POLYMERIZABLE AND CLIVABLE HETEROCYCLIC COMPOUND

Abstract

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.

Description

Title of the invention: POLYMERIZABLE AND CLIVABLE HETEROCYCLIC COMPOUND

[0001] 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 also forms part of the invention.

[0002] 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 once they have been used. Preferably, they should be able to degrade in a controlled manner or degrade naturally.

[0003] It is therefore particularly useful to have polymerizable compounds that allow the controlled introduction of cleavable functions 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.

[0004] These polymerizable compounds should allow the introduction of various cleavable functions within these copolymers. In particular, the variety of cleavable functions introduced should make it possible to obtain copolymers that are degradable under different conditions.

[0005] Furthermore, the methods for preparing these cleavable and polymerizable compounds should be efficient and easy to implement. These preparation methods should also allow for good yields, particularly by limiting the number of steps or by using readily available reagents. In particular, these compounds should be prepared in a dilute reaction medium while controlling the formation of reaction by-products.

[0006] Also, the use of these cleavable compounds by polymerization should be facilitated while improving the variety of accessible copolymers, particularly through the implementation of different types of comonomers. The reactivity of these polymerizable compounds with different types of monomers is therefore a desirable property.

[0007] The preparation of copolymers of different forms that are degradable is also an important objective. These copolymers can be They are water-soluble. They can be in the form of a dispersion or an emulsion in a liquid medium, particularly an aqueous medium. They can also be in the form of 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 different conditions. In particular, these copolymers should be degradable by hydrolysis, by chemical action, by mechanical activation, by irradiation, or by biological action.

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

[0010] Thus, there is an important need to have 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.

[0011] Polymerizable cleavable compounds in the prior art and their preparation methods are not always satisfactory for providing a solution to all or some of the problems encountered. Thus, the invention provides a polymerizable and cleavable compound that makes it possible to provide a solution to all or some of the known compounds.

[0012] Thus, the invention provides a heterocyclic compound A comprising: - an exocyclic ethylenic unsaturation, - two intracyclic sulfide groups, each in the [3] position of the ethylenic exo-unsaturation and - a cleavable intracyclic chemical group G.

[0013] 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 groups of compound A are in the [3] position of an ethylenic exo-unsaturation; they are reactive in a ring-opening radical polymerization reaction. The G group of compound A is cleavable or degradable, particularly under specific conditions.

[0014] Preferably for compound A according to the invention, the intracyclic sulfide groups are reactive under ring-opening radical polymerization conditions, particularly in the presence of at least one initiator compound radical and at a temperature ranging from room temperature to 150°C, preferably ranging from 50°C to 100°C.

[0015] Advantageously for the copolymer P according to the invention, the exocyclic ethylenic unsaturation of compound A is polymerizable, in particular polymerizable in aqueous media, preferably polymerizable in water, alone or optionally combined with a protic solvent, such as acetic acid and alcohols, in particular isopropanol. According to the invention, the exocyclic ethylenic unsaturation of compound A can be polymerized in water alone.

[0016] 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 chosen 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.

[0017] For compound A according to the invention, the cleavable group G can be chosen from a group G1 of formula: -Si(Q')(Q2)- ; a group G2 of formula: -P(OH) (=O)- ; a group G3 of formula: -P(OQ')(=O)- ; a group G4 of formula: -P(=O)(OH)-OP(=O)(OH)- ; a group G5 of formula: -P(E1OQ1)(=O)- ; a group G6 of formula: -P(E1OQ1)(=O)- ; a group G7 of formula: -CQ'(OQ2)- ; a group G8 of formula: -C(Q')(Q2)- ; a group G9 of formula: -C(=O)- ; a group G10 of formula: -C(Q')(Q2)- ; a group G11 of formula: -C(=S)- ; a G12 group with the formula: a direct bond; a G13 group with the formula: -C(OH)(Q')-; a G14 group with the formula: -C(OQ *)(Q2)-; a G15 group with the formula: -C(=O)-; a G16 group with the formula: -C(=O)-O-(O=)C-; a ​​G17 group with the formula: -C=N-; a G18 group with the formula: -C(=O)-; a G19 group with the formula: -C(=O)-; a G20 group with the formula: -C(=O)-;a grouping G21 of formula: -C(=O)- ; a grouping G22 of formula: -S(=O)2- ; a grouping G23 of formula: -C(=O)-Si- ; preferably chosen from G1 to G12 and G18 ; more preferably chosen from G1, G7, G8, G9 and G18, in which: ; - E1 represents a divalent alkylene group, preferably a divalent Ci-Cio-alkylene group, linear or branched, - Q1 and Q2 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.

