FR3113676A1 - POLYMERS CONTAINING REPEATING UNITS WITH SEVERAL METALLIC OR ORGANIC SULPHONATE PATTERNS, THEIR PREPARATION METHODS AND THEIR USES - Google Patents

Abstract

POLYMERS CONTAINING REPEATING UNITS WITH SEVERAL METALLIC OR ORGANIC SULPHONATE PATTERNS, THEIR PREPARATION METHODS AND THEIR USES The present invention relates to new polymers containing randomly several sulfonic units or metal sulfonates per repeating unit, their methods of preparation and their uses as antibacterials, fungicides, antivirals and catalysts.

Description

POLYMERS CONTAINING REPEATING UNITS WITH SEVERAL METALLIC OR ORGANIC SULPHONATE MOTIFS, METHOD FOR PREPARING THEM AND USES THEREOF

The present invention relates to new polymers containing randomly several sulfonic units or metal sulfonates per repeating unit, their methods of preparation and their uses as antibacterials, fungicides, antivirals and catalysts. The polymers can be used in acid form or in the form of metal salts chosen from the elements of columns (Ib), (IIb), (IIIa), (IIIb), (IVa), (IVb), (Va), (Vb ), (VIb), (VIIb), (VIII) or organic ammonium or phosphonium salts.

More specifically in the field of antibacterials and catalysis, the subject of the present invention is new polymers obtained from commercially available polymers as well as the formulations containing them.

At the level of antibacterials, there are many antibacterial, antimicrobial, antifungal and antiviral substances presented in the form of a solution or suspension. This is the case of quaternary ammonium salts used in many fields such as cleaning products, cosmetics. However, these compounds have several drawbacks. The antimicrobial dispersed in the environment ends up in the biotopes and hinders the development of the bacteria or fungi necessary for the biotransformations essential to the living world. Antibacterials are also found in wastewater treatment plants where they cause damage to the bacterial flora necessary for the proper functioning of wastewater treatment plants. In addition, quaternary ammonium salts are not very effective in the presence of organic compounds. Quaternary ammonium salts are deactivated by soaps and other anionic detergents, as well as cotton fibers. Also, they should not be used in hard water. Effective levels are estimated at 200 ppm. They degrade at temperatures above 100°C and thus lose all effectiveness.

Small molecules like triclosan are widely used in many formulations such as cosmetics, dental hygiene products, gels. Here again, toxic effects have been observed by B. Gaume, N. Bourgougnon, S. Auzoux-Bordenave, B. Roig, B. Le Bot, G. Bedoux* (Comparative Biochemistry and Physiology, Part C, (2012), 156 , 87–94). Small organic molecules have the disadvantage of penetrating very easily through the skin.

More recently, there has been the development of nanoparticles, in particular silver nanoparticles, as a bactericide. These antibacterials which are, among other things, used in cosmetics, have the disadvantage of easily passing through cell membranes and the skin wall, which induces a risk of toxicity for living organisms as mentioned in the work of Soohee Kim, Doug-Young Ryu (J. Appl. Toxicol., (2013), 33, 78-89), by Fateme Mirzajani, Hossein Askari, Sara Hamzelou, Mohsen Farzaneh, Alireza Ghassempour (J. Appl. Toxicol., (2012), 32, 867 –879) or G.E. Batley*, J.K. Kirby, M.J. McLaughlin (Acc. Chem. Res., (2013), 46(3), 854–862); Fashui Hong*, Yingjun Zhou, Jianhui Ji, Juan Zhuang, Lei Sheng, Ling Wang (J. Agric. Food Chem., (2018), 66, 11767−11774); Tianshu Wu, Meng Tang (J. Appl. Toxicol., (2018), 38, 25–40); Srinath Patibandla, Yinan Zhang, Ali Mohammad Tohari, Peng Gu, James Reilly, Yu Chen, Xinhua Shu (J. Appl. Toxicol., (2018), 38, 1153–1161). Furthermore, the industry needs both soluble antibacterial, fungicidal and antimicrobial agents that do not cross the membrane walls and solid antibacterial agents to ensure preventive antibacterial, fungicidal or antimicrobial activity, in particular to limit the risks of diseases. nosocomial. In its patent EP 3237490, the applicant had described the antibacterial, fungicidal and antimicrobial properties of metal salts of polymers of the polyaryl (ether ketones) or poly (aryl (ether sulfones) monosulfonated type. However, these polymers are insufficiently soluble to respond well to the constraints of liquid formulations and not mechanically strong enough to meet market expectations in the field of solid products.

For more than fifty years, sulphonic resins of the Amberlyst® type have been used as catalysts in the field of organic synthesis. But they show limits due in particular to limited mechanical strength (time, pressure, etc.), limited thermal stability and incompatibility with certain solvents. The activity of zeolites, another important family of solid catalysts, is based on shape selectivity which makes them substrate specific. Zeolites are poorly suited to fine chemical processes where very different reagents are used.

The first subject of the invention is polymers of the family of polyaryl ether ketones or polyether sulfone polymers corresponding to formulas I, II, III, IV, V, VI, and VII in which: - M ^{z +} represents one or more corresponding cations to an oxidized form of the elements of columns IA, IB, IIA, IIB, IIIA, IIIB, IVA, IVB, VA, VB, VIB, VIIB and VIII of the periodic table of the elements or an ammonium, phosphonium or iodonium cation; - z represents an integer from 1 to 6 corresponding to the degree of oxidation of the cation; - y represents an integer or fractional number equal to 1/z so as to ensure neutrality between the negative and positive charges; - a, b, c, d, e, f, g represent whole or decimal numbers whose sum a+b+c+d+e+f+g is greater than 1 and less than or equal to 4, preferably the sum a+b+c+d+e+f+g is greater than 1 and less than or equal to 3; - W represents a spacer in which the sulfur atom and the spacer are linked by carbon or nitrogen atoms; - m represents the percentage of unbridged repeat units having an oxoaryl or dioxoaryl unit possessing several sulfonyl functions per repeat unit; this percentage varies between 60% and 100%, preferably between 80% and 100%; - n represents the percentage of repeat units bridged by a unit W and having one or more sulfonyl functions per repeat unit; this percentage varies between 0% and 40%, preferably between 0% and 20%; - the sum m + n represents 100%; - q represents the number of repeating units of the polymer; q varies from 40 to 300, preferably between 60 and 200.

