids, polyepoxide (PEO, PPO) chains, cationic substituents, quaternary ammonium salts. R represents C1-C 20 Alkyl or aryl, (R)2 functional group, the two R groups can be the same or different from each other. R 4 It can also represent a hydrogen atom; G includes A and / or Q.

[0020] A is a single unit or includes n A A linear or structured polymer chain of identical or different hydrophilic monomers, wherein the hydrophilic monomers contain at least one olefinic unsaturated functional group, wherein n A It is an integer between 0 and 500. Q is a single unit or a component. n Q A linear or structured polymer chain of monomers, wherein the monomers are selected from monomers having at least one reactive functional group (frQ), wherein the at least one reactive functional group is an epoxide and / or anhydride and / or hydroxyl and / or isocyanate and / or acetal and / or aldehyde and / or carboxylic acid and / or ester and / or vinyl type, wherein n Q It is an integer between 1 and 1000. A and Q can statistically, gradient-wise, or block-wise aggregate to form G. Its features The biopolymer B1 is natural or modified and contains at least one reactive functional group (frB), which is a hydroxyl and / or carboxyl and / or acid anhydride and / or amine and / or amide and / or vinyl, and / or phosphate ester and / or sulfonate and / or ester and / or aldehyde and / or ketone and / or silane, and / or isocyanate and / or nitrile and / or acyl halide type.

[0021] The present invention also relates to the use of a water-soluble hybrid polymer HP according to the invention in the selection of: hydrocarbon (oil or natural gas) recovery; drilling; cementing; production enhancement of hydrocarbon (oil or natural gas) wells, such as hydraulic fracturing, profile control, and diversion; water treatment in open, closed, or semi-closed loops; treatment of fermented grape juice; sludge treatment; construction industry; paper or paperboard manufacturing; battery industry; wood treatment; treatment of hydraulic compositions (concrete, cement, mortar, and aggregates); mining industry; cosmetic formulation; detergent formulation; textile manufacturing; geothermal applications; or agriculture.

[0022] Finally, the present invention also relates to the use of the water-soluble hybrid polymer HP according to the invention as a flocculant, coagulant, dispersant, binder, fixative, viscosity reducer, thickener, friction reducer, dehydrating agent, filler retainer, dehydrating agent, regulator, stabilizer, film-forming agent, sizing agent or clay inhibitor. Attached Figure Description

[0023] Figure 1 [ Figure 1 Illustration of the hybrid polymer HP.

[0024] In this context, the thick black line represents a biopolymer chain, such as a polysaccharide; carboxymethyl cellulose, with an oligonucleotide initiator covalently bonded to the biopolymer chain. A hydrophilic monomer having at least one olefinic unsaturation is polymerized onto the oligonucleotide initiator (see arrow) to obtain a side chain L. The resulting hybrid polymer HP consists of a backbone formed from biopolymer B2, with the synthetic polymer side chain L covalently bonded to the backbone. The resulting hybrid polymer HP is water-soluble.

[0025] Figure 2 [ Figure 2 NMR spectrum of hybrid polymer HP1.

[0026] Figure 2 The spectrum of the water-soluble hybrid polymer HP1 exemplified in this application is shown.

[0027] NMR analysis was performed on a Bruker 400 MHz Ascend laser equipped with a BBFO+ probe. TM This was performed on an Avance III HD device. Detailed Implementation

[0028] Unless otherwise expressly stated, the following definitions shall apply throughout this application.

[0029] The term "hybrid polymer" refers to a hybrid polymer produced by the method according to the invention. That is, a polymer containing portions of natural and / or renewable sources, as well as a synthetic polymer derived from fossil resources.

[0030] "Water-soluble hybrid polymer" means a hybrid polymer in which all fractions of the tested hybrid polymer have a solubility of >2 g / L, as demonstrated by any suitable method when dissolved in deionized water at 20°C, pH 7 by stirring for 24 hours and at a concentration of 10 g / 1000 ml, according to OECD specifications (test 120, test 105).

[0031] "Biopolymer" is understood to mean polymers derived from living organisms or polymers synthesized from renewable resources.

[0032] "Renewable resources" refers to natural resources that are generally inexhaustible in terms of reserves, usually because they can be continuously replenished.

[0033] According to the present invention, "biopolymer B1" is understood to refer to the biopolymer before it is functionalized by the oligonucleotide initiator. According to the present invention, "biopolymer B2" is understood to refer to biopolymer B1 after it is functionalized by the oligonucleotide initiator.

[0034] In this application, the term "synthetic side chain L" refers to a product formed by polymerization of at least one synthetic hydrophilic monomer having at least one degree of olefinic unsaturation. The term "synthetic" does not exclude monomers or polymers derived from the following patents: FR3125048, FR3125045, FR3125044, FR3125043, FR3125046, WO2023 / 281233, EP4175939, WO2023 / 281088, WO2023 / 281077, WO2023 / 281076, WO2023 / 281078, WO2023 / 281084, and WO2023 / 281081.

[0035] As used herein, the term "hydrophilic monomer" refers to a monomer with a log(octanol / water partition coefficient) less than 1.5, measured at a temperature of 25°C and a pH between 6 and 8.

[0036] The allocation coefficient Kow is defined as follows: [Mathematical Formula 1]

[0037] in =Equilibrium solubility concentration of monomer in n-octanol (g / l) =Equilibrium concentration of the monomer in water (g / l).

[0038] In one embodiment, the side chain L has a bio-source carbon content ranging from 5 wt% to 100 wt% relative to the total carbon weight in the side chain L, particularly from 50 wt% to 100 wt%, and preferably from 90 wt% to 100 wt%.

[0039] In the context of this invention, ASTM D6866-21 Standard Method B is used to characterize the bio-origin properties of chemical compounds and determine the bio-origin carbon content of said compounds. The value is expressed as a weight percentage (wt%) of bio-origin carbon relative to the total carbon weight in said compound.

[0040] "X and / or Y" is understood to mean "X", or "Y", or "X and Y".

[0041] "Oligonucleotide initiator" refers to a free radical initiator that can form free radicals.

[0042] Structured polymer chains refer to nonlinear polymer chains with one or more side chains.

[0043] All possible combinations of the various embodiments disclosed, whether they are preferred embodiments or embodiments given by way of example, are also part of the invention. Additionally, when indicating a range of values, the limit value is a part of those ranges. This disclosure also includes all combinations between the limit values ​​of these value ranges. For example, the range of values ​​“1-20, preferably 5-15” means the disclosed ranges “1-5”, “1-15”, “5-20”, and “15-20”, as well as the values ​​1, 5, 15, and 20.

[0044] The present invention provides a water-soluble hybrid polymer HP obtained according to a synthetic method comprising functionalizing biopolymer B1 by reacting a reactive functional group of biopolymer B1 with a reactive functional group of an oligonucleotide initiator, thereby enabling the extension of the synthetic side chain L.

[0045] Oligonucleotide initiators One aspect of the present invention is to provide an oligonucleotide initiator.

[0046] The oligonucleotide initiator allows for the synthesis of water-soluble polymers, and more specifically, water-soluble hybrid polymers.

[0047] The weight-average molecular weight of the oligonucleotide initiator is preferably between 350 Da and 1,500,000 Da, more preferably between 500 Da and 500,000 Da, and even more preferably between 1,500 Da and 100,000 Da.

[0048] According to the present invention, the oligonucleotide initiator has the formula (I): [Chemical Formula 1]

[0049] (I) in: W= R 1 Or W = ZR 3 Where Z = O, S, or NR 4 , R 1 R 2 R 3 and R 4 They can be the same or different and represent: Optionally substituted alkyl, acyl, aryl, olefinic, or alkyne groups (i), or Optionally substituted or aromatic saturated or unsaturated carbonyl rings (ii), or Optionally substituted saturated or unsaturated heterocycles (ii). These groups, as well as rings (i), (ii), and (iii), may be substituted with substituted phenyl groups, substituted aromatic groups, or the following groups: alkoxycarbonyl or aryloxycarbonyl (-COOR), carboxyl (-COOH), acyloxy (-O2CR), carbamoyl (-CON(R)2), cyano (-CN), alkylcarbonyl, alkylarylcarbonyl, arylcarbonyl, arylalkylcarbonyl, phthalimide, maleimide, succinimide, amidoyl, guanidinyl, hydroxyl (-OH), amino (-N(R)2), halogen, allyl, epoxy, alkoxy (-OR), S-alkyl, S-aryl, groups with hydrophilic or ionic properties, such as alkali metal salts of carboxylic acids, alkali metal salts of sulfonic acids, polyepoxide (PEO, PPO) chains, cationic substituents, quaternary ammonium salts. R represents C1-C 20 Alkyl or aryl, (R)2 functional group, the two R groups can be the same or different from each other. R 4 It can also represent a hydrogen atom; G includes A and / or Q.

[0050] A is a single unit or includes n A A linear or structured polymer chain of identical or different hydrophilic monomers, wherein the hydrophilic monomers contain at least one olefinic unsaturated functional group, wherein n A It is an integer between 0 and 500. Q is a single unit or a component. nQ A linear or structured polymer chain of monomers, wherein the monomers are selected from monomers having at least one reactive functional group (frQ), wherein the at least one reactive functional group is an epoxide and / or anhydride and / or hydroxyl and / or isocyanate and / or acetal and / or aldehyde and / or carboxylic acid and / or ester and / or vinyl type, wherein n Q It is an integer between 1 and 1000.

[0051] It should be understood that when A is a single unit, G can contain n A The aforementioned monolithic unit. When Q is a monolithic unit, G can contain n. Q Each of the aforementioned single-unit cells.

[0052] A and Q can be statistically, gradient-wise, or block-wise copolymerized to form G.

[0053] The context of R, R1, R2, R3, and R4 alkyl "Specifically refers to C1 to C" 20 Alkyl group. The expression " C 1 To C 20 alkyl "" refers to a straight-chain or branched alkyl group containing 1 to 20 carbon atoms. (C1 to C2) 20 Alkyl groups, especially C2 to C3 20 Alkyl, C5 to C 20 Alkyl or C5 to C 10 alkyl.