[0018] 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.

[0019] Preferably for Q1 and Q2, the Ci-C20-alkyl group can be independently chosen from a linear Ci-Cio-alkyl group, a branched C3-Cio-alkyl group.

[0020] Also preferably for Q1 and Q2, the Ci-C20-heteroalkyl group can be independently chosen from a linear CrCio-heteroalkyl group, a branched C3-Ci0-heteroalkyl group.

[0021] Preferably, E1 represents a divalent alkylene group, preferably chosen from a linear divalent Ci-Cio-alkylene group, a branched divalent C3-Cio-alkylene group, more preferably a divalent Ci-C4-alkylene group, in particular a divalent C2-C3-alkylene group.

[0022] Particularly efficiently according to the invention, the implemented group G makes it possible to obtain a compound A which is cleavable. Preferably, depending on the group G chosen, the compound A then comprises a group selected from among a diethersilyl group including a Gl 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 Gl1 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 G17 group, an ester group including a G18 group, an amide group including a G19 group, a methane 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.

[0023] Preferably, compound A according to the invention is a compound of formula I: [chem I]

[0024]

[0025]

[0026] in which: - T1, T2, T3 and T4 independently 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-C20-alkyl group, more preferably a linear Ci-Cio-alkyl group or a branched C3-Ci0-alkyl group, most preferably a linear Ci-C6-alkyl group or a branched C3-C6-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; - X1 and X2 independently represent a direct bond, O, S, NH or NQ3, - Q3 represents an alkyl group, preferably a CrC2o-alkyl group, preferably a linear Ci-CiO-alkyl group or a branched C3-CiO-alkyl group, - G is a cleavable intracyclic chemical group G, preferably G is chosen from G1 to G23. More preferably, compound A according to the invention is a compound of formula I in which T1, T2, T3 and T4 independently represent H or a methyl group; more preferably they represent H. Also, more preferably, compound A according to the invention is a compound of formula I in which x and y simultaneously represent 2. Also more preferably, compound A according to the invention is a compound of formula I in which X1 and X2 are identical or independently represent a direct bond, O or S; more preferably they represent O.

[0027] Also more preferably, compound A according to the invention is a compound of formula I in which G is chosen from G1 to G12 and G18; more preferably G is chosen from G11, G7, G8, G9 and G18.

[0028] The method for preparing compound A according to the invention is particularly advantageous. Thus, the invention also provides a method V for preparing a compound A. Preferably, the preparation method V according to the invention is selected from a preparation method VI by simple cyclization of a final intermediate compound. Also preferably, the preparation method V according to the invention is selected from a preparation method V2 by simple reaction of a dithiol compound with a compound comprising two leaving groups.

[0029] More preferably according to the invention, preparation method VI comprises the reaction of a compound of formula IA: [chem IA] T-, H t-T5 4 HJ S s xhi wherein T1, T2, T3, T4, X1, X2, x and y are defined independently according to the invention, with a compound of formula IB: [chem IB] GL2 in which G is chosen from Gl to G12 according to the invention and L1 and L2, identical or different, independently represent a leaving group, preferably a mesylate group or a tosylate group, or a halide, preferably chloride or bromide.

[0030] Particularly preferred 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 V1 then comprises the direct cyclization of the compound of formula IA.

[0031] Also, more preferably according to the invention, the preparation method V2 comprises the reaction of a compound of formula IC: [chem IC] in which T1, T2, T3 and T4 are defined independently according to the invention and L1 and L2, 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: [chem ID] in which G, X1, X2, x and y are defined independently according to the invention. Particularly preferred for preparation method V2, G is selected from G1 to G23 according to the invention.