Advantageously: - ▪ M is chosen from the cations of hydrogen, titanium, zirconium, vanadium, chromium, molybdenum, tungsten, manganese, iron, ruthenium, osmium, cobalt, nickel, palladium, platinum, copper, silver, gold, zinc, aluminum, gallium, indium, tin, bismuth, magnesium, sodium, potassium, calcium, lithium, or when M is an ammonium or a phosphonium, M is preferably chosen from the cations N,N,N,N-tetramethylammonium, N,N,N,N-tetraethylammonium, N, N,N,N-tetrapropylammonium, N,N,N,N-tetrabutylammonium, N-methyl-N,N,N-tributylammonium, N-ethyl-N,N,N-tributylammonium, N,N,N,N- tetrapentylammonium, N,N,N,N-tetrahexylammonium, N,N,N,N-tetraoctylammonium, N,N,N,N-tetraphenylammonium, N,N,N-trimethyl-N-hydroxyethylammonium, N,N,N- trimethyl-N-phenylammonium, N,N,N-triethyl-N-phenylammonium, N-methyl-N,N,N-tridodecylammonium, pentamethylguanidinium, pentaethylguanidinium, tetrame thylphosphonium, tetraethylphosphonium, tetrapentylphosphonium, tetrahexylphosphonium, methyltriphenylphosphonium, tetraphenylphosphonium, 1,1,2,2,3,4,4-heptamethylphosphonium, tetradecylphosphonium, isopropyltriphenylphosphonium, 1-adamantyl[tris(hydroxymethyl)]phosphonium, bis(4-bromophenyl)iodonium , bis(4-tert-butylphenyl)iodonium, bis(4-fluorophenyl)iodonium, bis(4-methylphenyl)iodonium,(2-bromophenyl)(2,4,6-trimethylphenyl)iodonium, (3-bromophenyl)(2 ,4,6-trimethylphenyl)iodonium, (2-methylphenyl)(2,4,6-trimethylphenyl)iodonium, (3-methylphenyl)(2,4,6-trimethylphenyl)iodonium, (4-methylphenyl)(2,4 ,6-trimethylphenyl)iodonium, (4-nitrophenyl)phenyliodonium triflate, (4-nitrophenyl)(2,4,6-trimethylphenyl)iodonium, phenyl[3-(trifluoromethyl)phenyl]iodonium, 4-biphenylyl(2,4, 6-trimethoxyphenyl)iodonium, bis(pyridine)iodonium, bis(2,4,6-trimethylphenyl)iodonium, Bis(2,4,6-trimethylpyridine)iodonium, [4-(bromomethyl)phenyl](2,4,6 -trimethoxyphenyl)iodonium, (3-bromophenyl)(mesityl)iodonium , (3,5-dichlorophenyl)(2,4,6-trimethoxyphenyl)iodonium, (5-fluoro-2-nitrophenyl)(2,4,6-trimethoxyphenyl)iodonium, ethynyl(phenyl)iodonium, [4-fluoro- 3-(trifluoromethyl)phenyl](2,4,6-trimethoxyphenyl)iodonium, [4-[(2-hydroxytetradecyl)oxy]phenyl]phenyliodonium, 4-isopropyl-4'-methyldiphenyliodonium, (2-methylphenyl)(2, 4,6-trimethylphenyl)iodonium; ▪ a, b, c, d, e, f, g represent whole or decimal numbers whose sum a+b+c+d+e+f+g is greater than 1 and less than or equal to 3; ▪ m varies between 80% and 100%, preferably between 90% and 100%; ▪ n varies between 0% and 20%, preferably between 0 and 10%; ▪ the sum m + n represents 100%; - the spacer W is chosen from ethyl-1,2-diamino, propyl-1,3-diamino, butyl-1,4-diamino, pentyl-1,5-diamino, 4-methylpentyl-1,5- diamino, hexyl-1,6-diamino, dodecyl-1,12-diamino, N,N'-dimethylethyl-1,2-diamino, N,N'-dimethylpropyl-1,3-diamino, N,N'-dimethylbutyl -1,4-diamino, N,N'-dimethylpentyl-1,5-diamino, N,N'-piperazinediyl, N,N'-dimethylhexyl-1,6-diamino, N,N'-dimethyldodecyl-1,12 -diamino, 1,3-diaminobenzene, 1,4-diaminobenzene, 1,5-diamino-3-oxapentane, 1,8-diamino-3,6-dioxaoctane, 1,11-diamino-3,6,9-trioxaundecane , 1,14-diamino-3,6,9,12-tetraoxatetradecane, 4,13-diaza-18-crown-6-ether, 4,4'-diaminodiphenylether, 1,4-bis(4-aminophenoxy)benzene, 1,3-benzenedisulfonylamido, 1,4-diphenyletherdiyl, 1,4-bis(1-phenoxy-4-yl)benzene, a polyamide in which the terminal groups are amino groups such as 1,3-benzenedisulfonylamide or 1 ,4-benzenedisulfonamide.

A second subject of the invention is a process for the synthesis of polymers I, II, III, IV, V, VI and VII as defined above, characterized in that it comprises the following steps: - polychlorosulfonation of the polymers of formula VIII, XIX, X, XI, XII, XIII and XIV with a mixture of chlorosulfonic acid, thionyl chloride and an amide, in which ▪ q represents the number of polymeric units of the polymer; q varies from 40 to 300, preferably between 60 and 200; to obtain the polymers of formula XV, XVI, XVII, XVIII, XIX, XX and XXI in which ▪ a, b, c, d, e, f, g represent whole or decimal numbers whose sum a+b+c+ d+e+f+g is greater than 1 and less than or equal to 4, and preferably greater than 1 less than or equal to 3; and ▪ m and n represent the percentage of repeating units having an oxoaryl or dioxoaryl motif; - optional crosslinking of the polymers of formula XV, XVI, XVII, XVIII, XIX, XX and XXI to obtain the polymers of formula XXII, XXIII, XXIV, XXV, XXVI, XXVII and XXVIII in which ▪ W represents a spacer in which the sulfur atom and the spacer are linked by carbon or nitrogen atoms; ▪ m represents the percentage of unbridged repeat units having an oxoaryl or dioxoaryl motif possessing several sulfonyl functions per repeat unit; this percentage varies between 60% and 100%, preferably between 80% and 100%; ▪ n represents the percentage of repeat units bridged by a W motif and possessing one or more sulfonyl functions; this percentage varies between 0% and 40%, preferably between 0% and 20%; and ▪ the sum m + n represents 100%; - functionalization of the polymers of formula XXII, XXIII, XXIV, XXV, XXVI, XXVII and XXVIII to obtain the polymers of formula I, II, III, IV, V, VI and VII.

