Polymerizable and cleavable heterocyclic compound

Abstract

The invention relates to a polymerizable cleavable compound that makes it possible to prepare a copolymer that is degradable under controlled conditions. This polymerizable compound is heterocyclic; it comprises an exocyclic ethylenic unsaturation, two intracyclic sulfide groups and one intracyclic cleavable group. The invention also provides a method for preparing this compound as well as its use in a ring-opening radical polymerization reaction. The resulting copolymer also forms part of the invention.

Description

[0001] POLYMERIZABLE AND CLIVABLE HETEROCYCLIC COMPOUND

[0002] The invention relates to a polymerizable cleavable compound that allows the preparation of a copolymer that is degradable under controlled conditions. This polymerizable compound is heterocyclic; it comprises an exocyclic ethylenic unsaturation, two intracyclic sulfide groups, and an intracyclic cleavable group. The invention also provides a method for preparing this compound and for its use in a ring-opening radical polymerization reaction. The resulting copolymer is also part of the invention.

[0003] For a long time, many technical fields have required the use of polymers chosen for their specific properties. In addition to their functional properties, these polymers should now be able to degrade after use. Preferably, they should be able to degrade in a controlled manner or degrade naturally.

[0004] It is therefore particularly useful to have polymerizable compounds that allow the controlled introduction of cleavable functional groups into these polymers in order to make them degradable. In particular, it is very useful to have polymerizable compounds that allow the controlled introduction of heteroatoms or heteroatomic groups during the preparation of degradable copolymers.

[0005] These polymerizable compounds should allow the introduction of various cleavable functionalities within these copolymers. In particular, the variety of cleavable functionalities introduced should make it possible to obtain copolymers that are degradable under different conditions.

[0006] Furthermore, the methods for preparing these cleavable and polymerizable compounds should be efficient and easy to implement. These methods should also allow for good yields, particularly by limiting the number of steps or using readily available reagents. Specifically, these compounds should be prepared in a dilute reaction medium while controlling the formation of reaction byproducts.

[0007] Furthermore, the polymerization of these cleavable compounds should be facilitated, while simultaneously improving the range of available copolymers, particularly through the use of different types of comonomers. The reactivity of these polymerizable compounds with different types of monomers is therefore a desirable property. The preparation of copolymers in various forms and that are biodegradable is also an important objective. These copolymers can be water-soluble. They can exist as a dispersion or emulsion in a liquid medium, especially an aqueous one. They can also exist as an emulsion within a lipophilic medium.

[0008] Copolymers prepared using these cleavable compounds should be degradable under controlled conditions. Preferably, these copolymers should be degradable under various conditions. In particular, these copolymers should be degradable by hydrolysis, chemical action, mechanical activation, irradiation, or biological action.

[0009] Advantageously, the formation of degradation products from these degradable copolymers should also be controllable. Specifically, the type and properties of these degradation products should be controlled. In particular, all or some of these degradation products should possess specific properties. Preferably, these degradation products should be composed of polymerizable compounds.

[0010] Document WO 2023111340 describes the fabrication of objects by 3D printing using a photoactivatable resin prepared with a poly(meth)acrylate monomer, a thiolactone, and a photoinitiator compound. The article by Jos Paulusse et al. (Langmuir, July 22, 2009) describes the preparation of functionalized cyclic monomers that are copolymerized with dimethylaminoethyl methacrylate or with 1'-hydroxyethyl methacrylate. The article by Cornells Moorhoff et al. (Monatsch Chem, 2013) mentions 3,7-bis(methylene)-1,5-dithiocane and 3-methylene-1,5-dithia-8,1-dioxotridecane as reaction byproducts of photoplastic polymers.

[0011] Document CN 116635366 discloses a composition for selective absorption of visible light that includes a salt whose anion is a substituted bicyclic compound comprising several conjugated unsaturations. The article by Buter et al. (J. Chem. Soc., Chemical Communication, January 1, 1991) discloses ketone crown thioethers used as chelating agents. The article by Buter et al. (J. Chem. Soc., Chemical Communication, January 1, 1990) also discloses the preparation of thia-macrocycles for chelating heavy metals using isobutenyl.

[0012] Thus, there is an important need for polymerizable and cleavable compounds that are easy to prepare and that allow for the efficient preparation of degradable copolymers, in particular copolymers that are degradable in a controlled manner and provide degradation products, in particular polymerizable degradation products.

[0013] The prior art polymerizable cleavable compounds and their preparation methods are not always satisfactory in providing a solution to all or some of the problems encountered. Thus, the invention provides a polymerizable and cleavable compound that offers a solution to all or some of the known compounds.

[0014] Thus, the invention provides a heterocyclic compound A comprising:

[0015] - an exocyclic ethylenic unsaturation,

[0016] - two intracyclic sulfide groups, each in the P position of the ethylenic exo-unsaturation and

[0017] - a cleavable intracyclic chemical group G.

[0018] Essentially, according to the invention, compound A is multifunctional; it comprises at least three types of chemical groups possessing specific functions that confer its properties. The intracyclic sulfide (or thioether) groups of compound A are located at position P of an ethylenic exo-unsaturation; they are reactive in a ring-opening radical polymerization reaction. These intracyclic sulfide groups are linked by saturated covalent bonds within compound A according to the invention. Located at position P of the ethylenic exo-unsaturation, the two sulfide groups are separated from this ethylenic exo-unsaturation by alkylenic groups. These thioether groups are distinct from intracyclic thioester groups. The G group of compound A is cleavable or degradable, particularly under specific conditions.

[0019] Preferably for compound A according to the invention, the intracyclic sulfide groups are reactive under ring-opening radical polymerization conditions, in particular in the presence of at least one radical initiator compound and at a temperature ranging from room temperature to 150°C, preferably from 50°C to 100°C.

[0020] Advantageously for the copolymer P according to the invention, the exocyclic ethylenic unsaturation of compound A is polymerizable, particularly in aqueous media, preferably in water, alone or optionally in combination with a protic solvent, such as acetic acid and alcohols, especially isopropanol. According to the invention, the exocyclic ethylenic unsaturation of compound A can be polymerized in water alone. Particularly preferred for compound A according to the invention, the intracyclic group G is cleavable by at least one external stimulus. Preferably, according to the invention, this stimulus can be selected from:

[0021] - hydrolysis, preferably basic hydrolysis or acid hydrolysis,

[0022] - chemical action, preferably action by means of at least one reactive compound of the G group, for example tetra-n-butylammonium fluoride, a primary amine, redox compounds,

[0023] - mechanical activation,

[0024] - irradiation,

[0025] - biological action, in particular by action using an enzyme or a microorganism.