[0054] The context of R1, R2, R3, and R4 Olefins "Specifically refers to straight chains or branched chains C2 to C..." 20 Alkyl group, containing one or more carbon-carbon double bonds. C2 to C3 20 Olefins, especially C2 to C3 10 Olefins, C5 to C 20 Olefins or C5 to C 10 Olefins.

[0055] The context of R1, R2, R3, and R4 alkynes "Specifically refers to straight chains or branched chains C2 to C..." 20 Alkyl group, containing one or more carbon-carbon triple bonds. C2 to C3 20 Alkynes, especially C2 to C 10 Alkynes, C5 to C 20 Alkynes or C5 to C 10 Alkynes.

[0056] The context of R, R1, R2, R3, and R4 Aryl "Specifically refers to C1 to C" 20Aryl, such as C6 to C 20 Aryl or C1 to C 10 Aryl.

[0057] In the context of R1, R2, R3, and R4, "saturated or unsaturated carbonyl ring" specifically refers to C3 to C4 rings that optionally contain one or more double bonds. 20 Cycloalkyl.

[0058] In the context of R1, R2, R3, and R4, "saturated or unsaturated heterocycles" specifically refers to C3 through C4 as defined above. 20 Cycloalkyl groups, which further contain heteroatoms in their rings, particularly O, S, or N.

[0059] The preferences listed below can be chosen independently or in combination with each other.

[0060] Preferably, the oligonucleotide initiator has the formula (I), where Z = O.

[0061] Preferably, the oligonucleotide initiator has formula (I), wherein: Z = O and; R 2 and R 3 This indicates an alkyl, acyl, aryl, olefinic, or alkyne group that may be optionally substituted.

[0062] In one embodiment, G may contain only Q, i.e., n A It is 0.

[0063] Preferably, G comprises A as a monomer unit or a linear or structured polymer chain comprising 1 to 300 monomer units. It should be understood that when A is a monomer unit, G comprises 1 to 300 of the monomer units.

[0064] Preferably, G comprises Q as a monomer unit or a linear or structured polymer chain comprising 1 to 500 monomer units. It should be understood that when Q is a monomer unit, G comprises 1 to 500 of the monomer units.

[0065] Preferably, A is a monomer unit or a polymer chain containing a hydrophilic monomer, wherein the hydrophilic monomer contains at least one olefinic unsaturated functional group selected from nonionic and / or anionic and / or cationic and / or zwitterionic monomers.

[0066] The nonionic monomer is preferably selected from the group consisting of: water-soluble vinyl monomers, such as acrylamide, methacrylamide, N-alkylacrylamide, N-alkylmethylacrylamide, N,N-dialkylacrylamide (e.g., N,N-dimethylacrylamide or N,N-diethylacrylamide), N,N-dialkylmethylacrylamide, alkoxylated esters of acrylic acid, alkoxylated esters of methacrylic acid, N-vinylpyrrolidone, N-hydroxymethyl (meth)acrylamide, N-vinylcaprolactam, N-vinylformamide (NVF), N-ethyl... Alkenylacetamide, N-vinylimidazolium, N-vinylsuccinimide, acrylamide (ACMO), glycidyl methacrylate, glyceryl methacrylate, diacetone acrylamide, methacrylic anhydride, acrylonitrile, maleic anhydride, itaconic anhydride, itaconic acid, vinylpyridine, hydroxyalkyl (meth)acrylate, thioalkyl (meth)acrylate, isoprene alcohol and its alkoxylated derivatives, hydroxyethyl (meth)acrylate and its alkoxylated derivatives, hydroxypropyl acrylate and its alkoxylated derivatives, vinyl acetate and mixtures thereof. In these nonionic monomers, the alkyl group is advantageously C1-C5, more advantageously C1-C3. They are preferably straight-chain alkyl groups.

[0067] The anionic monomer is preferably selected from acrylic acid; methacrylic acid; dimethacrylic acid; itaconic acid; crotonic acid; maleic acid; fumaric acid; acrylamidoundecanoic acid; 3-acrylamido-3-methylbutyric acid; maleic anhydride; strong acid monomers having functional groups of the type of sulfonic acid or phosphonic acid, such as vinylsulfonic acid, vinylphosphonic acid, allylsulfonic acid, methylallylsulfonic acid, 2-methylenepropane-1,3-disulfonic acid, 2-sulfoethyl methacrylate, sulfopropyl methacrylate, sulfopropyl acrylate, allylphosphonic acid, styrenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid (ATBS), 2-acrylamido-2-methylpropanedisulfonic acid; water-soluble salts of these monomers, such as their alkali metal salts (different from the crystal form of sodium 2-acrylamido-2-methylpropanesulfonate), alkaline earth metal salts or ammonium salts; and mixtures thereof.

[0068] In certain embodiments, the anionic hydrophilic monomer can be salted.

[0069] The term "salting" refers to the substitution of a proton for at least one acidic functional group of the anionic monomer -R(=O)-OH (where R = P, S, or C) by a metal cation or an ammonium cation to form a salt of the type -R(=O)-OX (where X is a metal cation or an ammonium cation). In other words, the non-salting form corresponds to the acidic form of the monomer, such as RC(=O)-OH in the case of a carboxylic acid functional group, while the salting form of the monomer corresponds to the form RC(=O)O. - X + X +Corresponding to alkali metal cations or ammonium cations. The salting of acid functional groups in polymers can be partial or complete.

[0070] The salting form advantageously corresponds to alkali metal (Li, Na, K, etc.) salts, alkaline earth metal (Ca, Mg, etc.) salts, or ammonium salts (e.g., ammonium ions or tertiary ammonium salts). The preferred salt is a sodium salt.

[0071] Salting can be performed before or after polymerization.

[0072] The cationic monomer is preferably selected from monomers derived from vinyl-type (favorably acrylamide, acrylic acid, allyl or maleic acid-type) units, which have phosphonium or quaternary ammonium functional groups.

[0073] In particular and in a non-limiting manner, reference may be made to diallyl dialkylammonium salts, such as diallyl dimethylammonium chloride (DADMAC); acidified or quaternized salts of dialkylaminoalkylacrylamides; acidified or quaternized salts of dialkylaminoalkylmethylacrylamides, such as methacrylamidopropyltrimethylammonium chloride (MAPTAC), acrylamidopropyltrimethylammonium chloride (APTAC); acidified or quaternized salts of dialkylaminoalkyl acrylates, such as quaternized or salted dimethylaminoethyl acrylate (ADAME); acidified or quaternized salts of dialkylaminoalkyl methacrylates, such as quaternized or salted dimethylaminoethyl methacrylate (MADAME); and mixtures thereof. Advantageously, the alkyl group is C1-C3 alkyl.

[0074] Those skilled in the art will know how to prepare quaternized monomers, for example, by using RX-type quaternizing agents, where R is an alkyl group and X is a halogen or sulfate.

[0075] "Quaternary ammonifying agent" refers to a molecule that can alkylate tertiary amines.

[0076] The quaternizing agent can be selected from dialkyl sulfates containing 1 to 6 carbon atoms or alkyl halides containing 1 to 6 carbon atoms. Preferably, the quaternizing agent is selected from methyl chloride, benzyl chloride, dimethyl sulfate, or diethyl sulfate. Additionally, the present invention also covers monomers of the DADMAC, APTAC, and MAPTAC types, wherein the counterion is sulfate, fluoride, bromide, or iodide rather than chloride.

[0077] The zwitterionic monomer is preferably selected from derivatives having vinyl-type (especially acrylamide, acrylic acid, allyl, or maleic acid-type) units. Preferably, the monomer contains amine or quaternary ammonium functional groups and acid functional groups of the type of carboxylic acid (or carboxylate), sulfonic acid (or sulfonate), or phosphoric acid (or phosphate). In particular, and in a non-limiting manner, reference may be made to derivatives of dimethylaminoethyl acrylate, such as 2-((2-(acryloyloxy)ethyl)dimethylammonium)ethane-1-sulfonate, 3-((2-(acryloyloxy)ethyl)dimethylammonium)propane-1-sulfonate, 4-((2-(acryloyloxy)ethyl)dimethylammonium)butane-1-sulfonate, and [2-(acryloyloxy)ethyl](dimethylammonium)acetate; and derivatives of dimethylaminoethyl methacrylate, such as 2-((2-(methacryloyloxy)ethyl)dimethylammonium)ethane-1-sulfonate, 3-((2-(methacryloyloxy)ethyl)dimethylammonium)propane-1-sulfonate, 4-(2-(methacryloyloxy)ethyl)dimethylammonium)butane-1-sulfonate, and [2-(methacryloyloxy)ethyl](dimethylammonium)acetate. [3-(3-acrylamidopropyl)dimethylammonium)acetate; derivatives of dimethylaminopropylacrylamide, such as 2-((3-acrylamidopropyl)dimethylammonium)ethane-1-sulfonate, 3-((3-acrylamidopropyl)dimethylammonium)propane-1-sulfonate, 4-((3-acrylamidopropyl)dimethylammonium)butane-1-sulfonate, [3-(acryloyl)oxy)propyl](dimethylammonium)acetate; dimethylaminopropylmethacrylamide, 2-((3-methacrylamidopropyl)dimethylammonium)ethane-1-sulfonate, 3-((3-methacrylamidopropyl)dimethylammonium)propane-1-sulfonate, 4-((3-methacrylamidopropyl)dimethylammonium)butane-1-sulfonate, [3-(methacryloyloxy)propyl](dimethylammonium)acetate; and mixtures thereof.

[0078] Other zwitterionic monomers are described by the applicant in document WO 21123599.

[0079] Preferably, A is a monomer unit or a linear or structured polymer chain, characterized in that the monomer of the monomer unit or polymer chain is selected from: acrylamide, acrylic acid, 2-acrylamido-2-methylpropanesulfonic acid (ATBS) and / or its salts, N-vinylformamide (NVF), N-vinylpyrrolidone (NVP), dimethyl diallyl ammonium chloride (DADMAC), dimethylaminoethyl quaternized acrylate (ADAME), dimethylaminoethyl quaternized methacrylate (MADAME), and itaconic acid.