[0032] 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.

[0033] 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 group G selected from the groups G1, G2, G3, G4, G5, G6, G9, G11, G18, G21, G22, and G23.

[0034] Also preferably according to the invention, the preparation method V can employ an acid, preferably an acid chosen from para-toluene sulfonic acid and methanesulfonic acid, in the preparation of compound A comprising a group G chosen from groups G7, G8, G10, G13, G14 and G17.

[0035] 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, preparation method V 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.

[0036] 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 depending on the specific conditions chosen. 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 a temperature 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.

[0037] Preferably for the preparation of the copolymer P according to the invention, the compound M is chosen 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 their combinations.

[0038] More preferably for this preparation method according to the invention, the compound Ml is chosen from a compound comprising one or two carboxylic acid functions, preferably a single carboxylic acid function. More preferably, compound Ml is chosen 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.

[0039] More 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, n-propyl acrylate, isopropyl acrylate, isobutyl acrylate, n-butyl acrylate, alkyl methacrylate, in particular Ci-Cio-alkyl methacrylate, preferably Ci-C4-alkyl methacrylate, more preferably methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, n-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 chosen from ethyl methacrylate, ethyl acrylate, butyl acrylate, ethylhexyl acrylate, styrene, vinyl acetate and their combinations.

[0040] 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.

[0041] More preferably for this preparation method according to the invention, compound M4 is a compound of formula II: [Chem II] in which: - D1 and D4, whether identical or different, independently represent H or CH3. - D2 independently represents a grouping chosen from C(O), CH2, CH2-CH2 and o-ch2-ch2-ch2-ch2, - D3 independently represents a group chosen from (CH2-CH2O)a, (CH2 CH(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.

[0042] 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 amount of monomers.

[0043] More 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-(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 sulfate, dimethyl-diallyl-ammonium sulfate, [3-(methacrylamido)propyl]trimethylammonium sulfate and their combinations.

[0044] For the method of preparing the copolymer P according to the invention, the polymerization reaction involves: - from 2 mol% to 30 mol% of compound A, preferably from 5 mol% to 30 mol% of compound A, - from 70 molar to 98 molar of compound M, preferably from 70 molar to 95 molar of compound M, relative to the molar amount of compounds M and A.

[0045] Preferably for the method of preparing copolymer P according to the invention, the polymerization reaction involves: - 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, - 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.

[0046] 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.

[0047] 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 selected 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 Fe11, Fe111, Cu1, Cu11 and their combinations.

[0048] 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.

[0049] 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 µL. 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 chain and process the results. It allows the determination of the number-average molar mass (Mn), the weight-average molar mass (Mw), and the polydispersity index of the polymers. Where applicable, 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 shows no precipitate.

[0050] 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: - from 2 mol% to 30 mol% of residue of compound A, preferably from 5 mol% to 30 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, relative to the molar amount of residues of compounds M and A.

[0051] More preferably, the copolymer P according to the invention comprises: - 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 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.

[0052] 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.

[0053] In addition to its functional properties useful in many technical fields, the copolymer P according to the invention is degradable or cleavable. This makes it possible to obtain 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.

[0054] 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 reduced by 40%, more preferably reduced by 50% or reduced by 60%, much more preferably reduced by 75% or reduced by 90%, compared to the weight molar mass Mw of the copolymer P.

[0055] 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 of degradation of this copolymer P and a method of preparation of a polymer Pd which are also particular, advantageous or preferred.

[0056] The following examples illustrate the different aspects of the invention, in particular the preparation, characterization and use of compound A according to the invention. EXAMPLES

[0057] Preparation and characterization of compound A 1 - Method V1

[0058] Preparation and characterization of compound IA1 of formula IA according to the invention

[0059] 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 then 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 give a clear oil (2.10 g, 100%) which was analyzed by *H NMR (400 MHz, CDC13). The resulting compound is IA1 with formula IA, where T1, T2, T3 and T4 represent H, x and y represent 2, and X1 and X2 represent O.