[0026] For compound A according to the invention, the cleavable group G can be chosen from a group G1 of formula: -Si(Q 1 )(Q 2 )- ; a G2 group with the formula: -P(OH)(=O)- ; a G3 group with the formula: -P(OQ 1 )(=O)- ; a G4 group of formula: - P(=O)(OH)-OP(=O)(OH)-; a G5 group of formula: -P(E 1 OQ 1 )(=O)- ; a grouping G6 of formula: -P(E 1 OQ 1 )(=O)- ; a G7 grouping with the formula: - CQ^OQ 2 )- ; a group G8 of formula: -C(Q 1 )(Q 2 )- ; a group G9 with the formula: -C(=O)- ; a group G10 with the formula: -C(Q 1 )(Q 2)- ; a G11 group with the formula: -C(=S)- ; a G12 group with the formula: a direct bond ; a G13 group with the formula: -C(OH)(Q 1 )- ; a G14 grouping with the formula: -C(OQ 1 )(Q 2 )- ; a grouping G15 with the formula: -C(=O)- ; a grouping G16 with the formula: -C(=O)-O-(O=)C- ; a grouping G17 with the formula: -C=N- ; a grouping G18 with the formula: -C(=O)- ; a grouping G19 with the formula: -C(=O)- ; a grouping G20 with the formula: -C(=O)- ; a grouping G21 with the formula: -C(=O)- ; a grouping G22 with the formula: -S(=O)2- ; a grouping G23 with the formula: -C(=O)-Si- ; preferably chosen from G1 to G12 and G18; more preferably chosen from G1, G7, G8, G9 and G18, in which:

[0027] - E 1 represents a divalent alkylene group, preferably a divalent Ci-Cio-alkylene group, linear or branched,

[0028] - Q 1 and Q 2independently represent H or a group chosen from an alkyl group, a heteroalkyl group, an aryl group, a heteroaryl group, preferably chosen from H, a Ci-C2o-alkyl group, a Ci-C2o-heteroalkyl group, a phenyl group, a phenoxy group.

[0029] According to the invention, the heteroalkyl group is an alkyl group comprising at least one heteroatom, preferably chosen from O, S, and NH. According to the invention, the heteroaryl group is an aryl group comprising at least one heteroatom, preferably chosen from O, S, and NH.

[0030] Preferably for Q 1 and Q 2 The Ci-C2o-alkyl group can be independently selected from a linear Ci-Cio-alkyl group or a branched Cs-Cio-alkyl group. Also preferentially for Q 1 and Q 2, the Ci-C2o-heteroalkyl group can be independently chosen from a linear Ci-Cio-heteroalkyl group, a branched Cs-Cio-heteroalkyl group.

[0031] Preferably, E 1 represents a divalent alkylene group, preferably chosen from a linear divalent Ci-Cio-alkylene group or a branched divalent Cs-Cio-alkylene group, more preferably a divalent Ci-C4-alkylene group, in particular a divalent C2-C3-alkylene group.

[0032] According to the invention, the implemented group G makes it possible to obtain a cleavable compound A. Preferably, depending on the group G chosen, compound A then comprises a group selected from among a diethersilyl group including a G1 group, a phosphoryl group including a G2 group, a hydroxylalkylene-phosphoryl group including a G3 group, a pyrophosphonate group including a G4 group, a phosphoraramidate group including a G5 group, an ether-phosphoryl group including a G6 group, an orthoester group including a G7 group, an acetal group including a G8 group, a carbonate group including a G9 group, a thioacetal group including a G10 group, a thiocarbonate group including a G1 group, a disulfide group including a G12 group, a hydroxyacetal group including a G13 group,an alkyleneoxyacetal group including a G14 group, a ketone group including a G15 group, an anhydride group including a G16 group, an imine group including a Gl7 group, an ester group including a Gl8 group, an amide group including a G19 group, a urethane group including a G20 group, a thioester group including a G21 group, a sulfonic ester group including a G22 group, an acylsilane group including a G23 group.

[0033] Preferably, compound A according to the invention is a compound of formula I: in which:

[0034] - T 1 , T 2 , T 3 and T 4independently represent H or an aryl group or an alkyl group, preferably a Ci-C2o-alkyl group, preferably a linear Ci-C2o-alkyl group or a branched C3-C2o-alkyl group, more preferably a linear Ci-Cio-alkyl group or a branched Cs-Cio-alkyl group, most preferably a linear Ci-Cô-alkyl group or a branched C3-Cô-alkyl group, even more preferably a linear Ci-C3-alkyl group or a branched C3-C4-alkyl group,

[0035] - x and y independently represent a number from 1 to 5, preferably 1, 2 or 3, more preferably x and y simultaneously represent 2 or one represents 2 and the other represents 3;

[0036] - X 1 and X 2 independently represent a direct bond, O, S, NH or NQ 3 ,

[0037] - Q 3represents an alkyl group, preferably a Ci-C2o-alkyl group, preferably a linear Ci-Cio-alkyl group or a branched C3-Cio-alkyl group,

[0038] - G is a cleavable intracyclic chemical group G, preferably G is chosen from G1 to G23.

[0039] More preferably, compound A according to the invention is a compound of formula I in which T 1 , T 2 , T 3 and T 4 independently represent H or a methyl group; more preferentially they represent H.

[0040] Also, more preferably, compound A according to the invention is a compound of formula I in which x and y simultaneously represent 2.

[0041] More preferably, compound A according to the invention is a compound of formula I in which X 1 and X 2are identical or independently represent a direct bond, O or S; more preferably they represent O. Also more preferably, compound A according to the invention is a compound of formula I in which G is selected from G1 to G12 and G18; more preferably G is selected from G11, G7, G8, G9 and G18.

[0042] The method for preparing compound A according to the invention is particularly advantageous. Thus, the invention also provides a method V for preparing compound A. Preferably, the preparation method V according to the invention is selected from a preparation method VI involving simple cyclization of a final intermediate compound. Also preferably, the preparation method V according to the invention is selected from a preparation method V2 involving the simple reaction of a dithiol compound with a compound comprising two leaving groups.

[0043] More preferably according to the invention, preparation method VI comprises the reaction of a compound of formula IA: in which T 1 , T 2 , T 3 , T 4 X 1 X 2 x and y are defined independently according to the invention, with a compound of formula IB:

[0044] The GL 2 IB in which G is chosen from Gl to G12 according to the invention and L 1 and L 2 , identical or different, independently represent a leaving group, preferably a mesylate group or a tosylate group, or a halide, preferably chloride or bromide.

[0045] In a particularly preferred manner for preparation method VI, G is selected from G1 to G11 and G12 according to the invention. Preferably according to the invention, compound A can be obtained by direct cyclization of the compound of formula IA. Preferably for the preparation of compound A of formula I in which G is represented by G12, preparation method VI can be carried out in the absence of compound of formula IB; preparation method VI then comprises the direct cyclization of the compound of formula IA.