Advantageously: - the method comprises the step of crosslinking the polymers of formula XV, XVI, XVII, XVIII, XIX, XX and XXI to obtain the polymers of formula XXII, XXIII, XXIV, XXV, XXVI, XXVII and XXVIII in which ▪ m represents the percentage of unbridged repeat units having an oxoaryl or dioxoaryl motif possessing several sulfonyl functions per repeat unit; this percentage varies between 60% and 99.99%, preferably between 80% and 99.99%; ▪ n represents the percentage of repeat units bridged by a W motif and possessing one or more sulfonyl functions per repeat unit; this percentage varies between 0.01% and 40%, preferably between 0.01% and 20%; and ▪ the sum m + n represents 100%; - the crosslinking step is carried out, at a temperature between 10 and 40°C, in a solvent such as THF or water, in the presence of a tertiary amine such as triethylamine, diisopropylamine, diisopropylethylamine , tripropylamine, tributylamine, N,N-dimethylaniline or N,N-diethylaniline and the group W is a diamine chosen from ethyl-1,2-diamine, propyl-1,3-diamine, butyl -1,4-diamine, pentyl-1,5-diamine, 4-methylpentyl-1,5-diamine, hexyl-1,6-diamine, dodecyl-1,12-diamine, N,N '-ethyl-1,2-diamine, N,N'-dimethylpropyl-1,3-diamine, N,N'-dimethylbutyl-1,4-diamine, N,N'-dimethylpentyl-1,5- diamine, piperazine, N,N'-dimethylhexyl-1,6-diamine, N,N'-dimethyldodecyl-1,12-diamine, 1,3-diaminobenzene, 1,4-diaminobenzene, 1, 5-diamino-3-oxapentane, 1,8-diamino-3,6-dioxaoctane, 1,11-diamino-3,6,9-trioxaundecane, 1,14-diamino-3,6,9,12 -tetraoxatetradecane, 4,13-diaza-18-crown-6-ether, N,N'-4,4'-diamino diphenyl ether, and 1,4-bis(4-aminophenoxy)benzene; or implementation, at a temperature between 10 and 40°C, in a solvent such as THF or 2-methyltetrahydrofuran, in the presence of a strong base such as lithin, sodium hydroxide, lithium methoxide, methylate sodium, lithium ethoxide, sodium ethoxide, lithium isopropoxide, sodium isopropoxide, lithium tert-butoxide, sodium tert-butoxide, lithium hydride, sodium hydride, n-butyllithium, n-butylsodium, s-butyllithium, lithium diisopropylamide, tert-butyllithium, methyllithium phenyllithium, phenylsodium, benzyllithium, benzylsodium, lithium dimsylate, sodium dimesylate, carbonate lithium, sodium carbonate, lithium acetate or sodium acetate, preferably sodium hydride or butyllithium, and the group W is a disulfonamide such as 1,3-benzenedisulfonylamide or 1, 4-benzensulfonamide; or implementation, at a temperature between 10 and 40° C., in the presence of a Lewis acid such as bismuth triflate, and the W group is an aromatic derivative such as 1,4-diphenyl ether, 1 ,4-bis(phenoxy)benzene or 1,3-bis(phenoxy)benzene; the Lewis acid being introduced in an amount varying from 2 to 10%; - the functionalization comprises a reaction of the polymers of formulas XXII, XXIII, XXIV, XXV, XXVI, XXVII and XXVIII with ▪ a metal hydroxide such as soda, lithium, potash, magnesium hydroxide; or ▪ a metallic carbonate such as zinc carbonate, iron carbonate, silver carbonate, copper carbonate, sodium carbonate, potassium carbonate; or ▪ a metal carboxylate, such as metal acetates, metal propionates; or ▪ a metal in the oxidation state (0), under ultrasound; to obtain the polymers of formulas I, II, III, IV, V, VI and VII; - the functionalization comprises hydrolysis of the polymers of structure XXII, XXIII, XXIV, XXV, XXVI, XXVII, XXVIII, with water, at a temperature between 60 and 130° C., to obtain the polymers of formula XXIX,XXX , XXXI, XXXII, XXXIII, XXXIV and XXXV in which ▪ a, b, c, d, e, f, g represent integers or decimal numbers whose sum a+b+c+d+e+f+g is greater than to 1 and less than or equal to 4, preferably greater than 1 and less than or equal to 3; ▪ W represents a spacer in which the sulfur atom and the spacer are linked by carbon or nitrogen atoms; ▪ m represents the percentage of unbridged repeat units having an oxoaryl or dioxoaryl motif possessing several sulfonyl functions; this percentage varies between 60% and 100%, preferably between 80% and 100%; ▪ n represents the percentage of repeat units bridged by a W motif and possessing one or more sulfonyl functions; this percentage varies between 0% and 40%, preferably between 0% and 20%; ▪ the sum m + n represents 100%; ▪ q represents the number of repeating units of the polymer; q varies from 40 to 300, preferably between 60 and 200; - the functionalization further comprises a reaction of the polymers of formula XXIX, XXX, XXXI, XXXII, XXXIII, XXXIV and XXXV with salts chosen from carbonates, hydroxides, acetates, propionates, or benzoates of an element of columns IA, IB, IIA, IIB, IIIA, IIIB, IVA, IVB, VA, VB, VIB, VIIB or VIII to obtain the polymers of formulas I, II, III, IV, V, VI and VII; - the salts are salts of weak acids, whose pKa is greater than 0, such as carbonates, acetates, or benzoates; and - the functionalization further comprises a reaction of the polymers of formula XXIX, XXX, XXXI, XXXII, XXXIII, XXXIV and XXXV with a metal in oxidation state 0 such as indium, iron, or copper, under ultrasound .

The third subject of the invention is synthetic intermediates for the preparation of the polymers described above, characterized in that they correspond to the formulas XV, XVI, XVII, XVIII, XIX, XX, XXI, XXII, XXIII, XXIV, XXV, XXVI, XXVII, XXVIII, XXIX, XXX, XXXI, XXXII, XXXIII, XXXIV or XXXV.

A fourth subject of the invention is a use of the polymers described above, to form films with a thickness of between 10 and 200 μm.

A fifth subject of the invention is a use of the polymers of formula I, II, III, IV, V, VI, and VII described above, or films of these polymers, as antibacterial, fungicide, antimicrobial or catalyst.

A sixth subject of the invention is an antibacterial agent characterized in that it comprises a polymer of formula I, II, III, IV, V, VI or VII described above, or a film of one of these polymers, in solution or in the solid state.

Advantageously, the antibacterial has bactericidal activity against a bacterium chosen from Staphylococcus Aureus and Pseudomonas Aeruginosa .

A seventh subject of the invention is a fungicide characterized in that it comprises a polymer of formula I, II, III, IV, V, VI or VII described above, or a film of one of these polymers, in solution or in the solid state.

The eighth subject of the invention is an antiviral characterized in that it comprises a polymer of formula I, II, III, IV, V, VI or VII described above, or a film of one of these polymers, in solution or in the solid state.

A ninth subject of the invention is a catalyst characterized in that it comprises a polymer of formula I, II, III, IV, V, VI or VII described above, or a film of one of these polymers, in solution or in the solid state.

DETAILED DESCRIPTION

In order to overcome these major drawbacks, the applicant has developed new polymers of formulas I, II, III, IV, V, VI and VII which can be used as antibacterial, antifungal, antiviral agents or as catalysts.

in which :

- M ^{z +} represents one or more cations corresponding to an oxidized form of the elements of columns IA, IB, IIA, IIB, IIIA, IIIB, IVA, IVB, VA, VB, VIB, VIIB and VIII of the periodic table of the elements or an ammonium, phosphonium or iodonium cation;

- z represents an integer from 1 to 6 corresponding to the degree of oxidation of the cation;

- y represents an integer or fractional number equal to 1/z so as to ensure neutrality between the negative and positive charges;

- a, b, c, d, e, f, g represent whole or decimal numbers whose sum a+b+c+d+e+f+g is greater than 1 and less than or equal to 4, preferably the sum a+b+c+d+e+f+g is greater than 1 and less than or equal to 3;

- W represents a spacer in which the sulfur atom and the spacer are linked by carbon or nitrogen atoms;

- m represents the percentage of unbridged repeat units having an oxoaryl or dioxoaryl motif possessing several sulfonyl functions; this percentage varies between 60% and 100%, preferably between 80% and 100%;

- n represents the percentage of repeat units bridged by a W motif and possessing one or more sulfonyl functions; this percentage varies between 0% and 40%, preferably between 0% and 20%;

- the sum m + n represents 100%;

- q represents the number of repeating units of the polymer; q varies from 40 to 300, preferably between 60 and 200.