[0060] Preparation and characterization of compound IA1 of formula IA according to the invention

[0061] 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, 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. Next, the flask was placed in an ice bath at 0°C and filtered. The filtrate was mixed with ice. Then, the organic phase was separated and dried with sodium sulfate. Then, the filtrate was evaporated to give 2-methanesulfonyloxymethylallyl methanesulfonate (1.03g, 42%) analyzed by *H NMR (500 MHz, CDC13).

[0062] 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 mL to 30 mL). The organic phase... The sample 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, CDC13).

[0063] Preparation and characterization of compound Al according to the invention - Method V1

[0064] 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 L1 and L2 represent Cl, G represents -Si(Q')(Q2)- in which Q1 and Q2 represent iPr) was added dropwise over 5 min. The mixture was stirred for 12 hours. Then, it was diluted with 100 mL of water and extracted with 2 times 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 a 93 / 7 eluent, to obtain 0.33 g (35%) of the Al compound (Mn = 320 g / mol), which was analyzed by ¹H NMR (400 MHz, CDC13).We obtain the compound Al of formula I in which T1, T2, T3 and T4 represent H, x and y represent 2, X1 and X2 represent O and G represents -Si(Q')(Q2)- in which Q1 and Q2 represent iPr. .

[0065] Preparation and characterization of compound A2 according to the invention - Method V1

[0066] In a balloon 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) was dissolved in 120 mL of anhydrous dichloromethane. Then, 0.77 mL of dichlorodimethylsilane (6.4 mmol, 1 eq) (compound IB2 of formula IB, where L1 and L2 represent Cl, and G represents -Si(Q')(Q2)-, where Q1 and Q2 represent Me) was added dropwise over 5 min. The mixture was stirred for 12 hours. It was then 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 the filtrate was evaporated to give a clear oil of 1.2 g (71%) of compound A2 (Mn = 264 g / mol), which was analyzed by 1H NMR (400 MHz, CDC13). We obtain the compound A2 of formula I in which T1, T2, T3 and T4 represent H, x and y represent 2, X1 and X2 represent O and G represents -Si(Q1 )(Q2)- in which Q1 and Q2 represent Me.

[0067] Preparation and characterization of PI to P9 copolymers

[0068] Preparation and characterization of the PI copolymer according to the invention

[0069] 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 and stirred for 3 hours and 30 minutes. 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 the PI polymer in the form of a powder and whose average molar mass by weight Mw, measured by CES, is 70,000 g / mol.

[0070] Preparation and characterization of the P2 copolymer according to the invention

[0071] 0.14 g of compound Al was placed in a flask with 0.7 mL of methacrylate methyl (compound M2), 0.007 g of AIBN, and 0.4 mL of toluene were used. 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 P2, which has a weight-average molar mass (Mw), measured by CES, of 28,000 g / mol.

[0072] Preparation and characterization of the P3 copolymer according to the invention

[0073] 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, whose weight-average molar mass (Mw), measured by CES, is 34,000 g / mol.

[0074] Preparation and characterization of the P4 copolymer according to the invention

[0075] 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, whose weight-average molar mass (Mw), measured by CES of the previously methylated polymer P4, is 72,000 g / mol.

[0076] Preparation and characterization of the P5 copolymer according to the invention

[0077] 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, whose weight-average molar mass (Mw), measured by CES, is 8000 g / mol.

[0078] Preparation and characterization of the P6 copolymer according to the invention

[0079] 0.18 g of compound Al was placed in a flask with 1.082 mL of diethylacrylamide (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, whose weight-average molar mass (Mw), measured by CES, is 14,000 g / mol.

[0080] Preparation and characterization of the P7 copolymer according to the invention

[0081] In a round-bottom flask, 0.30 g of compound Al and 0.96 mL of methyl methacrylate (compound M2) were added and then placed under an inert atmosphere after degassing the mixture at 0°C for 30 minutes. 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 placed under an inert atmosphere after degassing the mixture at 0°C for 30 minutes. 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 size of the P7 polymer particles is approximately 34 nm.

[0082] Preparation and characterization of the P8 terpolymer according to the invention

[0083] 0.18 g of compound Al was placed in a flask with 0.26 mL of methyl acrylate, 0.61 mL of isobornyl acrylate, 0.009 g of AIBN, and 1.5 mL of toluene were used. 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 P8, which has a weight-average molar mass (Mw), measured by CES, of 13,000 g / mol.