[0046] Also, more preferably according to the invention, the preparation method V2 comprises the reaction of a compound of formula IC: in which T 1 , T 2 , T 3 and T 4 are defined independently according to the invention and L 1 and L 2, identical or different, independently represent a leaving group, preferably a mesylate group or a tosylate group, or a halide, preferably chloride or bromide, with a compound of formula ID: in which G, X 1 X 2 x and y are defined independently according to the invention. Particularly preferred for preparation method V2, G is chosen from G1 to G23 according to the invention.

[0047] The conditions for carrying out the preparation method V according to the invention can be adapted, particularly depending on the group G according to the invention. Generally, the preparation method V according to the invention is carried out at a temperature ranging from 0°C to 150°C. Preferably, the preparation method V according to the invention is carried out in a solvent, preferably an organic solvent. Preferred solvents can be chosen from dichloromethane, tetrahydrofuran, methyl tetrahydrofuran, toluene, cyrene, acetonitrile, ethyl acetate, and combinations thereof.

[0048] The preparation method V according to the invention may also use one or more catalysts such as bases, acids, oxidizing agents, or coupling agents. Preferably, according to the invention, the preparation method V may employ a base, preferably a base selected from triethylamine, pyridine, imidazole, and potassium carbonate, in the preparation of compound A comprising a G group selected from the groups G1, G2, G3, G4, G5, G6, G9, G11, G18, G21, G22, and G23. Also preferably, according to the invention, the preparation method V may employ an acid, preferably an acid selected from para-toluenesulfonic acid and methanesulfonic acid, in the preparation of compound A comprising a G group selected from the groups G7, G8, G10, G13, G14, and G17.Also preferably according to the invention, preparation method V may employ an oxidizing agent during the preparation of compound A comprising a G12 group. Also preferably according to the invention, the preparation method may employ a coupling agent, preferably a coupling agent selected from among the carbodiimides, in particular N,N'-dicyclohexylcarbodiimide and l-ethyl-3-carbodiimide hydrochloride, during the preparation of compound A comprising a G16 group.

[0049] The invention provides a multifunctional compound A that combines several types of functional groups and thus possesses unique properties. It is polymerizable and is cleavable or degradable, particularly under specific conditions. Thus, the invention provides a method for preparing a copolymer P comprising a ring-opening radical polymerization reaction of compound A, particularly in aqueous or protic solvent media, at temperatures ranging from room temperature to 150°C, and in the presence of at least one radical-generating compound, at least one compound A according to the invention, and at least one polymerizable compound M comprising at least one polymerizable olefinic unsaturation.

[0050] Preferably, for the preparation of the copolymer P according to the invention, compound M is selected from an anionic compound M1, a nonionic compound M2, a sulfur-containing compound M3, a hydrophobic or associative compound M4, a crosslinking compound M5 comprising at least two ethylenic unsaturations, a cationic compound M6, and combinations thereof. More preferably, for this preparation method according to the invention, compound M1 is selected from a compound comprising one or two carboxylic acid functional groups, preferably a single carboxylic acid functional group. Even more preferably, compound M1 is selected from acrylic acid, methacrylic acid, an acrylic acid salt, a methacrylic acid salt, itaconic acid, maleic acid, maleic anhydride, and combinations thereof, most preferably acrylic acid, methacrylic acid, an acrylic acid salt, a methacrylic acid salt, and combinations thereof.

[0051] Preferably for this preparation method according to the invention, compound M2 is a non-ionic compound comprising at least one polymerizable ethylenic unsaturation, more preferably a polymerizable vinyl function. Much more preferably, compound M2 is selected from vinyl acetate, styrene, vinylcaprolactam, esters of an acid comprising at least one monocarboxylic acid function, in particular an ester of an acid selected from acrylic acid, methacrylic acid, and their combinations, for example hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, alkyl acrylate, in particular Ci-Cio-alkyl acrylate, preferably Ci-C4-alkyl acrylate, more preferably methyl acrylate, ethyl acrylate, I-propyl acrylate, isopropyl acrylate, isobutyl acrylate, I-butyl acrylate, alkyl methacrylate, in particular Ci-Cio-alkyl methacrylate,Preferably C4-alkyl methacrylate, more preferably methyl methacrylate, ethyl methacrylate, 1 / 3-propyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, 1 / 3-butyl methacrylate, aryl acrylate, preferably phenyl acrylate, benzyl acrylate, phenoxyethyl acrylate, aryl methacrylate, preferably phenyl methacrylate, benzyl methacrylate, phenoxyethyl methacrylate. The preferred compound M2 is selected from ethyl methacrylate, ethyl acrylate, butyl acrylate, ethylhexyl acrylate, styrene, vinyl acetate and combinations thereof.

[0052] Preferably for this preparation method according to the invention, compound M3 is selected from 2-acrylamido-2-methylpropane sulfonic acid, a salt of 2-acrylamido-2-methylpropane sulfonic acid, 2-(methacryloyloxy)ethanesulfonic acid, a salt of 2-(methacryloyloxy)ethanesulfonic acid, sodium methallyl sulfonate, styrene sulfonate and their combinations.

[0053] Preferably for this preparation method according to the invention, compound M4 is a compound of formula II: in which:

[0054] - D 1 and D 4 , identical or different, independently represent H or CH3

[0055] - D 2 independently represents a grouping chosen from C(O), CH2, CH2-CH2 and O-CH2-CH2-CH2-CH2

[0056] - D 3 independently represents a group chosen from (CH2-CH2O) a , (CH2CH(CH3)O)b, (CH(CH3)CH2O)C and their combinations and

[0057] - a, b, and c, whether identical or different, independently represent 0 or an integer or decimal number between 1 and 150, and the sum a+b+c is between 10 and 150. More preferably, for this preparation method according to the invention, compound M5 is a crosslinking compound or a compound comprising at least two olefinic unsaturations. Preferably, it is used in an amount of less than 5% by weight, also preferably from 0.01 to 4% by weight, in particular from 0.02 to 4% by weight or from 0.02 to 2% by weight, in particular from 0.02 to 1% by weight, relative to the total weight of monomers.

[0058] Preferably for this preparation method according to the invention, compound M6 is selected from methacrylic esters of cationic monomers, acrylic esters of cationic monomers, preferably from [2-(methacryloyloxy)ethyl]trimethylammonium chloride, [2-

[0059] (acryloyloxy)ethyl]trimethylammonium, [3-(acrylamido)propyl]trimethylammonium chloride, dimethyl-diallyl-ammonium chloride, [3-

[0060] (methacrylamido)propyl]trimethylammonium, [2-

[0061] (methacryloyloxy)ethyl]trimethylammonium, [2-(acryloyloxy)ethyl]trimethylammonium sulfate, [3-(acrylamido)propyl]trimethylammonium sulfate, dimethyl-dialyl-ammonium sulfate, [3-(methacrylamido)propyl]trimethylammonium sulfate and their combinations.