According to one embodiment, the polymers of the invention correspond to formulas I, II, III, IV, V, VI and VII in which:

- m represents the percentage of unbridged repeat units having an oxoaryl or dioxoaryl motif possessing several sulfonyl functions; this percentage varies between 60% and 100%, preferentially between 80% and 100%, and when the polymer is of formula V, VI or VII m varies between 60% and 99.99%, preferentially between 80% and 99.99% ;

- n represents the percentage of repeat units bridged by a W motif and possessing one or more sulfonyl functions; this percentage varies between 0% and 40%, preferentially between 0% and 20%, and when the polymer is of formula V, VI or VII n varies between 0.01% and 40%, preferentially between 0.01% and 20% ;

- the sum m + n represents 100%.

In this embodiment, crosslinking is optional for the polymers of formulas I, II, III and IV, while the polymers of formulas V, VI, VII and VIII are crosslinked.

Preferably, the polymers of formulas I, II, III, IV, V, VI and VII will be chosen in which:

- M is chosen from the cations of hydrogen, titanium, zirconium, vanadium, chromium, molybdenum, tungsten, manganese, iron, ruthenium, osmium, cobalt, nickel, palladium, platinum, copper, silver, gold, zinc, aluminum, gallium, indium, tin, bismuth, magnesium, sodium, potassium, calcium, lithium, or when M is an ammonium, a phosphonium or an iodonium, M is preferably chosen from the cations N,N,N,N-tetramethylammonium, N,N,N,N-tetraethylammonium, N, N,N,N-tetrapropylammonium, N,N,N,N-tetrabutylammonium, N-methyl-N,N,N-tributylammonium, N-ethyl-N,N,N-tributylammonium, N,N,N,N- tetrapentylammonium, N,N,N,N-tetrahexylammonium, N,N,N,N-tetraoctylammonium, N,N,N,N-tetraphenylammonium, N,N,N-trimethyl-N-hydroxyethylammonium, N,N,N- trimethyl-N-phenylammonium, N,N,N-triethyl-N-phenylammonium, N-methyl-N,N,N-tridodecylammonium, pentamethylguanidinium, pentaethylguanidinium, tetramethylpho sphonium, tetraethylphosphonium, tetrapentylphosphonium, tetrahexylphosphonium, methyltriphenylphosphonium, tetraphenylphosphonium, 1,1,2,2,3,4,4-heptamethylphosphonium, tetradecylphosphonium, isopropyltriphenylphosphonium, 1-adamantyl[tris(hydroxymethyl)]phosphonium , bis(4-bromophenyl)iodonium , bis(4-tert-butylphenyl)iodonium, bis(4-fluorophenyl)iodonium, bis(4-methylphenyl)iodonium,(2-bromophenyl)(2,4,6-trimethylphenyl)iodonium, (3-bromophenyl)(2 ,4,6-trimethylphenyl)iodonium, (2-methylphenyl)(2,4,6-trimethylphenyl)iodonium, (3-methylphenyl)(2,4,6-trimethylphenyl)iodonium, (4-methylphenyl)(2,4 ,6-trimethylphenyl)iodonium, (4-nitrophenyl)phenyliodonium triflate, (4-nitrophenyl)(2,4,6-trimethylphenyl)iodonium, phenyl[3-(trifluoromethyl)phenyl]iodonium, 4-biphenylyl(2,4, 6-trimethoxyphenyl)iodonium, bis(pyridine)iodonium, bis(2,4,6-trimethylphenyl)iodonium, Bis(2,4,6-trimethylpyridine)iodonium, [4-(bromomethyl)phenyl](2,4,6 -trimethoxyphenyl)iodonium, (3-bromophenyl)(mesityl)iodonium, (3.5 -dichlorophenyl)(2,4,6-trimethoxyphenyl)iodonium, (5-fluoro-2-nitrophenyl)(2,4,6-trimethoxyphenyl)iodonium, ethynyl(phenyl)iodonium, [4-fluoro-3-(trifluoromethyl) phenyl](2,4,6-trimethoxyphenyl)iodonium, [4-[(2-hydroxytetradecyl)oxy]phenyl]phenyliodonium, 4-isopropyl-4'-methyldiphenyliodonium, (2-methylphenyl)(2,4,6-trimethylphenyl )iodonium;

- a, b, c, d, e, f, g represent whole or decimal numbers whose sum a+b+c+d+e+f+g is greater than 1 and less than or equal to 3;

- m varies between 80% and 100%, preferably between 90% and 100%;

- n varies between 0% and 20%, preferably between 0% and 10%;

- the sum m + n represents 100%.

According to one embodiment of the invention, the spacer W is chosen from the groups ethyl-1,2-diamino, propyl-1,3-diamino, butyl-1,4-diamino, pentyl-1,5-diamino , 4-methylpentyl-1,5-diamino, hexyl-1,6-diamino, dodecyl-1,12-diamino, N,N'-dimethylethyl-1,2-diamino, N,N'-dimethylpropyl-1,3 -diamino, N,N'-dimethylbutyl-1,4-diamino, N,N'-dimethylpentyl-1,5-diamino, N,N'-piperazinediyl, N,N'-dimethylhexyl-1,6-diamino, N ,N'-dimethyldodecyl-1,12-diamino, 1,3-diaminobenzene, 1,4-diaminobenzene, 1,5-diamino-3-oxapentane, 1,8-diamino-3,6-dioxaoctane, 1,11- diamino-3,6,9-trioxaundecane, 1,14-diamino-3,6,9,12-tetraoxatetradecane, 4,13-diaza-18-crown-6-ether, 4,4'-diaminodiphenyl ether, 1,4 -bis(4-aminophenoxy)benzene, 1,3-benzenedisulfonylamido, 1,4-diphenyletherdiyl, 1,4-bis(1-phenoxy-4-yl)benzene, a polyamide in which the terminal groups are amino groups such as 1,3-benzenedisulfonylamide or 1,4-benzenedisulfonamide.

The polymers of the present invention, corresponding to formulas I, II, III, IV, V, VI and VII, are polysulfonated polymers. These polymers therefore comprise several sulphonyl functions per repeat unit, i.e. a statistical distribution of sulphonyl functions resulting, on average, in several sulphonyl functions per repeat unit. Thus, in the polymers of the invention, a non-bridged repeat unit, that is to say a non-bridged repeat unit having an oxoaryl or dioxoaryl unit, the percentage of which is defined by m, comprises statistically more than one sulfonyl function. A bridging repeat unit, that is to say a repeat unit bridged by a unit W having an oxoaryl or dioxoaryl unit and whose percentage is defined by n, comprises statistically zero, one or more sulfonyl functions in addition to the group bridging, that is to say, on average, one or more sulfonyl functions in addition to the bridging group per repeat unit.

The invention also relates to a process for the synthesis of the compounds of formulas I, II, III, IV, V, VI and VII. The process of the invention comprises a polychlorosulfonation step, a crosslinking step and a functionalization step.

Polychlorosulfonation

According to one embodiment, the polymers of formulas I, II, III, IV, V, VI and VII can be obtained by carrying out in a first step the polychlorosulfonation of a polymer of formulas VIII, IX, X, XI, XII, XIII and XIV

in which q represents the number of polymeric units of the polymer; q varies from 40 to 300, preferably between 60 and 200, by a mixture of chlorosulfonic acid, thionyl chloride and an amide.