[0080] Preferably, Q is a monomer unit or a linear or structured polymer chain, characterized in that the monomer of the monomer unit or polymer chain is selected from glycidyl methacrylate, methacrylic anhydride, maleic anhydride, itaconic anhydride, hydroxy(alkyl) acrylate, glycidyl acrylate, allyl glycidyl ether, and (meth)acrylate allyl ester.

[0081] In the preferred mode, based on the total weight of carbon in the relevant monomers, the bio-based carbon content of monomers A and Q is between 5% by weight and 100% by weight, preferably between 10% by weight and 100% by weight, said bio-based carbon content being measured according to ASTM D6866-21, Method B.

[0082] When A and Q combine and polymerize, G is formed. The groups G, which include A and Q, can be statistical copolymers, block copolymers, or gradient copolymers.

[0083] "Statistical copolymer" refers to a copolymer in which the monomers are randomly organized. Statistical copolymers are obtained by placing all the monomers that make up the copolymer at the start of polymerization.

[0084] Instances are structural features, such as: -SAQAQR 2 "Block copolymers" refers to diblock, grafted block polymers, and branched block polymers (also known as linear star polymers).

[0085] Block copolymers are polymers composed of blocks of at least two different monomers. Diblock polymers have two different blocks. These diblock polymers are advantageously obtained by continuously polymerizing different monomer species.

[0086] In a specific pattern, when composed of two different monomers, the polymer has an XY-type structure. In other words, the first fraction contains only monomer X. These polymerize first, and once all monomer X has reacted, a second fraction containing monomer Y is added.

[0087] Instances are structural features, such as: -SA nA -Q nQ -R 2 Or SQ nq -A nA -R 2 "Gradient copolymer" refers to a polymer in which the monomer composition varies in a controlled manner throughout the polymer chain.

[0088] Polymers with gradient structures are polymers composed of at least two monomers, where the monomer composition changes gradually, as opposed to block polymers with abrupt compositional changes and random polymers with discontinuous compositional changes. In gradient polymers, intra- and inter-chain repulsive forces are relatively small because the composition changes gradually along the polymer chain length.

[0089] Gradients can be formed by spontaneous gradients or forced gradients. Spontaneous gradient polymerization is caused by differences in monomer reactivity. Forced gradient polymerization involves altering the monomer composition introduced throughout the polymerization process.

[0090] The gradient forcing process includes (1) The first monomer fraction is introduced into the reactor. (2) Add at least one additional monomer fraction, advantageously different from the first, and (3) The monomers introduced into the reactor are polymerized. Once the first fraction is introduced, the polymerization of the monomers is started.

[0091] The addition of additional monomer fractions can be performed concurrently with the introduction of the first monomer fraction into the reactor (therefore, the introduction of fractions can begin and end simultaneously). Alternatively, the first monomer (first fraction) can be started being fed into the reactor before the second monomer fraction is added. Alternatively, the first and second fractions can be introduced simultaneously, but the time required to add the second fraction can be longer than the time required to introduce the first fraction into the reactor. This method is also suitable for processes using three or more monomer fractions.

[0092] Preferably, the oligonucleotide initiator has formula (I), wherein: Z = O and; R 2 and R 3 This indicates an optionally substituted alkyl, acyl, aryl, olefin, or alkyne group, and A is a monomeric unit or a linear or structured polymer chain containing 1 to 300 monomeric units, preferably selected from: acrylamide, acrylic acid, 2-acrylamido-2-methylpropanesulfonic acid (ATBS) and / or its salts, N-vinylformamide (NVF), N-vinylpyrrolidone (NVP), dimethyl diallyl ammonium chloride (DADMAC), quaternized dimethylaminoethyl acrylate (ADAME), quaternized dimethylaminoethyl methacrylate (MADAME), and itaconic acid.

[0093] Q is a monomer unit or a linear or structured polymer chain containing 1 to 500 monomer units, preferably selected from: glycidyl methacrylate, methacrylic anhydride, maleic anhydride, itaconic anhydride, hydroxy(alkyl) acrylate, glycidyl acrylate, allyl glycidyl ether, and (meth)acrylate allyl ester.

[0094] According to a preferred embodiment of the present invention, the oligonucleotide initiator has the following formula (II): [Chemical Formula 2]

[0095] (II) Wherein nA, acrylamide unit, is between 1 and 300, and nQ, glycidyl methacrylate unit, is between 1 and 500.

[0096] According to a second preferred embodiment of the present invention, the oligonucleotide initiator has the following formula (III): [Chemical Formula 3]

[0097] (III) Where nA, itaconic acid unit, is between 1 and 300, and nQ, itaconic anhydride unit, is between 1 and 500.

[0098] Another aspect of the present invention is to provide a method for synthesizing such oligonucleotide initiators.

[0099] Oligonucleotide initiators are obtained through free radical polymerization. Free radical polymerization includes polymerization using photochemical (UV or radiation) initiators, azo initiators, thermal initiators, or redox salts, as well as controlled radical polymerization (CRP) or matrix polymerization techniques.

[0100] As controlled radical polymerization techniques, techniques may be mentioned in a non-limiting manner, such as iodine transfer polymerization (ITP), nitro oxygen-mediated polymerization (NMP) or atom transfer radical polymerization (ATRP), reversible addition-fragmentation chain transfer (RAFT) polymerization, which includes macromolecular design (MADIX) technology via xanthate salt exchange, various variations of polymerization using organometallic compounds (organometallic-mediated radical polymerization (OMRP)) and organic heteroatom-mediated radical polymerization (OHRP).

[0101] In a preferred embodiment, polymerization is carried out by reversible addition-fracture chain transfer (RAFT) polymerization.

[0102] The oligonucleotide initiator is preferably obtained by reacting at least one molecule of formula (IV) with at least one monomer (selected from the monomers having at least one reactive functional group (frQ) described above) and at least one hydrophilic monomer containing at least one olefinic unsaturated functional group described above, as follows: [Chemical Formula 4]

[0103] (IV) Following this reaction, the oligonucleotide initiator contains at least one reactive functional group (frQ) capable of reacting with the complementary functional group.

[0104] Advantageously, polymerization initiators can be selected from compounds that dissociate into free radicals under polymerization conditions, such as organic peroxides, hydroperoxides, hydrogen peroxide, persulfates, azo compounds, and redox catalysts. The use of water-soluble initiators is preferred. In some cases, it is advantageous to use mixtures of various polymerization initiators, such as mixtures of redox salts and azo compounds.

[0105] Advantageously, the amount of initiator is between 5 ppm and 1000 ppm relative to the total weight of the polymerization raw materials, preferably between 10 ppm and 500 ppm, and more preferably between 20 ppm and 100 ppm.

[0106] The initiator can be added to the reaction mixture in one pour or added to the medium in batches.

[0107] Oligonucleotide initiators can be prepared alone or in solution in water or in a solvent, particularly alcohol solvents such as methanol, ethanol, and isopropanol. Preferably, the oligonucleotide initiator is prepared in water.

[0108] Preferably, the oligonucleotide initiator is prepared at a temperature between 5°C and 100°C, more preferably between 10°C and 80°C, and more preferably between 15°C and 75°C.

[0109] Advantageously, the synthesis of this oligonucleotide initiator is carried out over a period of 1 to 12 hours, preferably 1 to 5 hours. Preferably, it is carried out at atmospheric pressure.

[0110] The present invention also relates to the use of an oligonucleotide initiator according to the invention for producing water-soluble polymers, preferably water-soluble hybrid polymers.

[0111] According to one aspect of the invention, oligonucleotide initiators are advantageously used in the synthesis of water-soluble hybrid polymers.

[0112] According to this aspect of the invention, a water-soluble hybrid polymer HP is obtained by functionalizing biopolymer B1 with an oligonucleotide initiator of the above general formula (I), followed by polymerization of at least one hydrophilic monomer having at least one olefinic unsaturated functional group.

[0113] Biopolymer B1 Biopolymer B1 is a polymer derived from natural and / or renewable resources, that is, a polymer derived from living organisms or synthesized from renewable resources.

[0114] Preferably, the biopolymer B1 according to the invention is water-soluble. Water-soluble is understood to mean soluble across the entire pH range of water, which includes biopolymers such as chitosan, which is soluble in acidified water. Insoluble biopolymers may also be used after being treated to make them soluble, according to techniques known to those skilled in the art.

[0115] According to the present invention, the biopolymer B1 synthesized from renewable resources may be, but is not limited to, biopolymers derived from the hydrolysis and / or fermentation of renewable resource products.

[0116] For example, this includes products obtained through polycondensation, such as polyesters, phenolic derivatives such as tannins or lignin, or products obtained through biomass fermentation, such as microbial polymers: itaconic acid polymers, polyhydroxyalkanoates (HPA), xanthan gum, pullullan, lactic acid polymers, glycolic acid polymers, succinic acid, or polyesters, polyhydroxybutyrates.

[0117] As used herein, the term "biopolymer" includes native or natural biopolymers, biopolymers synthesized from natural compounds, biopolymer derivatives, and modified biopolymers. The term "modified biopolymer" refers to a natural biopolymer that has undergone one or more treatments. These treatments may impart physical and / or chemical and / or enzymatic properties.

[0118] According to this application, the biopolymer B1 derived from a living organism is preferably selected from polysaccharides or proteins.

[0119] Proteins are obtained using conventional methods known to those skilled in the art, such as by dissolving, grinding, screening, and sorting.

[0120] The proteins according to the invention may be of animal origin. Examples of animal proteins that may be mentioned include: milk proteins, such as β-lactoglobulin, casein, whey; serum proteins, such as horse serum; placental proteins; and fibrous dermal proteins, such as collagen, elastin, and silk fibroin.

[0121] The proteins according to the invention can be of plant origin, such as corn, wheat, barley, oats, soybeans, and peas, and include, for example, gluten, gliadin, zein, and gluten. Advantageously, the plant proteins are selected from soybean protein, wheat protein, oat protein, and pea protein. The proteins can be obtained from seeds, such as soybeans, cottonseed, peanuts, sunflower seeds, rapeseed, coconut, flaxseed, sesame, safflower, peas, kidney beans, or lentils.