[0062] For the method of preparing copolymer P according to the invention, the polymerization reaction involves:

[0063] - from 2 mol% to 30 mol% of compound A, preferably from 5 mol% to 30 mol% of compound A,

[0064] - from 70 mol% to 98 mol% of compound M, preferably from 70 mol% to 95 mol% of compound M, relative to the molar amounts of compounds M and A. Preferably, for the method of preparing copolymer P according to the invention, the polymerization reaction involves:

[0065] - from 5 mol% to 25 mol% of compound A, more preferably from 10 mol% to 20 mol% of compound A or from 10 mol% to 15 mol% of compound A,

[0066] - from 75 mol% to 95 mol% of compound M, more preferably from 80 mol% to 90 mol% of compound M or from 85 mol% to 90 mol% of compound M, relative to the molar amount of compounds M and A.

[0067] Preferably, the polymerization reaction is carried out at a temperature above 50°C. Also preferably, the polymerization reaction is carried out at a temperature below 120°C, preferably below 100°C. Also preferably, the polymerization reaction is carried out in water, alone or in a mixture with at least one polar, protic solvent, preferably an alcohol, more preferably isopropanol. According to the invention, the copolymer P is prepared by a ring-opening radical polymerization reaction carried out in the presence of at least one radical-generating compound.Preferably, the radical-generating compound is chosen from 4,4'-azobis-4-cyanopentanoic acid (ACPA), hydrogen peroxide, benzoyl peroxide, acetyl peroxide, lauryl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, ammonium persulfate, an alkali metal persulfate (in particular sodium persulfate, potassium persulfate), an azo compound and their respective combinations or associations with an ion chosen from Fe. 11 Fe 111 Cu 1 Cu 11 and their combinations.

[0068] The copolymer P obtained by a ring-opening radical polymerization reaction of compound A is also part of the invention. The invention therefore provides a copolymer P prepared according to the method of the invention. Preferably, the copolymer P has a weight molar mass Mw, measured by CES, ranging from 800 g / mol to 10,000,000 g / mol; more preferably from 800 g / mol to 1,000,000 g / mol or from 800 g / mol to 100,000 g / mol, more preferably from 1,000 g / mol to 50,000 g / mol or from 1,000 g / mol to 20,000 g / mol.

[0069] According to the invention, the molar mass Mw is determined by Size Exclusion Chromatography (CES) or in English "Gel Permeation Chromatography" (GPC). The analyses were performed using an EcoSEC system (“TOSOH”) with a differential refractometer as the primary detector. The eluent used was tetrahydrofuran (THF), pre-filtered through a polytetrafluoroethylene membrane with a porosity of 0.45 µm. The flow rate was set at 0.3 mL / min. The entire system was thermostated at 40°C, and the injection volume was 20 pL. Samples were prepared at a concentration of 0.25 wt% in a THF mixture containing 0.25 vt of toluene, which was used as a flow marker. One ResiPore PL pre-column (50 mm x 4.6 mm) and two ResiPore PL columns (250 mm x 4.6 mm) (“Agilent”) were used in series. The system was calibrated with polystyrene standards in the range of 100 g / mol to 400,000 g / mol. (EasiVial, "Agilent").The "WinGPC Unichrom" software is used to control the chromatographic process and process the results. It allows for the determination of the number-average molar mass (Mn), the weight-average molar mass (Mw), and the polydispersity index of the polymers. If necessary, the molar mass of the polymers according to the invention can be measured after prior methylation of the copolymer, particularly when the polymer is water-soluble, i.e., when the mixture of the polymer in water is homogeneous and does not form any precipitates.

[0070] The polymerization reaction according to the invention makes it possible to prepare a copolymer P while controlling the respective amounts of residues of compound M and compound A incorporated within the polymer chain. Thus, the copolymer P according to the invention can comprise varying amounts of residues of compound M and compound A. Preferably, the copolymer P according to the invention comprises:

[0071] - from 2 mol% to 30 mol% of residue of compound A, preferably from 5 mol% to 30 mol% of residue of compound A,

[0072] - from 70 mol% to 98 mol% of residue of compound M, preferably from 70 mol% to 95 mol% of residue of compound M, relative to the molar amount of residues of compounds M and A.

[0073] More preferably, the copolymer P according to the invention comprises:

[0074] - from 5 mol% to 25 mol% of residue of compound A, more preferably from 10 mol% to 20 mol% of residue of compound A or from 10 mol% to 15 mol% of residue of compound A,

[0075] - from 75 mol% to 95 mol% of residue of compound M, more preferably from 80 mol% to 90 mol% of residue of compound M or from 85 mol% to 90 mol% of residue of compound M, relative to the molar amount of residues of compounds M and A.

[0076] According to the invention, the copolymer P can be water-soluble. Advantageously, a water-soluble polymer is a polymer capable of forming a solution in water. Generally, the solubility of polymers in water arises from the presence of hydrophilic groups. The copolymer P according to the invention can also be in the form of an emulsion.

[0077] In addition to its useful functional properties in numerous technical fields, the copolymer P according to the invention is degradable or cleavable. This allows for the production of a degradation product Pd, which is generally in the form of a polymer. Thus, the invention also provides a method for preparing a polymer Pd by degrading at least one copolymer P according to the invention. Preferably, the degradation of the copolymer P is carried out by at least one external stimulus, more preferably a stimulus selected from hydrolysis, preferably basic hydrolysis or acid hydrolysis, chemical action, preferably action by means of at least one reactive compound of the G group, for example tetra-n-butylammonium fluoride, a primary amine, redox compounds, mechanical activation, irradiation, biological action, in particular by means of an enzyme or a microorganism.

[0078] Advantageously, according to the invention, the polymer Pd has a weight molar mass Mw, measured by CES, which is lower than the mass of the copolymer P according to the invention. Preferably, according to the invention, the degradation method thus makes it possible to obtain a degraded polymer Pd which has a weight molar mass Mw, measured by CES, reduced by 10%, preferably reduced by 25% or 40%, more preferably reduced by 50% or 60%, much more preferably reduced by 75% or 90%, compared to the weight molar mass Mw of the copolymer P.

[0079] The particular, advantageous or preferred characteristics of compound A according to the invention define methods for preparing compound A, a copolymer P and methods for its preparation or for its use, as well as methods for degrading this copolymer P and a method for preparing a polymer Pd which are also particular, advantageous or preferred.

[0080] The following examples illustrate the different aspects of the invention, in particular the preparation, characterization and use of compound A according to the invention.