Advantageously, the polychlorosulphonation is carried out at a temperature between 60° C. and 150° C., preferably between 80° C. and 130° C., in the presence of 1 to 30 equivalents of chlorosulphonic acid, preferably between 1 to 10 equivalents, with a chlorosulfonic acid whose titer is greater than 90%, preferably greater than or equal to 95%, of 1 to 30 equivalents of thionyl chloride, 1 to 10 equivalents of an amide such as N,N-dimethylformamide, dimethylacetamide, N,N-dimethylisobutyramide in order to obtain the polymers of formulas XV, XVI, XVII, XVIII, XIX, XX and XXI

in which a, b, c, d, e, f, g represent whole or decimal numbers whose sum a+b+c+d+e+f+g is greater than 1 and less than or equal to 4, and preferably greater than 1 less than or equal to 3 and m and n represent the percentage of repeating units having an oxoaryl or dioxoaryl unit.

The polymers of formulas XV, XVI, XVII, XVIII, XIX, XX and XXI thus obtained are new synthesis intermediates.

The starting polymers are commercial products. The polymer of formula VIII is known commercially under the name of poly(ether ether ketone) or PEEK, for poly(ether ether ketone) in English. The polymer of formula IX is known commercially under the name of poly(ether ketone ketone) or PEKK, for poly(ether ketone ketone) in English. The polymer of formula X is known commercially as poly(ether ether sulfone) or PEES. The polymer of formula XI is known commercially as poly(ether sulfone) or PES. The polymer of formula XII is part of the family of poly(arene ether ketone) and is known commercially under the name of PAEK, for poly(aryl ether ketone) in English. The polymer of formula XIII belongs to the family of poly(arene ether sulfone) and is known commercially under the name of PAES, for poly(aryl ether sulfone) in English. The polymer of formula XIV is known commercially under the name of poly(ether ketone ether ketone ketone) or PEKEKK, for poly(ether ketone ether ketone ketone) in English.

According to one embodiment, the polychlorosulfonation is carried out at a temperature of between 60°C and 150°C, preferably between 80°C and 130°C. A temperature of between 60 to 150° C., and in particular between 80° C. and 130° C., makes it possible to promote a polychlorosulfonation reaction rather than a monochlorosulfonation reaction. According to one embodiment, the polychlorosulfonation is carried out in the presence of 1 to 30 equivalents of chlorosulfonic acid, preferably between 1 to 10 equivalents, with a chlorosulfonic acid whose titer is greater than 90%, preferably greater than or equal to 95 %. Polychlorosulfonation is carried out in the presence of 1 to 30 equivalents of thionyl chloride and 1 to 10 equivalents of an amide. Chlorosulfonic acid can be generated in-situ, for example from sulfuric acid and thionyl chloride (C. Moureu, Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences (1894), 119, 337-340). Advantageously, the amide is an N,N-dimethylamide, preferably chosen from N,N-dimethylformamide, N,N-dimethylacetamide, or N,N-dimethylisobutyramide. The polychlorosulfonation can be implemented with or without a solvent. The preferred solvents according to the invention are THF, 2-methyltetrahydrofuran (methylTHF), dichloromethane, dichloroethane. The polychlorosulfonated polymers XV, XVI, XVII, XVIII, XIX, XX and XXI are given by way of example. Other isomers may be formed during polychlorosulfonation.

Crosslinking

From the polymers of formulas XV, XVI, XVII, XVIII, XIX, XX and XXI, it is possible to obtain the polymers of formulas XXII, XXIII, XXIV, XXV, XXVI, XXVII and XXVIII which are new synthesis intermediates .

in which

- a, b, c, d, e, f, g represent whole or decimal numbers whose sum a+b+c+d+e+f+g is greater than 1 and less than or equal to 4, preferably greater than 1 and less than or equal to 3;

- W represents a spacer in which the sulfur atom and the spacer are linked by carbon or nitrogen atoms;

- m represents the percentage of unbridged repeat units having an oxoaryl or dioxoaryl motif possessing several sulfonyl functions; this percentage varies between 60% and 100%, preferably between 80% and 100%;

- n represents the percentage of repeat units bridged by a W motif and possessing one or more sulfonyl functions; this percentage varies between 0% and 40%, preferably between 0% and 20%;

- the sum m + n represents 100%;

- q represents the number of repeating units of the polymer; q varies from 40 to 300, preferably between 60 and 200.

According to one embodiment of the invention, the step of crosslinking the polymers of formula XIX, XX and XXI makes it possible to obtain the polymers of formula XXVI, XXVII or XXVIII in which m varies between 60% and 99.99%, preferably between 80% and 99.99%; and n varies between 0.01% and 40%, preferably between 0.01% and 20%, and the sum m+n represents 100%. In other words, according to this embodiment of the process of the invention, the crosslinking step is only optional for the polymers of formula XV, XVI, XVII and XVIII. Thus, the intermediate polymers, of formula XXII, XXIII, XXIV and XXV are not necessarily crosslinked and n may be equal to 0%.

According to one embodiment, during the crosslinking, the polymers XV, XVI, XVII, XVIII, XIX, XX and XXI are reacted with:

- a diamine chosen from diamines such as ethyl-1,2-diamine, propyl-1,3-diamine, butyl-1,4-diamine, pentyl-1,5-diamine, 4-methylpentyl- 1,5-diamine, hexyl-1,6-diamine, dodecyl-1,12-diamine, N,N'-ethyl-1,2-diamine, N,N'-dimethylpropyl-1,3 -diamine, N,N'-dimethylbutyl-1,4-diamine, N,N'-dimethylpentyl-1,5-diamine, piperazine, N,N'-dimethylhexyl-1,6-diamine, N ,N'-dimethyldodecyl-1,12-diamine, 1,3-diaminobenzene, 1,4-diaminobenzene, 1,5-diamino-3-oxapentane, 1,8-diamino-3,6-dioxaoctane, 1,11-diamino-3,6,9-trioxaundecane, 1,14-diamino-3,6,9,12-tetraoxatetradecane, 4,13-diaza-18-crown-6-ether, N,N '-4,4'-diaminodiphenyl ether, 1,4-bis(4-aminophenoxy)benzene, in the presence of a base such as a tertiary amine, preferably such as triethylamine, diisopropylethylamine, tripropylamine, tributylamine , dimethylaniline, diethylaniline; Or

- a sulfonamide such as 1,3-benzenedisulfonylamide, or 1,4-benzenesulfonamide, in the presence of a strong base such as sodium hydride, butyllithium; Or

- an aromatic derivative such as 1,4-diphenyl ether, 1,4-bis(phenoxy)benzene, or 1,3-bis(phenoxy)benzene, in the presence of Lewis acids, more particularly such as bismuth triflate , the Lewis acid being used in an amount varying from 2% to 10%;

to obtain the polymers of formulas XXII, XXIII, XXIV, XXV, XXVI, XXVII and XXVIII.

The reaction is carried out at a temperature between 0°C and 80°C, preferably between 10°C and 40°C in a solvent such as THF, water, ethanol.

The degree of crosslinking n depends on the number of equivalents of crosslinking agent introduced into the reaction. For the crosslinking, 0.5 molar equivalent of diamines, sulfonamide or aromatic derivative is used relative to the number of SO ₂ Cl functions which it is desired to react.

Functionalization

Then, the polymers of formulas XXII, XXIII, XXIV, XXV, XXVI, XXVII and XXVIII are functionalized to lead to the polymers of formulas I, II, III, IV, V, VI and VII.