[0122] Other sources of protein include bacteria, fungi, algae, and yeast, such as Pseudomonas, Lactobacillus, Penicillium, Escherichia coli, cyanobacteria, green algae, Chlorella, Spirulina, and spent yeast.

[0123] Preferably, the selected protein is casein, serum protein, or wheat protein.

[0124] To convert proteins into a soluble form, digestion is typically required through physical, chemical, or enzymatic treatments, such as acid or alkaline hydrolysis, fermentation with yeast, bacteria, or enzymes, extraction methods to remove trace components, coagulation of the extract by heating, addition of electrolytes, pH adjustment, or the addition of precipitating agents. Pure products can be prepared, for example, by fractional dissolution and precipitation or by dialysis.

[0125] Proteins can exist in the form of mixtures. This means a mixture containing multiple proteins from the same biological kingdom or different kingdoms. For example, a mixture containing multiple animal-derived proteins, or a mixture containing at least one animal-derived protein and at least one plant-derived protein and / or one bacterial-derived protein.

[0126] Polysaccharides can be extracted from plants, produced by microorganisms such as bacteria, fungi, prokaryotes, and eukaryotes, or extracted from animals and / or humans. For example, xanthan gum can be produced by Xanthomonas campestris (…). Xanthomonas campestris Gel is produced by *Sphingosine monocytogenes* (S. oligokinesi). Sphingomonas paucimobilis Xyloglucan is produced and can be extracted from tamarind seeds.

[0127] Preferably, the polysaccharide is selected from the group consisting of: tamarind gum (preferably composed of xylo-glucan polymers), guar gum, locust bean gum (preferably composed of galactomannan polymers), and other industrial gums and polymers, including but not limited to tara gum, fenugreek gum, aloe vera gum, chia seed gum, flaxseed gum, plantain seed gum, quince seed gum, xanthan gum, gellan gum, vinylon gum, rhamn gum, dextran, gel polysaccharide, pullulan, stearyl glucan, schizocarpine, chitin, hydroxyalkyl cellulose, arabinogalactan (preferably derived from sugar beet), and arabinogalactan. Glucan, galactan (preferably from lupin and potato), pectin galactan (preferably from potato), galactomannan (preferably from carob tree, including both low and high viscosity), glucomannan, lichen polysaccharide (preferably from Iceland moss), mannan (preferably from ivory palm), pachymannan, rhamnogalacturonic acid polysaccharide, gum arabic, agar, alginate, carrageenan, chitosan, clavan, hyaluronic acid, heparin, inulin, cellodextrin, cellulose, cellulose derivatives, and mixtures thereof.

[0128] Polysaccharides can be linear, such as hydroxyalkyl cellulose; they can have alternating repeating units, such as carrageenan; they can have discontinuous repeating units, such as pectin; they can be block copolymers, such as alginate; they can be branched, such as dextran; or they can have complex repeating units, such as xanthan gum. Polysaccharides are described in "An Introduction to Polysaccharide Biotechnology," M. Tombs and SE Harding, TJ Press, 1998.

[0129] Polysaccharides can be modified by (primary, secondary, tertiary) amines, amides, esters, ethers, carbamates, alcohols, carboxylic acids, toluenesulfonates, sulfonates, sulfates, nitrates, phosphates, and mixtures thereof. Such modification can occur at positions 2, 3, and / or 6 of the sugar unit. These modified or derived polysaccharides, in addition to natural polysaccharides, may also be included in this invention.

[0130] Among the non-limiting examples of these modified polysaccharides, the following may be mentioned: carboxyl and hydroxymethyl substitutions (e.g., glucuronic acid instead of glucose); aminopolysaccharides (amine substitutions, e.g., glucosamine instead of glucose); C1-C6 alkyl polysaccharides; acetylated polysaccharide ethers; polysaccharides with attached amino acid residues (small glycoprotein fragments); and polysaccharides containing silicone groups. Suitable examples of these modified polysaccharides are commercially available from Carbomer, and in particular include alginate amines such as hexamethylenediamine alginate, amine-functionalized cellulose such as O-methyl-(N-1,12-dodecanediamine)cellulose, biotin-heparin, carboxymethylated dextran, guar gum polycarboxylic acid, carboxymethylated locust bean gum, carboxymethylated locust bean gum, carboxymethylated xanthan gum, chitosan phosphate, chitosan phosphate sulfate, diethylaminoethyl dextran, dodecylamide alginate, sialic acid, glucuronic acid, galacturonic acid, mannanuronic acid, guluronic acid, N-acetylglucosamine, N-acetylgalactosamine, and mixtures thereof.

[0131] Preferably, the polysaccharide is selected from the group consisting of: chitosan, xanthan gum, fenugreek gum, tara gum, locust bean gum, carrageenan gum, guar gum, alginate, agar, tragacanth gum, tamarind gum, gum arabic, cherry gum, ark tung gum, okra gum, cinnamon gum, gum arabic, konjac gum, glucomannan, gum arabic, pectin, sclerotium gum, gellan gum, derivatives thereof, and combinations thereof. Chemically modified forms of these polymers may also be used.

[0132] Even more preferably, the polysaccharides are cellulose and cellulose ether, carboxyl, methyl, hydroxymethyl, ester and carbamate derivatives.

[0133] According to a preferred embodiment, biopolymer B1 is a polysaccharide, preferably selected from: starch or its derivatives, such as carboxymethyl starch; cellulose or its derivatives, such as carboxymethyl cellulose and hemicellulose; polysaccharides extracted from algae, such as agarose, carrageenan, and alginate; pectin; inulin; guar gum; konjac gum; dextran; pullulan; gellan gum; and gel polysaccharides.

[0134] Even more preferably, the polysaccharide will be selected from starch derivatives and / or cellulose derivatives. Even more preferably, the polysaccharide is carboxymethyl cellulose and / or carboxymethyl starch.

[0135] According to the present invention, the natural or modified biopolymer B1 contains at least one reactive functional group (frB), said at least one reactive functional group being a hydroxyl and / or carboxyl and / or acid anhydride and / or amine and / or amide and / or vinyl, and / or phosphate ester and / or sulfonate ester and / or ester and / or aldehyde and / or ketone and / or silane, and / or isocyanate and / or nitrile and / or acyl halide type.

[0136] More preferably, the reactive functional group (frB) is a hydroxyl, carboxyl, or anhydride group. In other words, biopolymer B1 contains at least one reactive functional group (frB) selected from hydroxyl, carboxyl, or anhydride functional groups.

[0137] The functional group (frB) is in the form of a side group.

[0138] According to a preferred embodiment, these reactive functional groups (frB) are neutralized with a base before and / or during the synthesis of the side-chain L-polymerization in step 2. The base is selected from bases containing ions, wherein the ions are selected from the group consisting of: Li... + Na + K + Ca ++ Mg ++ Zn ++ Al +++ or mixtures thereof; preferably, the base is selected from hydroxides, carbonates and bicarbonates, comprising a component selected from Li + Na + K + Ca ++ Mg ++ Zn ++ Al +++ Ions of or mixtures thereof.

[0139] Without being bound by any theoretical constraints, the applicant discovered that the presence of free carboxylate functional groups on biopolymer B1 enhances the reactivity of its free hydroxyl functional groups, enabling it to form optimized covalent bonds with oligonucleotide initiators, thereby forming functionalized biopolymer B2. Figure 1 ) The water-soluble hybrid polymer HP was obtained using an oligonucleotide initiator according to a method comprising at least the following sequential steps: 1. To functionalize biopolymer B1 by reacting at least one reactive functional group (frB) of biopolymer B1 with at least one reactive functional group (frQ) of the oligonucleotide initiator to obtain functionalized biopolymer B2. 2. A hydrophilic monomer containing at least one olefinic unsaturation is polymerized on at least one oligonucleotide initiator of the functionalized biopolymer B2 to form at least one side chain L, and thus obtains the hybrid polymer HP. Step (1) - Functionalize biopolymer B1 with the oligonucleotide initiator according to the invention to obtain biopolymer B2. In step (1) of the method according to the invention, biopolymer B2 is obtained by functionalizing biopolymer B1 with at least one oligonucleotide initiator according to the invention and by reacting at least one reactive functional group (frB) of biopolymer B1 with at least one reactive functional group (frQ) of the oligonucleotide initiator.

[0140] Therefore, biopolymer B2 corresponds to biopolymer B1 after biopolymer B1 has been functionalized with an oligonucleotide initiator.

[0141] The percentage of reactive functional groups (frB) substituted by oligonucleotide initiators in biopolymer B2 is between 0.1% and 90%, preferably between 0.1% and 50%, and even more preferably between 0.1% and 25%.

[0142] The mass ratio of the biopolymer B2 (B1 / oligonucleotide initiator) is preferably between 50 / 50 and 97 / 3.

[0143] Functionalization is carried out by contacting biopolymer B1 with at least one oligonucleotide initiator under the following appropriate conditions.

[0144] Oligonucleotide initiators can be added to the solution continuously via static or dynamic mixers or in microreactors. Those skilled in the art are familiar with various suitable addition methods.

[0145] One aspect of the invention is based on “mild” conditions for obtaining the biopolymer B2. In fact, the functionalization reaction is preferably carried out without solvents harmful to humans and the environment. The functionalization reaction is preferably carried out without the use of a catalyst. The functionalization reaction is preferably carried out without a purification step.

[0146] Biopolymer B2 can optionally be dissolved prior to functionalization.

[0147] Preferably, biopolymer B2 is prepared in an aqueous solution. Very preferably, the only solvent used is water. The reaction temperature is preferably between 5°C and 85°C, more preferably between 10°C and 70°C, and even more preferably between 15°C and 65°C.

[0148] Advantageously, the functionalization reaction of biopolymer B2 is carried out over a period of 1 to 12 hours, preferably 1 to 5 hours. The functionalization reaction is preferably carried out at atmospheric pressure.

[0149] Step (2) - Polymerization to obtain synthetic side chain L During step (2), the hydrophilic monomer inserts itself into the thiol functional group with the A or Q portion corresponding to the oligonucleotide initiator (if...). n A Preferably, they are aggregated between (= 0).