[0081] EXAMPLES and characterization of the Al - Method VI and characterization of the IA1 of formula IA according to the invention

[0082] 2-Mercaptoethanol (2.00 g, 25.60 mmol, 2.5 eq) in butanone (10 mL) was added under an inert atmosphere to potassium carbonate (4.45 g, 32.20 mmol, 3.2 eq) and benzyltriethylammonium chloride (BTEAC, 0.06 g) as a phase-transfer catalyst. 3-Chloro-2(chloromethyl)-1-propene (1.27 g, 10.16 mmol, 1 eq) was then added to the reaction mixture with stirring at room temperature. This mixture was then stirred for 18 hours at 75°C. The mixture was subsequently diluted with ethyl acetate (12 mL) and filtered through 2.5 cm of silica gel. The filter was eluted with ethyl acetate (100 mL). The entire clear filtrate was evaporated to yield a clear oil (2.10 g, 100%) which was analyzed by NMR. 4 H (400 MHz, CDCL). We obtain the compound IA1 of formula IA in which T 1 , T 2 , T 3 and T 4 represent H, x and y represent 2, X 1 and X 2 represent O.

[0083] Preparation and characterization of IA1 of formula IA according to the invention

[0084] In a flask under an inert atmosphere and at 0°C, 0.88 g (10 mmol,l eq) of 2-methylene-1,3-propanediol was added to 7 mL of anhydrous dichloromethane. Then, 1.6 mL (20 mmol,

[0085] 2 eq) of pyridine was added. Finally, 1.70 mL (22 mmol, 2.2 eq) of mesytyl chloride was added. The mixture was stirred at 0°C for 30 minutes and then left at room temperature for 6 hours. The flask was then placed in an ice bath at 0°C and filtered. The filtrate was mixed with ice. The organic phase was then separated and dried with sodium sulfate. The filtrate was then evaporated to give 2-methanesulfonyloxymethylallyl methanesulfonate (1.03 g, 42%), which was analyzed by NMR. X H (500 MHz, CDCh).

[0086] Under an inert atmosphere, 0.5 g of 2-methanesulfonyloxymethylallyl methanesulfonate (2.05 mmol, 1 eq) was dissolved in absolute acetonitrile (10 mL). Potassium carbonate (0.71 g, 5.12 mmol, 2.5 eq) and mercaptoethanol (0.4 mL, 5.1 mmol, 2.5 eq) were added. The mixture was stirred at 85°C for 17.5 hours. After cooling to room temperature, water (20 mL) was added, and the aqueous phase was extracted with ethyl acetate (3 x 20 to 30 mL). The organic phase was dried with sodium sulfate, and the solvent was evaporated. Compound IA1 (0.05 g, 10%) was obtained and analyzed by ¹H NMR (400 MHz, CDCh).

[0087] Preparation and characterization of compound Al according to the invention - Method VI

[0088] In a flask under an inert atmosphere, 0.62 g (3 mmol, 1 eq) of compound IA1 and 0.41 g of imidazole (6 mmol, 2 eq) were dissolved in 60 mL of anhydrous dichloromethane. Then, 0.54 mL of dichlorodiisopropylsilane (3 mmol, 1 eq) (compound IB1 of formula IB in which L 1 and L 2 represent Cl, G represents -Si(Q 1 )(Q 2 )- in which Q 1 and Q 2 representing iPr) was added dropwise over 5 minutes. The mixture was stirred for 12 hours. Then, it was diluted with 100 mL of water and extracted with 2 x 150 mL of pentane. The separated organic phases were dried with sodium sulfate, and the filtrate was evaporated to give a clear oil. The oil was purified by flash chromatography using a 95 / 5 by mass pentane / ethyl acetate eluent, then 93 / 7, to obtain 0.33 g (35%) of compound Al (Mn = 320 g / mol), which was analyzed by ¹H NMR (400 MHz, CDCh). The compound Al is obtained with the formula I in which T1 , T 2 , T 3 and T 4 represent H, x and y represent 2, X 1 and X 2 represent O and G represents -Si(Q 1 )(Q 2 )- in which Q 1 and Q 2 represent iPr.

[0089] Preparation and characterization of compound A2 according to the invention - Method VI

[0090] In a flask under an inert atmosphere, 1.33 g (6.4 mmol, 1 eq) of compound IA1 and 0.87 g of imidazole (12.8 mmol, 2 eq) were dissolved in 120 mL of anhydrous dichloromethane. Then, 0.77 mL of dichlorodimethylsilane (6.4 mmol, 1 eq) (compound IB2 of formula IB in which L 1 and L 2 represent Cl, G represents -Si(Q 1 )(Q 2 )- in which Q 1 and Q 2(representing Me) was added dropwise over 5 minutes. The mixture was stirred for 12 hours. Then, it was diluted with 150 mL of water and extracted with 2 x 200 mL of pentane. The separated organic phases were dried with sodium sulfate, and then the filtrate was evaporated to give 1.2 g (71%) of clear oil of compound A2 (Mn = 264 g / mol), which was analyzed by ¹H NMR (400 MHz, CDCh). Compound A2 of formula I is obtained, in which T 1 , T 2 , T 3 and T 4 represent H, x and y represent 2, X 1 and X 2 represent O and G represents -Si(Q 1 )(Q 2 )- in which Q 1 and Q 2 represent Me.

[0091] Preparation and characterization of PI copolvmers at P9 and characterization of PI according to the invention

[0092] 0.15 g of compound Al was placed in a flask with 1.10 mL of styrene (compound M2) and 0.0079 g of azobisisobutyronitrile (AIBN). The mixture was degassed for 15 minutes and placed under an inert atmosphere. The flask was then placed in an oil bath and heated to 75°C, with stirring maintained for 3 hours and 30 minutes. The mixture was then solubilized in tetrahydrofuran and precipitated in cold methanol. Finally, the mixture was filtered using a Buchner funnel and dried with a rotary evaporator to obtain the PI polymer as a powder with a weight-average molar mass (Mw), measured by CES, of 70,000 g / mol. Preparation and characterization of the P2 according to the invention

[0093] 0.14 g of compound Al was placed in a flask with 0.7 mL of methyl methacrylate (compound M2), 0.007 g of AIBN, and 0.4 mL of toluene. The mixture was degassed for 15 minutes and placed under an inert atmosphere. The flask was then placed in an oil bath and heated to 75°C and stirred for 2 hours. The mixture was then solubilized in tetrahydrofuran and precipitated in cold methanol. Finally, the mixture was filtered using a Buchner funnel and dried with a rotary evaporator to obtain polymer P2, which has a weight-average molar mass (Mw), measured by CES, of 28,000 g / mol. Preparation and characterization of copolymer P3 according to the invention

[0094] 0.22 g of compound Al was placed in a flask with 0.99 mL of isobornyl acrylate (compound M2), 0.009 g of AIBN, and 0.5 mL of toluene. The mixture was degassed for 15 minutes and placed under an inert atmosphere. The flask was then placed in an oil bath and heated to 75°C, with stirring maintained for 2 hours. The mixture was then dissolved in tetrahydrofuran and precipitated in cold methanol. Finally, the mixture was filtered using a Buchner funnel and dried with a rotary evaporator to obtain polymer P3, which has a weight-average molar mass (Mw), measured by CES, of 34,000 g / mol.