According to a first embodiment of the functionalization step of the process of the invention, the polymers of formulas XXII, XXIII, XXIV, XXV, XXVI, XXVII and XXVIII are hydrolyzed to obtain the polymers XXIX, XXX, XXXI, XXXII, XXXIII, XXXIV and XXXV,

in which

- a, b, c, d, e, f, g represent whole or decimal numbers whose sum a+b+c+d+e+f+g is greater than 1 and less than or equal to 4, preferably greater than 1 and less than or equal to 3;

- W represents a spacer in which the sulfur atom and the spacer are linked by carbon or nitrogen atoms;

- m represents the percentage of unbridged repeat units having an oxoaryl or dioxoaryl motif possessing several sulfonyl functions; this percentage varies between 60% and 100%, preferably between 80% and 100%;

- n represents the percentage of repeat units bridged by a W motif and possessing one or more sulfonyl functions; this percentage varies between 0% and 40%, preferably between 0% and 20%;

- the sum m + n represents 100%;

- q represents the number of repeating units of the polymer; q varies from 40 to 300, preferably between 60 and 200.

According to one embodiment of the invention, the step of functionalizing the polymers of formula XXVI, XXVII and XXVIII makes it possible to obtain the polymers of formula XXXIII, XXXIV or XXXV in which m varies between 60% and 99.99%, preferably between 80% and 99.99%; and n varies between 0.01% and 40%, preferably between 0.01% and 20%, and the sum m+n represents 100%.

The polymers XXIX, XXX, XXXI, XXXII, XXXIII, XXXIV and XXXV are then, optionally, transformed in a second step of this embodiment, into polymers of formulas I, II, III, IV, V, VI and VII according to techniques known to those skilled in the art, such as those described in patent EP 3237490 and FR 3030534. Advantageously, this second step is implemented by a reaction of the polymers of formula XXIX, XXX, XXXI, XXXII, XXXIII, XXXIV and XXXV with a metal in oxidation state 0 such as indium, iron, or copper, under ultrasound, or by a reaction of the polymers of formula XXIX, XXX, XXXI, XXXII, XXXIII, XXXIV and XXXV with selected salts from carbonates, hydroxides, acetates, propionates, or benzoates of an element of columns IA, IB, IIA, IIB, IIIA, IIIB, IVA, IVB, VA, VB, VIB, VIIB or VIII. In particular, the salts are salts of weak acids, that is to say whose pKa is greater than 0, such as carbonates, acetates, or benzoates. It is entirely possible to use mixtures of metals or salts or a sub-stoichiometry in salts.

It should be noted that the hydrolyzed polymers, of formulas XXIX, XXX, XXXI, XXXII, XXXIII, XXXIV and XXXV, correspond to the polymers of formulas I, II, III, IV, V, VI and VII in which M^Z+is the cation H⁺. According to this embodiment, the second step aimed at introducing a cation M^Z+ corresponding to an oxidized form of an element of columns IA, IB, IIA, IIB, IIIA, IIIB, IVA, IVB, VA, VB, VIB, VIIB and, VIII or an ammonium, phosphonium or iodonium cation, is optional and n is implemented only when M^Z+ is different from H⁺. The ammonium, phosphonium and iodonium cations are introduced in stoichiometric or sub-stoichiometric quantities with respect to the H cation⁺.

The polymers of formulas XXII, XXIII, XXIV, XXV, XXVI, XXVII and XXVIII are, in a second embodiment of the functionalization step of the process of the invention, transformed into polymers of formulas I, II, III, IV , V, VI and VII

- by reaction with a metal hydroxide such as soda, lithin, potash, magnesium hydroxide; Or

- by reaction of a metallic carbonate such as zinc carbonate, iron carbonate, silver carbonate, copper carbonate, sodium carbonate, potassium carbonate; Or

- by reaction with a metal carboxylate, such as metal acetates, metal propionates; Or

- by reaction of a metal in the oxidation state (0), under ultrasound.

All of these functionalization techniques are implemented according to methods known to those skilled in the art, such as those described in patent EP 3237490.

All the reactions are preferably carried out with anhydrous solvents, preferably freshly distilled, and under an inert and anhydrous atmosphere. By inert atmosphere is meant an atmosphere under a stream of nitrogen or argon.

The process developed by the applicant uses inexpensive products and leads to antibacterial, fungicidal, antiviral and catalyst polymers compatible with market expectations and whose performance is greater than or equal to the best products.

The invention also relates to the synthesis intermediates for the preparation of the polymers of formula I, II, III, IV, V, VI and VII, corresponding to the formulas XV, XVI, XVII, XVIII, XIX, XX, XXI, XXII, XXIII , XXIV, XXV, XXVI, XXVII, XXVIII, XXIX, XXX, XXXI, XXXII, XXXIII, XXXIV, XXXV. These synthesis intermediates are as defined above. In particular, these synthesis intermediates are polysulfonated polymers. These polymers therefore comprise several sulfonyl functions, that is to say statistically more than one sulfonyl function per repeating unit. Thus, for the synthesis intermediates of the invention corresponding to formulas XV, XVI, XVII, XVIII, XIX, XX and XXI, each repeat unit statistically comprises several SO ₂ Cl functions. And for the synthesis intermediates of the invention corresponding to the formulas XXII, XXIII, XXIV, XXV, XXVI, XXVII, XXVIII, XXIX, XXX, XXXI, XXXII, XXXIII, XXXIV and XXXV, a non-bridging repeat unit, i.e. a non-bridging repeat unit bridged having an oxoaryl or dioxoaryl unit, the percentage of which is defined by m, statistically comprises several sulphonyl functions. A bridging repeat unit, that is to say a repeat unit bridged by a unit W having an oxoaryl or dioxoaryl unit and whose percentage is defined by n, comprises statistically zero, one or more sulfonyl functions in addition to the group bridging, resulting, on average, in one or more sulfonyl functions, in addition to the bridging group, per repeating unit.

Surprisingly and unexpectedly, it was found that the polymers of formulas I, II, III, IV, V, VI and VII were particularly film-forming, which is a clear advantage for the intended applications. They can be used to form films with a thickness between 10 μm and 200 μm, which exhibit remarkable mechanical properties and hardness. These excellent mechanical properties are also an advantage in certain applications by avoiding crumbling and attrition of the material. In practice, these films can be handled by an operator without being torn.

Thus, the invention also relates to the use of the polymers of formula I, II, III, IV, V, VI and VII according to the invention to form films with a thickness of between 10 μm and 200 μm, preferably between 50 to 150 µm.

The invention also relates to films of polymers of formula I, II, III, IV, V, VI and VII according to the invention. The polymers of formulas I, II, III, IV, V, VI and VII are as defined above. The polymer films according to the invention have a thickness of between 10 μm and 200 μm, preferably between 50 to 150 μm. The polymer films according to the invention can be used in a temperature range between 20°C and 150°C.

The invention also relates to a process for the preparation of films serving as an antibacterial, fungicide, antimicrobial, antivirus or catalyst in which one of the polymers of formula I, II, III, IV, V, VI and VII according to the invention is dissolved in a solvent such as water, the polymer solution thus obtained is deposited on a solid support, then the film is formed by evaporation of the solvent, said evaporation being carried out by heating to a temperature between 20°C and 80°C, by flushing with an inert gas or by placing under reduced pressure.