[0150] Step (2) consists of: polymerizing a hydrophilic monomer containing at least one olefinic unsaturation on at least one oligonucleotide initiator of the functionalized biopolymer B2 to form at least one side chain L, and thus obtaining the hybrid polymer HP.

[0151] In step (2) according to the invention, the polymerization of a hydrophilic monomer containing at least one olefinic unsaturation is carried out on an oligonucleotide initiator of functionalized biopolymer B2.

[0152] The hydrophilic monomer inserts itself into the thiol functional group and the A or Q part corresponding to the oligonucleotide initiator (if... n A Preferably, they are aggregated between (= 0).

[0153] Therefore, it is expected that there will be as many synthetic side chains L as there are bonds between the polymer chain of biopolymer B2 and the oligonucleotide initiator, corresponding to the number of sites (frB-frQ) on the functionalized biopolymer B2.

[0154] In other words, if there is only one bond between the functionalized biopolymer B2 and the oligonucleotide initiator, there will be only one synthetic side chain L. If there are two bonds between the functionalized biopolymer B2 and the oligonucleotide initiator, there will be two synthetic side chains L. If there are three bonds between the functionalized biopolymer B2 and the oligonucleotide initiator, there will be three synthetic side chains L, and so on.

[0155] Advantageously, the synthetic side chain L is obtained by free radical polymerization. Free radical polymerization includes polymerization using photochemical (UV or radiation) initiators, azo initiators, thermal initiators, or redox salts, as well as controlled radical polymerization (CRP) or matrix polymerization techniques.

[0156] As controlled radical polymerization techniques, techniques may be mentioned in a non-limiting manner, such as iodine transfer polymerization (ITP), nitro oxygen-mediated polymerization (NMP) or atom transfer radical polymerization (ATRP), reversible addition-fragmentation chain transfer (RAFT) polymerization, which includes macromolecular design (MADIX) technology via xanthate salt exchange, various variations of polymerization using organometallic compounds (organometallic-mediated radical polymerization (OMRP)) and organic heteroatom-mediated radical polymerization (OHRP).

[0157] In a preferred embodiment, the polymerization is carried out by reversible addition-fragmentation chain transfer (RAFT) polymerization of at least one hydrophilic monomer containing at least one olefinic unsaturation (a double bond between two carbon atoms).

[0158] The polymerization reaction in step (2) corresponds to the formation and elongation of the polymer chain on the oligonucleotide initiator, preferably through the cleavage and addition of monomer units. The hydrophilic monomer inserts itself into the thiol functional group corresponding to the A or Q portion of the oligonucleotide initiator (if...). n A Preferably, they are aggregated between (= 0).

[0159] The polymerization reaction in step (2) is carried out as follows: the functionalized biopolymer B2 is mixed, a hydrophilic monomer containing at least one olefinic unsaturation is poured (continuous or discontinuous), and then polymerization is initiated.

[0160] Preferably, the polymerization reaction is carried out in an aqueous medium, and most preferably in water. The reaction temperature is preferably between 5°C and 100°C, more preferably between 10°C and 70°C, and even more preferably between 15°C and 65°C.

[0161] Advantageously, the polymer reaction is carried out over a period of 1 to 12 hours, preferably 2 to 7 hours. The functionalization reaction is preferably carried out at atmospheric pressure.

[0162] The hydrophilic monomer is preferably selected from nonionic monomers and / or anionic monomers and / or cationic monomers and / or zwitterionic monomers.

[0163] Advantageously, the nonionic hydrophilic monomers that can be used in the context of this invention are particularly selected from the group comprising: water-soluble vinyl monomers such as acrylamide, methacrylamide, N-alkylacrylamide, N-alkylmethylacrylamide, N,N-dialkylacrylamide (e.g., N,N-dimethylacrylamide or N,N-diethylacrylamide), N,N-dialkylmethylacrylamide, alkoxylated esters of acrylic acid, alkoxylated esters of methacrylic acid, N-vinylpyrrolidone, N-hydroxymethylacrylamide, N-vinylformamide (NVF), N-vinylacetamide, N-vinylimidazolium, N-vinylsuccinimide, acryloylmorpholine (ACMO), acryloyl chloride, glycidyl methacrylate, glyceryl methacrylate, diacetone acrylamide, hydroxyalkyl (meth)acrylate, aminoalkyl (meth)acrylate, thioalkyl (meth)acrylate, hydroxyalkyl acrylate, hydroxyalkyl methacrylate, and mixtures thereof. Among these nonionic monomers, the alkyl group is advantageously C1-C5, and more advantageously C1-C3 alkyl. They are preferably straight-chain alkyl groups.

[0164] Advantageously, the anionic hydrophilic monomers that can be used in the context of this invention can be selected from a large class. These monomers may have vinyl functional groups (advantageously acrylic acid, maleic acid, fumaric acid, malonic acid, itaconic acid or allyl functional groups) and contain carboxyl, phosphonate, phosphate, sulfate or sulfonate groups, or another group with an anionic charge. Examples of suitable monomers include acrylic acid; methacrylic acid; dimethacrylic acid; itaconic acid; crotonic acid; maleic acid; fumaric acid; acrylamidoundecanoic acid; 3-acrylamido-3-methylbutyric acid; maleic anhydride; strong acid monomers having functional groups of the type of sulfonic acid or phosphonic acid, such as vinylsulfonic acid, vinylphosphonic acid, allylsulfonic acid, methylallylsulfonic acid, 2-methylenepropane-1,3-disulfonic acid, 2-sulfoethyl methacrylate, sulfopropyl methacrylate, sulfopropyl acrylate, allylphosphonic acid, styrenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid (ATBS), 2-acrylamido-2-methylpropanedisulfonic acid; water-soluble salts of these monomers, such as their alkali metal salts, alkaline earth metal salts, or ammonium salts; and mixtures thereof. Preferably, the anionic hydrophilic monomer is acrylic acid and / or its salts.

[0165] In certain embodiments of the invention, the anionic monomer may be salted. It may also be a mixture of acid and salted form, such as a mixture of acrylic acid and acrylate.

[0166] The term "salting" refers to the substitution of a proton for at least one acidic functional group of the anionic monomer -R(=O)-OH (where R = P, S, or C) by a metal cation or an ammonium cation to form a salt of the type -R(=O)-OX (where X is a metal cation or an ammonium cation). In other words, the non-salting form corresponds to the acidic form of the monomer, such as RC(=O)-OH in the case of a carboxylic acid functional group, while the salting form of the monomer corresponds to the form RC(=O)O. - X + X + Corresponding to alkali metal cations or ammonium cations. The salting of acid functional groups in aqueous polymers can be partial or complete.

[0167] The salting form advantageously corresponds to alkali metal (Li, Na, K, etc.) salts, alkaline earth metal (Ca, Mg, etc.) salts, or ammonium salts (e.g., ammonium ions or tertiary ammonium salts). The preferred salt is a sodium salt.

[0168] Salting can be performed before, during, or after polymerization in step (2).

[0169] Advantageously, in the context of this invention, the cationic hydrophilic monomer can be selected from monomers derived from vinyl-type (advantageously acrylamide, acrylic acid, allyl or maleic acid-type) units, which have phosphonium or quaternary ammonium functional groups.

[0170] In particular and in a non-limiting manner, reference may be made to diallyl dialkylammonium salts, such as diallyl dimethylammonium chloride (DADMAC); acidified or quaternized salts of dialkylaminoalkylacrylamides; acidified or quaternized salts of dialkylaminoalkylmethylacrylamides, such as methacrylamidopropyltrimethylammonium chloride (MAPTAC), acrylamidopropyltrimethylammonium chloride (APTAC); acidified or quaternized salts of dialkylaminoalkyl acrylates, such as quaternized or salted dimethylaminoethyl acrylate (ADAME); acidified or quaternized salts of dialkylaminoalkyl methacrylates, such as quaternized or salted dimethylaminoethyl methacrylate (MADAME); and mixtures thereof. Advantageously, the alkyl group is C1-C3 alkyl.

[0171] Those skilled in the art will know how to prepare quaternized monomers, for example, by using RX-type quaternizing agents, where R is an alkyl group and X is a halogen or sulfate.

[0172] "Quaternary ammonifying agent" refers to a molecule that can alkylate tertiary amines.

[0173] The quaternizing agent can be selected from dialkyl sulfates containing 1 to 6 carbon atoms or alkyl halides containing 1 to 6 carbon atoms. Preferably, the quaternizing agent is selected from methyl chloride, benzyl chloride, dimethyl sulfate, or diethyl sulfate. Additionally, the present invention also covers monomers of the DADMAC, APTAC, and MAPTAC types, wherein the counterion is sulfate, fluoride, bromide, or iodide rather than chloride.

[0174] Advantageously, the zwitterionic hydrophilic monomer can be a derivative of a vinyl type (advantageously acrylamide, acrylic acid, allyl or maleic acid type) unit, which has an amine or quaternary ammonium functional group and an acid functional group of the type of carboxylic acid (or carboxylate), sulfonic acid (or sulfonate) or phosphoric acid (or phosphate). In particular, and in a non-limiting manner, reference may be made to derivatives of dimethylaminoethyl acrylate, such as 2-((2-(acryloyloxy)ethyl)dimethylammonium)ethane-1-sulfonate, 3-((2-(acryloyloxy)ethyl)dimethylammonium)propane-1-sulfonate, 4-((2-(acryloyloxy)ethyl)dimethylammonium)butane-1-sulfonate, and [2-(acryloyloxy)ethyl](dimethylammonium)acetate; and derivatives of dimethylaminoethyl methacrylate, such as 2-((2-(methacryloyloxy)ethyl)dimethylammonium)ethane-1-sulfonate, 3-((2-(methacryloyloxy)ethyl)dimethylammonium)propane-1-sulfonate, 4-((2-(methacryloyloxy)ethyl)dimethylammonium)butane-1-sulfonate, and [2-(methacryloyloxy)ethyl]( [3-(3-acrylamidopropyl)dimethylammonium)acetate; derivatives of dimethylaminopropylacrylamide, such as 2-((3-acrylamidopropyl)dimethylammonium)ethane-1-sulfonate, 3-((3-acrylamidopropyl)dimethylammonium)propane-1-sulfonate, 4-((3-acrylamidopropyl)dimethylammonium)butane-1-sulfonate, [3-(acryloyloxy)propyl](dimethylammonium)acetate; derivatives of dimethylaminopropylmethacrylamide, such as 2-((3-methacrylamidopropyl)dimethylammonium)ethane-1-sulfonate, 3-((3-methacrylamidopropyl)dimethylammonium)propane-1-sulfonate, 4-((3-methacrylamidopropyl)dimethylammonium)butane-1-sulfonate and [3-(methacryloyloxy)propyl](dimethylammonium)acetate; and mixtures thereof.