[0084] Preparation and characterization of the P9 copolymer according to the invention

[0085] 0.11 g of compound A2 was placed in a flask with 0.91 mL of isobornyl acrylate (Compound M2) with 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 and 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.

[0086] The Al and A2 compounds according to the invention make it possible to prepare PI to P9 copolymers according to the invention whose composition, shape and molar mass can be controlled.

[0087] Degradation of PI polymers to P9 and characterization of Pdl to Pd9 copolymers according to the invention

[0088] Preparation and characterization of the Pdl polymer according to the invention

[0089] 15 mg of PI copolymer were treated with 1.2 molar equivalents of fluoride Tetra-n-butylammonium (TB AF, 0.3 mL of a 1.0 M TB AF solution) was added to 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.

[0090] Preparation and characterization of the Pd2 polymer according to the invention

[0091] Similarly, the degradation of polymer P2 is evaluated by replacing the polymer PI by polymer P2 and by treating it with TB AF. The degradation product Pd2 of the copolymer P2 has a weight average molar mass Mw, measured by CES, of 8500 g / mol.

[0092] Preparation and characterization of the Pd3 polymer according to the invention

[0093] Similarly, the degradation of polymer P3 is evaluated by replacing the The PI polymer is formed by polymer P3 and by treating it with TB AF. The Pd3 degradation product of the P3 copolymer has a weight average molar mass Mw, measured by CES, of 3500 g / mol.

[0094] Preparation and characterization of the Pd4 polymer according to the invention

[0095] Similarly, the degradation of polymer P4 is evaluated by replacing the The PI polymer is formed from the P4 polymer and treated 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.

[0096] Preparation and characterization of the Pd5 polymer according to the invention

[0097] Similarly, the degradation of polymer P5 is evaluated by replacing the The P5 polymer is formed by treating the P5 polymer with TB AF. The Pd5 degradation product of the P5 copolymer has a weight-average molar mass Mw, measured by CES, of 330 g / mol.

[0098] Preparation and characterization of the Pd6 polymer according to the invention

[0099] Similarly, the degradation of polymer P6 is evaluated by replacing the The P6 polymer is formed by treating the P6 polymer with TB AF. The Pd6 degradation product of the P6 copolymer has a weight-average molar mass Mw, measured by CES, of 5500 g / mol.

[0100] Preparation and characterization of the Pd7 polymer according to the invention

[0101] 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.

[0102] Preparation and characterization of the Pd8 polymer according to the invention

[0103] Similarly, the degradation of polymer P8 is evaluated by replacing the The PI polymer is formed by polymer P8 and by treating it with TB AF. The Pd8 degradation product of the P8 copolymer has a weight average molar mass Mw, measured by CES, of 4700 g / mol.

[0104] Preparation and characterization of the Pd9 polymer according to the invention

[0105] Similarly, the degradation of polymer P9 is evaluated by replacing the The PI polymer is formed by polymer P9 and by treating it with TB AF. The Pd9 degradation product of the P9 copolymer has a weight-average molar mass Mw, measured by CES, of 22,000 g / mol.

[0106] 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, could be degraded in a controlled manner.