Thus, films of the polymers of formulas I, II, III, IV, V, VI and VII can easily be obtained by evaporation of a polymer solution deposited on a surface of a material such as glass, Teflon, plastic or wood.

Uncrosslinked polychlorosulfonated and polysulfonated polymers have also been observed to be more soluble in solvents than their monosulfonated counterparts.

It should be noted that the polymers of formulas I, II, III, IV, V, VI and VII are antibacterials, fungicides, antimicrobials, antiviruses or catalysts both in solution and in the solid state.

The invention thus also relates to the use of polymers of formula I, II, III, IV, V, VI or VII, or powders, or films of these polymers, as antibacterial, fungicide, antimicrobial, antivirus or as catalysts. The polymers of formulas I, II, III, IV, V, VI and VII, or the films of these polymers, are as defined above.

The invention also relates to an antibacterial characterized in that it comprises a polymer of formula I, II, III, IV, V, VI or VII, or a powder or a film of one of these polymers, in solution or in in the solid state, the polymers of formulas I, II, III, IV, V, VI and VII, or the films of these polymers, being as defined above. In particular, the antibacterial of the invention exhibits bactericidal activity against a bacterium chosen from Staphylococcus Aureus and Pseudomonas Aeruginosa .

The invention also relates to a fungicide characterized in that it comprises a polymer of formula I, II, III, IV, V, VI or VII, or a film of one of these polymers, in solution or in the solid, the polymers of formulas I, II, III, IV, V, VI and VII, or the films of these polymers, being as defined above.

The invention also relates to an antimicrobial characterized in that it comprises a polymer of formula I, II, III, IV, V, VI or VII, or a film of one of these polymers, in solution or in the state solid, the polymers of formulas I, II, III, IV, V, VI and VII, or the films of these polymers, being as defined above.

The invention also relates to an antiviral material characterized in that it comprises a polymer of formula I, II, III, IV, V, VI or VII, or a film of one of these polymers, in solution or solid state, the polymers of formulas I, II, III, IV, V, VI and VII, or the films of these polymers, being as defined above.

The invention also relates to a catalyst characterized in that it comprises a polymer of formula I, II, III, IV, V, VI or VII, or a film of one of these polymers, in solution or in the state solid, the polymers of formulas I, II, III, IV, V, VI and VII, or the films of these polymers, being as defined above.

EXAMPLES

The examples given below are presented by way of non-limiting illustration of the subject of the present invention.

Example 1 - Polychlorosulfonation of PEEK . Preparation of the polymer of formula XV

In the examples below, S-Cl represents the following polymers

D-Cl represent all of the following compounds:

[Chem 39]
and T-Cl that of the following compounds:

1 g of poly(ether ether ketone) or PEEK (3.4 mmol) are introduced into a dry 100 mL flask, fitted with a magnetic bar and conditioned under an inert atmosphere, then 35 mL of dichloroethane (DCE) ( 0.099 mol/L). The solution is stirred and the chlorosulfonic acid (97%; 12 eq.; 41.4 mmol; 4.8 g; 2.8 mL) is introduced using a syringe under an inert atmosphere. The reaction mixture is heated under reflux of dichloroethane (T=83.5° C.) for 18 h. A red pasty solid is obtained. The supernatant is then eliminated and thionyl chloride (30 eq.; 103 mmol; 12.3 g; 7.5 mL) is introduced, then N,N-dimethylformamide (8 eq.; 27.6 mmol; 2.02 g; 2.1 mL) drop by drop using a syringe, taking care to handle under an inert atmosphere. The reaction mixture is stirred at ambient temperature until the red paste has completely dissolved. THF (30 mL) is added dropwise using a separatory funnel. The residual solution is transferred to the separatory funnel. The lower phase is eliminated and the upper phase is precipitated in 150 mL of isopropanol. A white precipitate is formed and filtered on a frit of porosity 3. The solid obtained is rinsed using isopropanol (2 x 50 mL) and acetonitrile (2 x 50 mL). The solid obtained is stirred in acetonitrile overnight in order to eliminate the residual acid. The suspension is filtered on frit (porosity 3) and the solid is dried under vacuum (1×10 ⁻² mbar) overnight. A white solid is obtained with a quantitative yield. By NMR analysis, this product is identified as being a mixture of dichlorosulfonated and trichlorosulfonated PEEK.

Essay Solvent Time T Eq. ClSO title ₃ H T-Cl D-Cl S-Cl 1 CH ₂ ClCH ₂ Cl 6 p.m. Reflux
88°C 12 97% 8% 92% /

Example 2 – polyc chlorosulfonation PEEK.Influence of reaction time

The procedure is carried out under the conditions of Example 1 by varying the reaction time

Essay Solvent Time T Eq. ClSO title ₃ H T-Cl D-Cl S-Cl 1 CH ₂ ClCH ₂ Cl 6 p.m. Reflux
88°C 12 97% 8% 92% / 2 CH ₂ ClCH ₂ Cl 48 hours Reflux
88x 12 97% 70% 30% /

Increasing the reaction time favors the formation of the trichlorosulfonated polymer.

Example s 3 to 5 – polyc chlorosulfonation PEEK.Influence of reaction temperature

The operation is carried out under the conditions of Example 1 by varying the reaction temperature.

Essay Solvent Time T Eq. ClSO title ₃ H T-Cl D-Cl S-Cl 3 CH ₂ ClCH ₂ Cl 6 p.m. 23°C 5 97% / / 99% 4 CH ₂ ClCH ₂ Cl 6 p.m. 42°C 5 97% / 6% 94% 5 CH ₂ ClCH ₂ Cl 6 p.m. 60°C 5 97% / 14% 86%

A rise in temperature promotes polychlorosulfonation.

Example s 6 to 10 – polyc chlorosulfonation PEEK.Influence of solvent and reaction time

The operation is carried out under the conditions of example 1 by varying the solvent, consequently the reaction temperature and the time.

Essay Solvent Time T Eq. ClSO title ₃ H T-Cl D-Cl S-Cl 6 _{CH2Cl2 _} 5 a.m. Reflux
40°C 5 >98% / 17% 83% 7 _{CH2Cl2 _} 3 p.m. Reflux
40°C 5 >98% / 52% 48% 8 CHCl ₃ 5 a.m. Reflux
62°C 5 >98% / 12% 88% 9 CHCl ₃ 3 p.m. Reflux
62°C 5 >98% / 65% 35% 10 CH ₂ ClCH ₂ Cl 5 a.m. Reflux
88°C 5 >98% 12% 88% /

Example s 11 to 16 – polyc chlorosulfonation PEEK in the absence of solvent . Solvent influence

One operates under the conditions of example 1, in the absence of solvent, and by increasing the temperature:

Essay Solvent Time T [PEEK] (g/mL) ClSO title ₃ H T-Cl D-Cl S-Cl
11 ClSO ₃ H 6 p.m. 80°C 0.067 97% / 64% 36% 12 ClSO ₃ H 6 p.m. 90°C 0.067 97% 45% 55% / 13 ClSO ₃ H 6 p.m. 100°C 0.067 97% 51% 49% / 14 ClSO ₃ H 6 p.m. 110°C 0.067 97% 60% 40% / 15 ClSO ₃ H 6 p.m. 120°C 0.067 97% 84% 16% / 16 ClSO ₃ H 6 p.m. 130°C 0.067 97% 100% / /

Example s 17 to 19 – polyc chlorosulfonation of S PEEK -Cl to obtain a polymer of formula XV

200 mg of 100% chlorosulphonated S-Cl type SPEEK-Cl (0.51 mmol) are introduced into a dry flask fitted with a magnetic bar and conditioned under an inert atmosphere.

then 2 mL of chlorosulphonic acid (ie a polymer concentration of 0.26 mol/L) are added. The solution is heated at 80° C. for 18 h. The polymer is precipitated in 50 mL of isopropanol. The solid thus obtained is filtered on frit (porosity 3) and rinsed with isopropanol (2×20 mL) and acetonitrile (2×20 mL). The white solid is stirred in 100 mL of acetonitrile overnight in order to eliminate the residual acid. The suspension is filtered on frit (porosity 3) and the polymer is left to dry under vacuum (1×10 ^-2 mbar). A white polymer of the D-Cl type is obtained with a quantitative yield.