[0095] Preparation and characterization of the P4 copolymer according to the invention

[0096] 0.17 g of compound Al was placed in a flask with 0.46 mL of acrylic acid (compound Ml), 0.0055 g of AIBN, and 0.6 mL of dioxane. The mixture was degassed for 15 minutes and placed under an inert atmosphere. The flask was then placed in an oil bath and heated to 75°C and stirred for 2 hours. Finally, the mixture was precipitated in cold diethyl ether. The mixture was then filtered using a Buchner funnel and dried with a rotary evaporator to obtain polymer P4, the weight-average molar mass (Mw), measured by CES, of the previously methylated polymer P4, of which is 72,000 g / mol. Preparation and characterization of the copolymer P5 according to the invention

[0097] 0.30 g of compound Al was placed in a flask with 0.86 mL of vinyl acetate (compound M2), 0.0045 g of AIBN, and 0.5 mL of ethyl acetate. The mixture was degassed for 15 minutes and placed under an inert atmosphere. The flask was then placed in an oil bath and heated to 75°C, with stirring maintained for 5 hours. The mixture was then precipitated in cold pentane. Finally, the mixture was filtered using a Buchner funnel and dried with a rotary evaporator to obtain polymer P5, which has a weight-average molar mass (Mw), measured by CES, of 8000 g / mol.

[0098] Preparation and characterization of the P6 copolymer according to the invention

[0099] 0.18 g of compound Al was placed in a flask with 1.082 mL of diethyl acrylamide (compound M2), 0.0025 g of AIBN, and 0.5 mL of methanol. The mixture was degassed for 15 minutes and placed under an inert atmosphere. The flask was then placed in an oil bath and heated to 75°C, with stirring maintained for 5 hours. Finally, the mixture was precipitated in cold pentane. The mixture was then filtered using a Buchner funnel and dried with a rotary evaporator to obtain polymer P6, which has a weight-average molar mass (Mw), measured by CES, of 14,000 g / mol.

[0100] Preparation and characterization of the P7 copolymer according to the invention

[0101] In a round-bottom flask, 0.30 g of compound Al and 0.96 mL of methyl methacrylate (compound M2) were added and then incubated under an inert atmosphere at 0°C for 30 minutes after degassing. In another round-bottom flask, 0.037 g of sodium lauryl sulfate, 0.011 g of potassium persulfate, and 0.16 mg of sodium bicarbonate were added to 10 mL of distilled water and then incubated under an inert atmosphere at 0°C for 30 minutes after degassing. Next, the two reaction media were mixed in a single round-bottom flask under an inert atmosphere and placed in an oil bath at 85°C for 1 hour. Finally, the mixture was allowed to cool to room temperature to obtain polymer P7, whose weight-average molar mass (Mw), measured by CES, is 85,000 g / mol. The pH of the final solution is 3–4. The particle size of polymer P7 is approximately 34 nm. Preparation and characterization of terpolymer P8 according to the invention

[0102] 0.18 g of compound Al was placed in a flask with 0.26 mL of methyl acrylate, 0.61 mL of isobotyl acrylate, 0.009 g of AIBN, and 1.5 mL of toluene. The mixture was degassed for 15 minutes and placed under an inert atmosphere. The flask was then placed in an oil bath and heated to 75°C and stirred for 2 hours. The mixture was then solubilized in tetrahydrofuran and precipitated in cold methanol. Finally, the mixture was filtered using a Buchner funnel and dried with a rotary evaporator to obtain polymer P8, whose weight-average molar mass (Mw), measured by CES, is 13,000 g / mol. Preparation and characterization of copolymer P9 according to the invention

[0103] 0.11 g of compound A2 was placed in a flask with 0.91 mL of isobornyl acrylate (compound M2), 0.004 g of AIBN, and 0.5 mL of toluene. The mixture was degassed for 15 minutes and placed under an inert atmosphere. The flask was then placed in an oil bath, heated to 75°C, and stirred for 2 hours. Finally, the mixture containing polymer P9 was analyzed; the weight-average molar mass (Mw), measured by CES, of polymer P9 was 33,000 g / mol.

[0104] The Al and A2 compounds according to the invention allow the preparation of PI to P9 copolymers according to the invention whose composition, shape and molar mass can be controlled.

[0105] Degradation of PI polymers to P9 and characterization of Pdl to Pd9 copolymers according to the invention Pdl according to the invention

[0106] 15 mg of PI copolymer were treated with 1.2 molar equivalents of tetra-n-butylammonium fluoride (TBAF, 0.3 mL of a 1.0 M TBAF solution) in 1.2 mL of tetrahydrofuran, and the mixture was stirred for 30 minutes. An excess of an ion-exchange resin (AmberChrom 50WX2) was added, and the mixture was allowed to stand for 5 minutes. Finally, the mixture was extracted with dichloromethane and filtered through a 0.2 µm nylon filter. The degradation product Pdl of the PI copolymer has a weight-average molar mass (Mw), measured by CES, of 64,000 g / mol.

[0107] Preparation and characterization of Pd2 according to the invention

[0108] Similarly, the degradation of polymer P2 is assessed by replacing polymer PI with polymer P2 and treating it using TBAF. The degradation product Pd2 of copolymer P2 has a weight-average molar mass Mw, measured by CES, of 8500 g / mol.

[0109] Preparation and characterization of Pd3 according to the invention

[0110] Similarly, the degradation of polymer P3 is assessed by replacing polymer PI with polymer P3 and treating it using TBAF. The degradation product Pd3 of copolymer P3 has a weight-average molar mass Mw, measured by CES, of 3500 g / mol.

[0111] Preparation and characterization of Pd4 according to the invention. Similarly, the degradation of the P4 polymer is evaluated by replacing the PI polymer with P4 polymer and treating it with TB AF. The Pd4 degradation product of the P4 copolymer has a weight-average molar mass (Mw), measured by CES, of 3100 g / mol.

[0112] Preparation and characterization of Pd5 according to the invention

[0113] Similarly, the degradation of polymer P5 is evaluated by replacing polymer PI with polymer P5 and treating it with TB AF. The degradation product Pd5 of copolymer P5 has a weight-average molar mass Mw, measured by CES, of 330 g / mol.

[0114] Preparation and characterization of Pd6 according to the invention

[0115] Similarly, the degradation of polymer P6 is evaluated by replacing polymer PI with polymer P6 and treating it with TB AF. The degradation product Pd6 of the P6 copolymer has a weight-average molar mass Mw, measured by CES, of 5500 g / mol.

[0116] Preparation and characterization of Pd7 according to the invention

[0117] Similarly, the degradation of polymer P7 is evaluated by replacing polymer PI with polymer P7 and treating it with TB AF. The degradation product Pd7 of copolymer P7 has a weight-average molar mass Mw, measured by CES, of 70,000 g / mol.