[0175] The weight-average molecular weight of the side chain L is between 5,000 Da and 1,000,000 Da, preferably between 10,000 Da and 800,000 Da, and even more preferably between 20,000 Da and 500,000 Da.

[0176] According to another embodiment of the invention, the polymerization can be a free radical ring-opening polymerization, which may be of the RAFT type.

[0177] Ring-opening polymerization (ROP) is a polymerization process in which cyclic monomers polymerize after the ring is opened. The polymerization can be ionic or free radical polymerization.

[0178] Radical ring-opening polymerization (rROP) for cyclic monomers combines the advantages of ring-opening polymerization and radical polymerization. Therefore, polymers with heteroatoms in the main chain (polymer backbone) can be prepared while benefiting from the simplicity and robustness of radical polymerization processes.

[0179] In this context, in addition to hydrophilic monomers containing at least one olefinic unsaturation, cyclic monomers that can be used in the context of this invention may be selected from: cyclic enone acetals, or thiocarbonyl lactones or mixtures thereof.

[0180] The cyclic enone acetal is advantageously selected from the following compounds: 2-methylene-1,3-dioxane-heptane (MDO), 5,6-benzo-2-methylene-1,3-dioxane-heptane (BMDO), 2-methylene-4-phenyl-1,3-dioxolane (MPDL), 2-methylene-1,3,6-trioxane-octane (MTC), and mixtures thereof. Preferably, it is 2-methylene-1,3-dioxane-heptane (MDO).

[0181] Advantageously, the amount of cyclic enone acetal in side chain L is between 5 mol% and 30 mol% relative to the total amount of monomers in side chain L, preferably between 5 mol% and 20 mol%.

[0182] The thiocarbonyl lactone is advantageously selected from: dibenzo[c,e]oxetane(7H)-5-thione (DOT), ε-thiocarbonylcaprolactone, 3,3-dimethyl-2,3-dihydro-5H-benzo[e][1,4]dioxetane-5-thione (DBT) and mixtures thereof. Preferably, it is 3,3-dimethyl-2,3-dihydro-5H-benzo[e][1,4]dioxetane-5-thione.

[0183] Advantageously, the amount of thiocarbonyl lactone in side chain L is between 2 mol% and 20 mol%, preferably between 5 mol% and 15 mol%, relative to the total amount of monomer in side chain L.

[0184] Advantageously, the amount of hydrophilic monomers containing at least one olefinic unsaturation in the side chain L is between 50 mol% and 93 mol%, preferably between 65 mol% and 90 mol%.

[0185] According to this embodiment, the side chain L is preferably obtained by free radical polymerization of at least two monomers: - At least one hydrophilic monomer, comprising at least one olefinic unsaturation selected from nonionic monomers, anionic monomers, cationic monomers and zwitterionic monomers; - At least one cyclic monomer selected from cyclic enone acetals, thiocarbonyl lactones and mixtures thereof.

[0186] Hybrid polymer HP According to the present invention, the above-described method is used to obtain the water-soluble hybrid polymer HP by functionalizing the biopolymer B1 with an oligonucleotide initiator of the general formula (I) according to the present invention, followed by polymerization of at least one hydrophilic monomer having at least one olefinic unsaturated functional group.

[0187] The same preferences described above in other sections apply to this section concerning hybrid polymers (HP), particularly the references related to oligonucleotide initiators.

[0188] Water-soluble hybrid polymers are preferably obtained using oligonucleotide initiators of formula (I), wherein: Z = O, R 1 and R 2 This indicates an optional substituted alkyl, acyl, aryl, olefin, or alkyne group. A is a single unit or includes n A Linear polymer chains consisting of 1 to 300 monomer units; Q is a single unit or a component. n Q Linear polymer chains of 1 to 500 monomer units.

[0189] The hybrid polymer HP consists of a main chain formed from the biopolymer B2, with the synthetic polymer side chain L covalently bonded to the main chain. Figure 1 and Figure 2 ).

[0190] The water-soluble hybrid polymer HP according to the present invention is characterized in that the monomer of the monomer unit or polymer chain A is selected from: acrylamide, acrylic acid, acrylic oligomer, 2-acrylamido-2-methylpropanesulfonic acid (ATBS) and / or its salts, N-vinylformamide (NVF), N-vinylpyrrolidone (NVP), dimethyl diallyl ammonium chloride (DADMAC), quaternized dimethylaminoethyl acrylate (ADAME), and quaternized dimethylaminoethyl methacrylate (MADAME).

[0191] In the water-soluble hybrid polymer HP, the percentage of reactive functional groups (frB) in biopolymer B2 that are replaced by oligonucleotide initiators is preferably between 0.1% and 90%.

[0192] According to the present invention, the biopolymer B1 used to generate the hybrid polymer HP preferably contains at least one reactive functional group (frB) selected from hydroxyl, carboxylate or anhydride functional groups.

[0193] Biopolymer B1 is preferably a polysaccharide. More preferably, biopolymer B1 is a polysaccharide selected from the following: starch; cellulose, cellulose sulfate, cellulose acetate, sulfoethyl cellulose, cyanoethyl cellulose, methyl cellulose, ethyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose or hydroxypropyl cellulose, hemicellulose; xylo-glucan, glucomannan, galactomannan, chitosan and chitosan salts; polysaccharides extracted from algae, such as agarose, carrageenan, alginate; pectin; dextran; pullulan; gellan gum; and combinations thereof.

[0194] In the water-soluble hybrid polymer, HP, the weight-average molecular weight of the side chain L is preferably between 5,000 Da and 1,000,000 Da.

[0195] The hybrid polymer HP can be readily separated using conventional separation, precipitation, evaporation, and / or drying methods known to those skilled in the art. The solvent, preferably water, can be extracted by filtration or distillation, advantageously by distillation.

[0196] The water-soluble hybrid polymer HP can be obtained and used in liquid form, i.e., solutions (emulsions, aqueous solutions, water-in-water dispersions) or in particulate form (powders, microspheres, aqueous or oily dispersions, agglomerates of fine powders). Advantageously, the water-soluble hybrid polymer HP is used in liquid form.

[0197] The powder form of the water-soluble hybrid polymer HP can be obtained by aqueous solution polymerization followed by drum drying, spray drying, or radiation drying such as microwave drying or fluidized bed drying. The powder form can also be obtained by water-in-oil emulsion (reverse emulsion) polymerization, emulsion polymerization, or dispersion polymerization, followed by distillation / concentration steps and spray drying of the resulting liquid.

[0198] The polymers according to the invention can have a weight-average molecular weight covering all applications in which synthetic water-soluble polymers can be used. Therefore, the weight-average molecular weight of the hybrid polymer HP according to the invention can be between 50,000 g / mol and 100,000 g / mol, or between 100,000 g / mol and 500,000 g / mol, or between 500,000 g / mol and 1,000,000 g / mol, or between 1,000,000 g / mol and 3,000,000 g / mol, or between 3,000,000 g / mol and 5,000,000 g / mol, or between 5,000,000 g / mol and 10,000,000 g / mol, or between 10,000,000 g / mol and 30,000,000 g / mol, or greater than 30,000,000 g / mol. This is the weight-average molecular weight.

[0199] Molecular weight is advantageously determined by the intrinsic viscosity of the polymer. Intrinsic viscosity can be measured by methods known to those skilled in the art and can be calculated graphically from specific viscosity values ​​at different concentrations, wherein the graphical method consists of plotting the specific viscosity values ​​(y-axis) relative to concentration (x-axis) and extrapolating the curve to zero concentration. The intrinsic viscosity values ​​are read on the y-axis or using the least squares method. The molecular weight can then be determined using the Mark-Houwink equation: [η] = K Mα [η] represents the intrinsic viscosity of the polymer as determined by a method used to measure solution viscosity.

[0200] K represents an empirical constant.

[0201] M represents the molecular weight of the polymer.

[0202] α represents the Mark-Hovink coefficient.

[0203] K and α depend on the specific polymer-solvent system.

[0204] Preferably, the hybrid polymer HP according to the invention comprises a bio-based carbon content between 30% and 100% by weight based on the total weight of carbon in the polymer, said bio-based carbon content being measured according to ASTM D6866-21, Method B.

[0205] Applications of hybrid polymers HP The present invention also relates to the use of a water-soluble hybrid polymer HP according to the invention in the selection of: hydrocarbon (oil or natural gas) recovery; drilling; cementing; production enhancement of hydrocarbon (oil or natural gas) wells, such as hydraulic fracturing, profile control, and diversion; water treatment in open, closed, or semi-closed loops; treatment of fermented grape juice; sludge treatment; construction industry; paper or paperboard manufacturing; battery industry; wood treatment; treatment of hydraulic compositions (concrete, cement, mortar, and aggregates); mining industry; cosmetic formulation; detergent formulation; textile manufacturing; geothermal applications; or agriculture.

[0206] Finally, the present invention also relates to the use of the water-soluble hybrid polymer HP according to the invention as a flocculant, coagulant, dispersant, binder, fixative, viscosity reducer, thickener, absorbent, friction reducer, dehydrating agent, filler retainer, dehydrating agent, regulator, stabilizer, film-forming agent, sizing agent or clay inhibitor.

[0207] Example The following examples best illustrate the advantages of the invention in a clear and non-limiting manner. More specifically, the following examples illustrate the synthesis of oligonucleotide initiators according to the invention and their use in the production of water-soluble hybrid polymers.