Claims

Demands

1. Heterocyclic compound A comprising: - an exocyclic ethylenic unsaturation, - two intracyclic sulfide groups, each in position [3 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 radial alar 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, 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 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 wherein: - group G is selected from a G1 group: -Si(Q')(Q2 )- ; a G2 group: -P(OH)(=O)- ; a G3 group: -P(OQ *)(=O)- ; a G4 group: -P(=O)(OH)-OP(=O)(OH)- ; a G5 group: -P(E1OQ1)(=O)- ; a grouping G6: -PCE'OQ1) (=0)- ; a grouping G7: -CQ'(OQ2)- ; a grouping G8: -C(Q*) (Q2)- ; a grouping G9: -C(=0)- ; a grouping G10: -C(Q')(Q 2)- ; a grouping G11: -C(=S)- ;a G12 group: a direct bond; a G13 group: -C(OH)(Q')- ; a G14 group: -C(OQ')(Q2)- ; a G15 group: -C(=O)- ; a G16 group: -C(=O)-O-(O=)C- ; a G17 group: -C=N- ; a G18 group: -C(=0)- ; a G19 group: -C(=0)- ; a G20 group: -C(=0)- ; a G21 group: -C(=0)- ; a G22 group: -; 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: * E1 represents a divalent alkylene group, preferably a linear divalent Ci-Cio-alkylene group or a branched divalent C3-CiO-alkylene group, preferably selected from a divalent C1-C4-alkylene group, in particular a divalent C2-C3-alkylene group, * Q1 and Q2 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 CrC2o-alkyl group, a CrC2o-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: [chem I] in which: - T1, T2, T3 and T4 independently represent H or an aryl group or an alkyl group, preferably a Ci-C2o-alkyl group, preferably a linear CrC2o-alkyl group or a branched C3-C20-alkyl group, more preferably a linear Ci-Cio-alkyl group or a branched C3-Ci0-alkyl group, most preferably a linear Ci-C6-alkyl group or a branched C3-C6-alkyl group, even more preferably a linear CrC3-alkyl group or a branched C3-C4-alkyl group,

5. - 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; - X1 and X2 independently represent a direct bond, O, S, NH or NQ3, - Q3 represents an alkyl group, preferably a Ci-C2o-alkyl group, preferably a linear Ci-Cio-alkyl group or a branched C3-Ci0-alkyl group, - G is defined according to one of claims 1 or 2. 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: [chem IA] wherein T1, T2, T3, T4, X1, X2, x and y are defined independently according to any one of claims 1 to 4, with a compound of formula IB: [chem IB] GL2 in which G is selected from G1 to G12 according to claim 3 and L1 and L2, 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: [chem IC] in which T1, T2, T3 and T4 are defined independently according to any one of claims 1 to 4 and L1 and L2, 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: [chem ID] SH SH v xt ,x2 G in which G, X1, X2, x and y are defined independently according to any one of claims 1 to 4, preferably G is selected from G1 to G23 according to claim 3.

6. Method of preparing a copolymer P comprising a ring-opening radical polymerization reaction of compound A, in particular in aqueous medium or protic solvent, 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 any 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. A preparation method according to any one of claims 6 or 7, wherein: compound M1 is selected from a compound comprising one or two carboxylic acid functions, preferably a single carboxylic acid function, more preferably a compound M1 selected from acrylic acid, methacrylic acid, a salt of acrylic acid, a salt of methacrylic acid, itaconic acid, maleic acid, maleic anhydride and combinations thereof, 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 a polymerizable vinyl function, much more preferably a compound M2 selected from vinyl acetate, styrene, vinylcaprolactam, the 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, n-propyl acrylate, isopropyl acrylate, isobutyl acrylate, n-butyl acrylate, alkyl methacrylate, in particular Ci-Cio-alkyl methacrylate, preferably Ci-C4-alkyl methacrylate, more preferably methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, n-butyl methacrylate, aryl acrylate, preferably phenyl acrylate,benzylacrylate, phenoxyethylacrylate, aryl methacrylate, preferably phenyl methacrylate, benzyl methacrylate, phenoxyethyl methacrylate; - the compound M3 is chosen 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; - Compound M4 is a compound of formula II: [Chem II] in which:

9. - D1 and D4, whether identical or different, independently represent H or CH3. - D2 independently represents a grouping chosen from C(O), CH2, CH2-CH2 and O-CH2-CH2-CH2-CH2, - D3 independently 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 M5 compound 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 1]trimethylammonium sulfate, [3-(acrylamido)propyl]trimethylammonium sulfate, dimethyl-diallyl-ammonium sulfate, [3-(methacrylamido)propyl]trimethylammonium sulfate and their combinations. 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% at 90 mol% of compound M or from 85 mol% to 90 mol% of compound M, relative to the molar amounts 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 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 (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 combinations or their respective associations with an ion chosen from Fe11, Fe111, Cu1, Cu11 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, of 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 quantity 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 means of 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%, compared to the weight molar mass Mw of the copolymer P.