[0118] Preparation and characterization of Pd8 according to the invention

[0119] Similarly, the degradation of polymer P8 is evaluated by replacing polymer PI with polymer P8 and treating it with TB AF. The degradation product Pd8 of the P8 copolymer has a weight-average molar mass Mw, measured by CES, of 4700 g / mol.

[0120] Preparation and characterization of Pd9 according to the invention

[0121] Similarly, the degradation of polymer P9 is evaluated by replacing polymer PI with polymer P9 and treating it with TB AF. The degradation product Pd9 of the P9 copolymer has a weight-average molar mass Mw, measured by CES, of 22,000 g / mol.

[0122] The molar mass of the Pdl to Pd9 polymers obtained by degradation of the PI to P9 polymers according to the invention is much lower than the mass of the starting PI to P9 copolymers. The P copolymers according to the invention, prepared using the A compounds according to the invention, were able to be degraded in a controlled manner.

Claims

DEMANDS 1. Heterocyclic compound A comprising: - an exocyclic ethylenic unsaturation, - two intracyclic sulfide groups, each in the P position of the ethylenic exo-unsaturation and - a cleavable intracyclic chemical group G.

2. Compound A according to claim 1 wherein the intracyclic sulfide groups are reactive under ring-opening radical polymerization conditions, in particular in the presence of at least one radical initiator compound and at a temperature ranging from room temperature to 150°C, preferably from 50°C to 100°C; or wherein the exocyclic ethylenic unsaturation is polymerizable, preferably polymerizable in aqueous media, more preferably polymerizable in water, alone or optionally combined with a protic solvent.

3. Compound A according to claim 1 or 2, wherein: - the intracyclic group G is cleavable by at least one external stimulus, preferably a stimulus selected from hydrolysis, preferably basic hydrolysis or acid hydrolysis, chemical action, preferably action by means of at least one reactive compound of the group G, for example tetra-n-butylammonium fluoride, a primary amine, redox compounds, mechanical activation, irradiation, biological action, in particular by means of an enzyme or a microorganism; or for which: - the group G is chosen from a group Gl: -Si(Q 1 )(Q 2 )- ; a G2 group: -P(OH)(=O)-; a G3 grouping: -P(OQ 1 )(=O)- ; a G4 group: -P(=O)(OH)-OP(=O)(OH)-; a G5 grouping: -P(E 1 OQ 1 )(=O)- ; a grouping G6 : -P(E 1 OQ 1 )(=O)- ; a G7 grouping: -CQ^OQ 2 )- ; a grouping G8: -C(Q 1 )(Q 2)- ; a G9 group: -C(=O)- ; a G10 group: -C(Q 1 )(Q 2 )- ; a Gl group: -C(=S)- ; a G12 group: a direct bond ; a G13 group: -C(OH)(Q 1 )- ; a G14 grouping: -C(OQ 1 )(Q 2 )- ; a grouping G15: -C(=O)- ; a grouping G16: -C(=O)-O-(O=)C- ; a grouping G17: - C=N- ; a grouping G18: -C(=O)- ; a grouping G19: -C(=O)- ; a grouping G20: -C(=0)- ; a group G21: -C(=O)- ; a group G22: -S(=O)2- ; a group G23: -C(=O)-Si- ; preferably chosen from G1 to G12 and G18; more preferably chosen from G1, G7, G8, G9 and G18, in which: • E 1 represents a divalent alkylene group, preferably a linear divalent Ci-Cio-alkylene group or a branched divalent C3-C10-alkylene group, preferably selected from a divalent C1-C4-alkylene group, in particular a divalent C2-C3-alkylene group, • Q 1 and Q 2 independently represent H or a group chosen from an alkyl group, a heteroalkyl group, an aryl group, a heteroaryl group; preferably chosen from H, a Ci-C2o-alkyl group, a Ci-C2o-heteroalkyl group, a phenyl group, a phenoxy group, preferably chosen from a linear Ci-Cio-alkyl group, a branched C3-Cio-alkyl group, more preferably chosen from a linear Ci-Cio-heteroalkyl group, a branched C3-Cio-heteroalkyl group.

4. Compound A according to any one of claims 1 to 3 of formula I: in which: - T 1 , T 2 , T 3 and T 4independently represent H or an aryl group or an alkyl group, preferably a Ci-C2o-alkyl group, preferably a linear Ci-C2o-alkyl group or a branched C3-C2o-alkyl group, more preferably a linear Ci-Cio-alkyl group or a branched C3-C10-alkyl group, most preferably a linear Ci-Co-alkyl group or a branched C3-Co-alkyl group, even more preferably a linear Ci-C3-alkyl group or a branched C3-C4-alkyl group, - x and y independently represent a number from 1 to 5, preferably 1, 2 or 3, more preferably x and y simultaneously represent 2 or one represents 2 and the other represents 3; - X 1 and X 2 independently represent a direct bond, O, S, NH or NQ 3 , - Q 3represents an alkyl group, preferably a Ci-C2o-alkyl group, preferably a linear Ci-Cio-alkyl group or a branched C3-C10-alkyl group, - G is defined according to one of claims 1 to 3.

5. Method V for preparing a compound A according to one of claims 1 to 4 selected from: - preparation method VI comprising the reaction of a compound of formula IA: in which T 1 , T 2 , T 3 , T 4 X 1 X 2 x and y are defined independently according to any one of claims 1 to 4, with a compound of formula IB: The GL 2 IB in which G is chosen from G1 to G12 according to claim 3 and L 1 and L 2, identical or different, independently represent a leaving group, preferably a mesylate group or a tosylate group, or a halide, preferably chloride or bromide; - the V2 preparation method comprising the reaction of a compound of formula IC: IC in which T 1 , T 2 , T 3 and T 4 are defined independently according to any one of claims 1 to 4 and L 1 and L 2 , identical or different, independently represent a departing group, preferably a mesylate group or a group tosylate, or a halide, preferably chloride or bromide, with a compound of formula ID: in which G, X 1 X 2 , x and y are defined independently according to any one of claims 1 to 4, preferably G is chosen from G1 to G23 according to claim 3.

6. Method for preparing a copolymer P comprising a ring-opening radical polymerization reaction of compound A, particularly in aqueous or protic solvent media, at a temperature ranging from room temperature to 150°C and in the presence of at least one radical-generating compound: - of at least one compound A according to one of claims 1 to 4 and - of at least one polymerizable compound M comprising at least one polymerizable olefinic unsaturation.

7. Method of preparing a copolymer P according to claim 6 wherein compound M is selected from an anionic compound M1, a non-ionic compound M2, a sulfur compound M3, a hydrophobic or associative compound M4, a crosslinking compound M5 comprising at least 2 ethylenic unsaturations, a cationic compound M6 and combinations thereof.