[0208] The following abbreviations were used.

[0209] AA: Acrylic acid.

[0210] AANa: Neutralized acrylic acid, i.e., sodium acrylate.

[0211] AM: Acrylamide.

[0212] ALG: Alginate.

[0213] CMC: Carboxymethyl cellulose.

[0214] CMS: Carboxymethyl starch.

[0215] GMA: Glycidyl methacrylate.

[0216] Synthesis of I-Oligonucleotide Initiators The controlled free radical polymerization reaction was carried out using 30% by mass of the active material.

[0217] First, weigh out 2.5 g of chain transfer agent according to formula (IV), 51% acrylamide (AM) (9.87 g, i.e., 5.03 g AM), glycidyl methacrylate (GMA) (1.51 g) and demineralized water (16.5 g).

[0218] The chain transfer agent was dissolved in a 50 ml single-necked flask with some demineralized water under stirring.

[0219] Once uniformly dispersed and dissolved, acrylamide (AM) is added. Glycidyl methacrylate (GMA) is then added to the reaction medium, which is accompanied by the formation of a suspension of droplets.

[0220] The initiator (96.05 mg) was then weighed and added to the reaction medium along with the remaining distilled water.

[0221] The flask was covered with a diaphragm and bubbled with argon in the reaction medium for 30 minutes. The flask was then placed in an oil bath preheated to 40°C–60°C and stirred. The flask was kept at this temperature for 3 hours, and then the mixture was cooled to room temperature. The mixture was then poured dropwise into cold acetone to precipitate the polymer, which was then separated by filtration, redissolved in demineralized water, and then frozen to recover the P(AM-co-GMA) oligonucleotide initiator obtained by freeze-drying.

[0222] The quality yield is approximately 85%.

[0223] Other syntheses were performed according to the same protocol, with variations in the proportions of AM, GMA, transfer agent, and initiator. Table 1 below summarizes information on oligonucleotide initiators (OIs) 1 through 8.

[0224] [Table 1]

[0225] Table 1: Monomer composition of oligonucleotide initiators 1 to 8. II- Functionalize biopolymer B1 to obtain B 2。

[0226] Biopolymer B1 is carboxymethyl cellulose (CMC) (Example II-1), alginate (Example II-2), or carboxymethyl starch (Example II-3). The oligonucleotide initiator used is a pre-prepared oligonucleotide initiator 4.

[0227] As a reminder, according to the present invention, biopolymer B1 is derived from natural and / or renewable resources, that is, a polymer derived from living organisms or synthesized from renewable resources. Biopolymer B2 corresponds to biopolymer B1 after functionalization with an oligonucleotide initiator.

[0228] II-1: Carboxymethyl cellulose At room temperature, CMC was dissolved in distilled water in a 50 ml round-bottom flask, resulting in a CMC concentration of 25 μg / L. -1 .

[0229] 175 mg of OI₄ was introduced into the CMC solution. The reaction was stirred at 50 °C for 24 hours. After the reaction medium was cooled to room temperature... A portion of the reaction medium was transferred to a dialysis membrane (Spectra-Por®) with a porosity of 50 kDa. The obtained compound was frozen and then freeze-dried. The CMC yield was 73%. Table 2 below summarizes information related to the obtained B2 polymer.

[0230] [Table 2]

[0231] *Sample was not dialyzed (purified by precipitation). Sample B 2b To B 2f Dialysis has been initiated.

[0232] Table 2: B2 obtained by changing the CMC / P (OI 4) mass ratio II-2: Alginate At room temperature, ALG was dissolved in distilled water in a 50 ml round-bottom flask, resulting in an ALG concentration of 25 μg / L. -1 .

[0233] 175 mg of OI 7 or OI 8 was introduced into the ALG solution. The reaction was stirred at 50 °C for 24 hours. The reaction medium was then cooled to room temperature. A portion of the reaction medium was transferred to a dialysis membrane (Spectra-Por®) with a porosity of 50 kDa. The obtained compound was frozen and then freeze-dried. The mass yield of ALG was 73%. Table 3 below summarizes the information related to the obtained B2 polymer. Epoxide:OH is equivalent to DS, calculated as follows: DS = (m OI x M B1 ) / (m B1 x M OI ).

[0234]

[0235] Table 3: B2 obtained via ALG II-3: Carboxymethyl starch CMS was dissolved in distilled water in a 50 ml round-bottom flask at room temperature, resulting in a CMS concentration of 25 μg / L. -1 .

[0236] 175 mg of OI 7 or OI 8 was introduced into the CMS solution. The reaction was stirred at 50 °C for 24 hours. The reaction medium was then cooled to room temperature. A portion of the reaction medium was transferred to a dialysis membrane (Spectra-Por®) with a porosity of 50 kDa. The obtained compound was frozen and then freeze-dried. The mass yield of CMS was 73%. Table 4 below summarizes information related to the obtained B2 polymer.

[0237]

[0238] Table 4: B2 obtained through CMS III-Extended synthetic polymer chains III-1: Starting with a carboxymethyl cellulose matrix: Add the following to the reactor: 13.19 g sodium acrylate and 46.01 g 51% AM, 600 g water and 30 g B. 2e Argon bubbling was performed in the reactor for 30 minutes. Then, 202.11 mg of azo initiator VA044 was added to the reaction medium and incubated at 40°C for 4 hours. Then, 1.39 g of sodium bisulfite (40% by weight in water) was added to perform a 'burn-off' step, which was carried out at 40°C for 1 hour.

[0239] Then the hybrid polymer HP1 was obtained. A portion was taken out for NMR analysis of the sample. Figure 2 ).

[0240] III-2: Starting with an alginate matrix Mix 13.19 g sodium acrylate, 46.01 g AM 51%, 600 g water, and 30 g B. 2h Add to the reactor. Bubble the reactor with argon for 30 minutes. Then add 202.11 mg of azo initiator VA044 to the reaction medium and incubate at 40°C for 4 hours. Then add 1.39 g of sodium bisulfite (40 wt% in water) to perform a burn-off step, which is carried out at 40°C for 1 hour.

[0241] The HP2 hybrid polymer was then obtained. A portion of it was taken for NMR analysis.

[0242] III-3: Starting with carboxymethyl starch matrix Mix 13.19 g sodium acrylate, 46.01 g AM 51%, 600 g water, and 30 g B. 2k Add to the reactor. Bubble the reactor with argon for 30 minutes. Then add 202.11 mg of azo initiator VA044 to the reaction medium and incubate at 40°C for 4 hours. Then add 1.39 g of sodium bisulfite (40 wt% in water) to perform a burn-off step, which is carried out at 40°C for 1 hour.

[0243] The HP3 hybrid polymer was then obtained. A portion of it was taken for NMR analysis.

[0244] Counterexample: Synthesizing hybrid polymers using a "graft-through" strategy: Dissolve 20 g of CMC overnight at room temperature with stirring in a jacketed reactor containing 560 g of water. Adjust the pH of the reaction medium to pH = 8 using a 50% NaOH solution. Add 2.2 g of GMA to the reactor.

[0245] The reactor was then heated to 50°C using a constant temperature control bath, and the reaction medium was left to stand for 24 hours with mechanical stirring. 13.19 g of acrylic acid (100%) was placed in an ice bath and neutralized with 10 M sodium hydroxide (approximately 18 ml) until the pH was between 6 and 7.

[0246] The obtained sodium acrylate (AANa) was added to the reactor along with 46.01 g of 51% AM. The reactor was then bubbled for 30 minutes using a long tube, after which the tube was placed directly above the reaction medium. 202.11 mg of initiator VA044 was then added to the reaction medium, and the mixture was incubated at 40°C for 4 hours. Subsequently, 1.39 g of sodium bisulfite (40% by weight in water) was introduced at 40°C for 1 hour to eliminate residual vinyl functional groups in the reactor.

[0247] This yields a counterexample hybrid polymer.

[0248] III - Application Example: Solubility Test The polymer HP according to the present invention is compared with the counterexample hybrid polymer.

[0249] The two polymers at 10 gl -1 The solution was dissolved at a concentration of [specific concentration not specified]. 250 g of these solutions were then filtered using a 50 µm filter. The mass of the recovered solution after filtration was then weighed, and the recovery rate was calculated as the ratio of the recovered mass to the initial mass. The results are shown in Table 5.

[0250] [Table 5]

[0251] Table 5: Mass of the recovered solution before and after 50 µm filtration In the case of the hybrid polymer HP according to the invention, almost all solutions passed through a 50 μm filter (recovery rate >99.5%), which demonstrates the water solubility of the hybrid polymer HP produced by the strategy of the invention.

[0252] On the other hand, in the case of the counterexample polymer, the amount of solution recovered was much smaller than the initial value, and insoluble gel fragments remained on the 50 μm filter. Therefore, the "grafting through" strategy cannot obtain water-soluble polymers as in this invention.

Claims

1. An oligonucleotide initiator having formula (I) （I） in: W= R 1 Or W = ZR 3 Where Z = O, S, or NR 4 , R 1 R 2 R 3 and R 4 Can be the same or different and can be expressed as: Optionally substituted alkyl, acyl, aryl, olefinic, or alkyne groups (i), or Optionally substituted or aromatic saturated or unsaturated carbonyl rings (ii), or Optionally substituted saturated or unsaturated heterocycles (ii). These groups, as well as rings (i), (ii), and (iii), can be substituted with substituted phenyl groups, substituted aromatic groups, or the following groups: alkoxycarbonyl or aryloxycarbonyl (-COOR), carboxyl (-COOH), acyloxy (-O2CR), carbamoyl (-CON(R)2), cyano (-CN), alkylcarbonyl, alkylarylcarbonyl, arylcarbonyl, arylalkylcarbonyl, phthalimide, maleimide, succinimide, amidoyl, guanidinyl, hydroxyl (-OH), amino (-N(R)2), halogen, allyl, epoxy, alkoxy (-OR), S-alkyl, S-aryl, groups with hydrophilic or ionic properties, such as alkali metal salts of carboxylic acids, alkali metal salts of sulfonic acids, polyepoxide (PEO, PPO) chains, cationic substituents, quaternary ammonium salts. R represents C1-C 20 Alkyl or aryl, (R)2 functional group, the two R groups can be the same or different from each other. R 4 It can also represent a hydrogen atom; G includes A and / or Q, A is a single unit or includes n A A linear or structured polymer chain of identical or different hydrophilic monomers, wherein the hydrophilic monomers contain at least one olefinic unsaturated functional group, wherein n A It is an integer between 0 and 500. Q is a single unit or a component. n Q A linear or structured polymer chain of monomers, wherein the monomers are selected from monomers having at least one reactive functional group (frQ), wherein the at least one reactive functional group is an epoxide and / or anhydride and / or hydroxyl and / or isocyanate and / or acetal and / or aldehyde and / or carboxylic acid and / or ester and / or vinyl type, wherein n Q It is an integer between 1 and 1000. A and Q can be statistically, gradient-wise, or block-wise copolymerized to form G.