8. Preparation method according to any one of claims 6 or 7 wherein: compound Ml is selected from a compound comprising one or two carboxylic acid functions, preferably a single carboxylic acid function, more preferably a compound Ml selected from acrylic acid, methacrylic acid, a salt of acrylic acid, a salt of methacrylic acid, itaconic acid, maleic acid, maleic anhydride and their combinations, most preferably acrylic acid, methacrylic acid, a salt of acrylic acid, a salt of methacrylic acid and their combinations; Compound M2 is a non-ionic compound comprising at least one polymerizable ethylenic unsaturation, more preferably one polymerizable vinyl function, much more preferably a compound M2 selected from vinyl acetate, styrene, vinylcaprolactam, esters of an acid comprising at least one monocarboxylic acid function, in particular an ester of an acid selected from acrylic acid, methacrylic acid, and their combinations, for example hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, alkyl acrylate, in particular C1-C10-alkyl acrylate, preferably Ci-C4-alkyl acrylate, more preferably methyl acrylate, ethyl acrylate, β-propyl acrylate, isopropyl acrylate, isobutyl acrylate, β-butyl acrylate, alkyl methacrylate, in particular Ci-Cio-alkyl methacrylate, preferably methacrylate Ci-C4-alkyl, more preferably methyl methacrylate,ethyl methacrylate, β-propyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, β-butyl methacrylate, aryl acrylate, preferably phenyl acrylate, benzyl acrylate, phenoxyethyl acrylate, aryl methacrylate, preferably phenyl methacrylate, benzyl methacrylate, phenoxyethyl methacrylate; compound M3 is selected from 2-acrylamido-2-methylpropanesulfonic acid, a salt of 2-acrylamido-2-methylpropanesulfonic acid, 2-(methacryloyloxy)ethanesulfonic acid, a salt of 2-(methacryloyloxy)ethanesulfonic acid, sodium methallyl sulfonate, styrene sulfonate and combinations thereof; compound M4 is a compound of formula II:, in which: - D 1 and D 4 , identical or different, independently represent H or CH3, - D 2 independently represents a grouping chosen from C(O), CH2, CH2-CH2 and O-CH2-CH2-CH2-CH2 - D 3independently represents a group chosen from (CH2- CH2O) a , (CH2CH(CH3)O)b, (CH(CH3)CH2O) c and their combinations and - a, b and c, identical or different, independently represent 0 or an integer or decimal number between 1 and 150 and the sum a+b+c is between 10 and 150; the compound M5 is a crosslinking compound or a compound comprising at least two olefinic unsaturations; preferably, used in an amount of less than 5% by weight, also preferably from 0.01 to 4% by weight, in particular from 0.02 to 4% by weight or from 0.02 to 2% by weight, in particular from 0.02 to 1% by weight, relative to the total amount by weight of monomers;compound M6 is selected from methacrylic esters of cationic monomers, acrylic esters of cationic monomers, preferably [2-(methacryloyloxy)ethyl]trimethylammonium chloride, [2-(acryloyloxy)ethyl]trimethylammonium chloride, [3-(acrylamido)propyl]trimethylammonium chloride, dimethyl-diallyl-ammonium chloride, [3-(methacrylamido)propyl]trimethylammonium chloride, [2-(methacryloyloxy)ethyl]trimethylammonium sulfate, [2-(acryloyloxy)ethyl]trimethylammonium sulfate, [3-; (acrylamido)propyl]trimethylammonium, dimethyl-diallyl-ammonium sulfate, [3-(methacrylamido)propyl]trimethylammonium sulfate and their combinations.

9. A preparation method according to any one of claims 6 to 8, wherein the polymerization reaction involves: - from 2% to 30% molar of compound A, preferably from 5% to 30% molar of compound A or from 5% to 25% molar of compound A, more preferably from 10% to 20% molar of compound A or from 10% to 15% molar of compound A, - from 70 mol% to 98 mol% of compound M, preferably from 70 mol% to 95 mol% of compound M or from 75 mol% to 95 mol% of compound M, more preferably from 80 mol% to 90 mol% of compound M or from 85 mol% to 90 mol% of compound M, relative to the molar amount of compounds M and A; or - the polymerization reaction is carried out at a temperature above 50°C; or - the polymerization reaction is carried out at a temperature below 120°C, preferably below 100°C; or - the polymerization reaction is carried out in water, alone or in a mixture with at least one polar, protic solvent, preferably an alcohol, more preferably isopropanol; or for which: - The radical-generating compound is chosen from 4,4'-azobis-4-cyanopentanoic acid (CPA), hydrogen peroxide, benzoyl peroxide, acetyl peroxide, lauryl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, ammonium persulfate, an alkali metal persulfate (in particular sodium persulfate, potassium persulfate), an azo compound, and their respective combinations or associations with an ion chosen from Fe 11 Fe 111 Cu 1 Cu 11 and their combinations.

10. Copolymer P prepared according to the method according to any one of claims 6 to 9, preferably copolymer P having a weight molar mass Mw, measured by CES, from 800 g / mol to 10,000,000 g / mol; more preferably from 800 g / mol to 1,000,000 g / mol or from 800 g / mol to 100,000 g / mol, more preferably from 1,000 g / mol to 50,000 g / mol or from 1,000 g / mol to 20,000 g / mol.

11. Copolymer P according to claim 10 comprising: - from 2 mol% to 30 mol% of residue of compound A, preferably from 5 mol% to 30 mol% of residue of compound A or from 5 mol% to 25 mol% of residue of compound A, more preferably from 10 mol% to 20 mol% of residue of compound A or from 10 mol% to 15 mol% of residue of compound A, - from 70 mol% to 98 mol% of residue of compound M, preferably from 70 mol% to 95 mol% of residue of compound M or from 75 mol% to 95 mol% of residue of compound M, more preferably from 80 mol% to 90 mol% of residue of compound M or from 85 mol% to 90 mol% of residue of compound M, relative to the molar amount of residues of compounds M and A.

12. Method of preparing a polymer Pd by degradation of at least one copolymer P according to any one of claims 10 or 11, preferably by at least one external stimulus, more preferably a stimulus selected from hydrolysis, preferably basic hydrolysis or acid hydrolysis, chemical action, preferably action by means of at least one reactive compound of the G group, for example tetra-n-butylammonium fluoride, a primary amine, redox compounds, mechanical activation, irradiation, biological action, in particular by action using an enzyme or a microorganism.

13. Method according to claim 12 wherein the degraded polymer Pd has a weight molar mass Mw, measured by CES, reduced by 10%, preferably reduced by 25% or reduced by 40%, more preferably reduced by 50% or reduced by 60%, much more preferably reduced by 75% or reduced by 90%, relative to the weight molar mass Mw of the copolymer P.

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