2. The oligonucleotide initiator according to claim 1, characterized in that, The monomer unit or polymer chain A comprises a hydrophilic monomer, which contains at least one olefinic unsaturated functional group selected from nonionic and / or cationic and / or anionic and / or zwitterionic monomers.

3. The oligonucleotide initiator according to claim 2, characterized in that, The nonionic monomer is selected from acrylamide, methacrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, N-hydroxymethylacrylamide, N-vinylformamide, N-vinylacetamide, N-vinylpyridine, N-vinylpyrrolidone, acryloylmorpholine (ACMO), diacetone acrylamide and glycidyl methacrylate.

4. The oligonucleotide initiator according to claim 2, characterized in that, The anionic monomers are selected from acrylic acid; methacrylic acid; dimethacrylic acid; itaconic acid; crotonic acid; maleic acid; fumaric acid; acrylamidoundecanoic acid; 3-acrylamido-3-methylbutyric acid; maleic anhydride; strong acid monomers having functional groups of the type of sulfonic acid or phosphonic acid, such as vinylsulfonic acid, vinylphosphonic acid, allylsulfonic acid, methylallylsulfonic acid, 2-methylenepropane-1,3-disulfonic acid, 2-sulfoethyl methacrylate, sulfopropyl methacrylate, sulfopropyl acrylate, allylphosphonic acid, styrenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid (ATBS), 2-acrylamido-2-methylpropanedisulfonic acid; water-soluble salts of these monomers, such as their alkali metal salts (different from the crystal form of sodium 2-acrylamido-2-methylpropanesulfonate), alkaline earth metal salts or ammonium salts; and mixtures thereof.

5. The oligonucleotide initiator according to claim 2, characterized in that, The cationic monomer is selected from dimethylaminoethyl methacrylate quaternized (ADAME), dimethylaminoethyl methacrylate quaternized (MADAME), dimethyl diallyl ammonium chloride (DADMAC), acrylamidopropyltrimethylammonium chloride (APTAC), and methacrylamidopropyltrimethylammonium chloride (MAPTAC).

6. The oligonucleotide initiator according to any one of the preceding claims, characterized in that, The monomer of the monomer unit or polymer chain Q is selected from glycidyl methacrylate, methacrylic anhydride, maleic anhydride, itaconic anhydride, hydroxy(alkyl) acrylate, glycidyl acrylate, allyl glycidyl ether, and (meth)acrylate allyl ester.

7. The oligonucleotide initiator according to any one of the preceding claims, characterized in that, The weight-average molecular weight of the oligonucleotide initiator is between 350 Da and 1,500,000 Da.

8. The oligonucleotide initiator according to any one of the preceding claims, characterized in that, The oligonucleotide initiator has formula (II). (II) Wherein nA, acrylamide unit, is between 1 and 300, and nQ, glycidyl methacrylate unit, is between 1 and 500.

9. Use of an oligonucleotide initiator according to any one of claims 1 to 8 for the production of a water-soluble polymer.

10. A water-soluble hybrid polymer HP, obtained using an oligonucleotide initiator according to any one of claims 1 to 8 and according to a method comprising at least the following sequential steps: (1) The biopolymer B1 is functionalized by reacting at least one reactive functional group (frB) of the biopolymer B1 with at least one reactive functional group (frQ) of the oligonucleotide initiator to obtain a functionalized biopolymer B2. (2) A hydrophilic monomer containing at least one olefinic unsaturation is polymerized on at least one oligonucleotide initiator of the functionalized biopolymer B2 to form at least one side chain L, and thus the hybrid polymer HP is obtained. Its features are, The oligonucleotide initiator has formula (I). （I） in: W= R 1 Or W = ZR 3 Where Z = O, S, or NR 4 , R 1 R 2 R 3 and R 4 Can be the same or different and can be expressed as: Optionally substituted alkyl, acyl, aryl, olefinic, or alkyne groups (i), or Optionally substituted or aromatic saturated or unsaturated carbonyl rings (ii), or Optionally substituted saturated or unsaturated heterocycles (ii). These groups, as well as rings (i), (ii), and (iii), can be substituted with substituted phenyl groups, substituted aromatic groups, or the following groups: alkoxycarbonyl or aryloxycarbonyl (-COOR), carboxyl (-COOH), acyloxy (-O2CR), carbamoyl (-CON(R)2), cyano (-CN), alkylcarbonyl, alkylarylcarbonyl, arylcarbonyl, arylalkylcarbonyl, phthalimide, maleimide, succinimide, amidoyl, guanidinyl, hydroxyl (-OH), amino (-N(R)2), halogen, allyl, epoxy, alkoxy (-OR), S-alkyl, S-aryl, groups with hydrophilic or ionic properties, such as alkali metal salts of carboxylic acids, alkali metal salts of sulfonic acids, polyepoxide (PEO, PPO) chains, cationic substituents, quaternary ammonium salts. R represents C1-C 20 Alkyl or aryl, (R)2 functional group, the two R groups can be the same or different from each other. R 4 It can also represent a hydrogen atom; G includes A and / or Q, A is a single unit or includes n A A linear or structured polymer chain of identical or different hydrophilic monomers, wherein the hydrophilic monomers contain at least one olefinic unsaturated functional group, wherein n A It is an integer between 0 and 500. Q is a single unit or a component. n Q A linear or structured polymer chain of monomers, wherein the monomers are selected from monomers having at least one reactive functional group (frQ), wherein the at least one reactive functional group is an epoxide and / or anhydride and / or hydroxyl and / or isocyanate and / or acetal and / or aldehyde and / or carboxylic acid and / or ester and / or vinyl type, wherein n Q It is an integer between 1 and 1000. A and Q can statistically, gradient-wise, or block-wise aggregate to form G. The biopolymer B1 is characterized in that it is natural or modified and contains at least one reactive functional group (frB), which is a hydroxyl and / or carboxyl and / or acid anhydride and / or amine and / or amide and / or vinyl, and / or phosphate ester and / or sulfonate and / or ester and / or aldehyde and / or ketone and / or silane, and / or isocyanate and / or nitrile and / or acyl halide type.

11. The water-soluble hybrid polymer HP according to claim 10, characterized in that, The oligonucleotide initiator has formula (I), wherein: Z = O, R 1 and R 2 This indicates an optional substituted alkyl, acyl, aryl, olefin, or alkyne group. G includes A and / or Q, A is a monomer unit or a linear polymer chain containing 1 to 300 monomer units of nA; Q is a monomer unit or a linear polymer chain containing nQ 1 to 500 monomer units.

12. The water-soluble hybrid polymer HP according to any one of claims 10 and 11, characterized in that, The monomer of the monomer unit or polymer chain A is selected from: acrylamide, acrylic acid, acrylic oligomer, 2-acrylamido-2-methylpropanesulfonic acid (ATBS) and / or its salts, N-vinylformamide (NVF), N-vinylpyrrolidone (NVP), dimethyl diallyl ammonium chloride (DADMAC), quaternized dimethylaminoethyl acrylate (ADAME), and quaternized dimethylaminoethyl methacrylate (MADAME).

13. The water-soluble hybrid polymer HP according to any one of claims 10 to 12, Its features The percentage of reactive functional groups (frB) in the biopolymer B2 that are replaced by the oligonucleotide initiator is between 0.1% and 90%.

14. The hybrid polymer HP according to any one of claims 10 to 13, Its features The biopolymer B1 contains at least one reactive functional group (frB) selected from hydroxyl, carboxylic acid ester or acid anhydride functional groups.

15. The hybrid polymer HP according to any one of claims 10 to 14, Its features The biopolymer B1 is a polysaccharide.

16. The hybrid polymer HP according to claim 15, Its features The polysaccharide is selected from starch or its derivatives, carboxymethyl starch; cellulose or its derivatives, carboxymethyl cellulose, hemicellulose; polysaccharides extracted from algae, agarose, carrageenan, alginate; pectin; inulin; guar gum; konjac gum; dextran; pullulan; gellan gum; and gel polysaccharide.

17. The water-soluble hybrid polymer HP according to any one of claims 10 to 16, Its features The weight-average molecular weight of the side chain L is between 5,000 Da and 1,000,000 Da.

18. The water-soluble hybrid polymer HP according to any one of claims 10 to 17, Its features According to standard ASTM D6866-21 Method B, the bio-based carbon content of the side chain L is between 5 wt% and 100 wt% relative to the total carbon weight in the side chain L.

19. Use of the water-soluble hybrid polymer HP according to any one of claims 10 to 18, selected from the fields of: hydrocarbon recovery; drilling and cementing; hydrocarbon well enhancement; water treatment; treatment of fermented grape juice; sludge treatment; paper or paperboard manufacturing; construction; wood processing; treatment of hydraulic compositions; mining; cosmetic formulation; detergent formulation; textile manufacturing; battery component manufacturing; geothermal applications; or agriculture.

20. Use of the water-soluble hybrid polymer HP according to any one of claims 10 to 18, for use as a flocculant, coagulant, dispersant, binder, fixative, viscosity reducer, thickener, absorbent, friction reducer, dehydrating agent, filter aid, filler retainer, dehydrating agent, regulator, stabilizer, film-forming agent, sizing agent, or clay inhibitor.

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