Essay Solvent Time T ClSO title ₃ H T-Cl D-Cl S-Cl 17 ClSO ₃ H 2 hours 80°C >98% / 59% 41% 18 ClSO ₃ H 5 a.m. 80°C >98% 16% 84% / 19 ClSO ₃ H 6 p.m. 80°C 97% / 98% 2%

We find an influence of the parameters comparable to that of the chlorosulfonation of PEEK, namely that the polychlorosulfonation is favored by an increase in the duration and by an increase in the titer of the chlorosulfonic acid.

Example s 20 To 2 2 – Cross-linking of SPEEK dichlorosulfones with 1,3-diaminopropane to obtain a polymer of formula XXII

In a 50 mL flask equipped with a magnetic stirrer, 400 mg of a dichlorosulfonated PEEK (D-Cl) (0.4 mmol), 20 mL of THF with x equivalents of 1,3-diaminopropane and 2x equivalents of triethylamine. The mixture is stirred at room temperature for 1 hour. The precipitate formed is filtered off and washed with diethyl ether. The solid obtained is dried under vacuum (1×10 ^-2 mbar).

Essay Diamine equivalents with respect to SO ₂ Cl functions Equivalents of N(C ₂ H ₅ ) ₃ weight yield Solubility in the reaction medium 20 5% 10% 100% Slightly
insoluble 21 10% 20% 102% Slightly
insoluble 22 20% 40% 98% Insoluble

The infrared spectra show the appearance of bands at 1340 and 1160 cm ^-1 characteristic of sulphonamides. The hydrolysis of the crosslinked polymers prepared makes it possible to quantify the degree of crosslinking of the polymer by titrimetric assay of the remaining sulphonic acid functions.

Example 2 3 – Cross-linking of SPEEK dichlorosulfones with the piperazine to obtain a polymer of formula XXII

The operation is carried out under the conditions of Example 27 to 29, replacing the 1,3-diaminopropane with piperazine (15 mol% with respect to the SO ₂ Cl functions). During the reaction, an insoluble polymer is formed. By filtration, 195 mg of a solid is isolated which is characterized by infrared as a SPEEK-Cl crosslinked with piperazine.

Example 24 – Cross-linking of SPEEK dichlorosulfones with the diph e nylether to obtain a polymer of formula XXII

In a 50 mL flask equipped with a magnetic stirrer, 400 mg of a dichlorosulfonated PEEK (D-Cl) (0.4 mmol), 20 mL of THF with 10 molar% of diphenyl ether relative to the SO functions are charged. ₂ Cl, 5 mol% bismuth triflate (Bi(O ₃ SCF ₃ ) ₃ ). The mixture is stirred at room temperature for 18 hours. By filtration, 195 mg of a solid is isolated which is characterized by infrared as a SPEEK-Cl crosslinked with diphenyl ether.

Example 25 – Hydrolysis of a cross-linked SPEEK-Cl diph e nyl e ther , to obtain a polymer of formula XXIX

550 mg of disulphonated SPEEK-Cl (2 SO ₂ Cl functions per repeat unit) are introduced into a 100 mL flask, 40% of the SO ₂ Cl functions of which have been crosslinked with diphenyl ether and 50 mL of water. The reaction mixture is heated under reflux for 18 h. After evaporation of the water, 496 mg of a solid are obtained. The acidimetric assay with 0.1N sodium hydroxide shows that the polymer contains 1.6 SO ₃ H functions per repeat unit.

Example 26 – Hydrolysis of a SPEEK-Cl disulphonated at 200% and reticle at 10% by 1,3-diaminopropane , to obtain a polymer of formula XXIX

Into a 100 mL flask, 550 mg of disulphonated SPEEK-Cl (2 SO ₂ Cl functions per repeating unit) are introduced, of which 20% of the SO ₂ Cl functions have been cross-linked with 1,3-diaminopropane and 50 mL of water. The reaction mixture is heated under reflux for 18 h. After evaporation of the water, 473 mg of a solid are obtained. The acidimetric assay with 0.1N sodium hydroxide shows that the polymer contains 1.5 SO ₃ H functions per repeat unit.

Example 27 – Hydrolysis of a cross-linked SPEEK-Cl by 1,3-diaminopropane with lithium , to get a po lymer of formula I

Into a 100 mL flask, 83 mg of disulphonated SPEEK-Cl (2 SO ₂ Cl functions per repeat unit) are introduced, of which 40% of the SO ₂ Cl functions have been crosslinked with 1,3-diaminopropane and 50 mL of water containing 0.01 mM LiOH. The reaction mixture is heated under reflux for 18 h. At the end of the reaction, the chloride ions released by the treatment with lithine are assayed and confirm in the starting SPEEK-Cl the presence of 2 SO ₂ Cl functions per repeat unit. The polymer obtained is a lithium salt of a SPEEK-OH crosslinked with 20% diaminopropane. This is characterized by infrared.

Example 28 – Hydrolysis of a SPEEK-Cl disulphonated to obtain a polymer of formula XXIX where n=0%

162 mg of disulphonated SPEEK-Cl (2 SO2Cl functions per repeating unit) and 20 mL of water are introduced into a 100 mL flask. The reaction mixture is heated under reflux for 18 h. After evaporation of the water, 167 mg of a solid are obtained. The acidimetric assay with 0.1N sodium hydroxide shows that the polymer consists on average of 90% SPEEK-OH having 2 SO ₃ H functions per repeat unit and 10% SPEEK-OH having 3 SO ₃ H functions per unit of repetition.

Example 29 – Preparation of a Fe(II) salt of a SPEEK disulphonated of formula I where n =0%

250 mg of disulphonated SPEEK-OH (2 SO ₃ H functions per repeat unit), 20 mL of water 0.5 equivalent of ferrous acetate are introduced into a 50 mL flask. The reaction mixture is heated, then the water and acetic acid are distilled off. The quantity of distilled acetic acid is measured by sodium hydroxide assay. The residue obtained is the iron(II) salt of the disulphonated SPEEK-OH.

Example 30 – polyc chlorosulfonation of the EP K K.Preparation of the PEKK disulphonated formula XVI where n= 0%

The operation is carried out under the conditions of Example 1 using PEKK as raw material. At the end of the polychlorosulfonation reaction, the reaction crude is hydrolyzed as in example 29. After evaporation of the water, 220 mg of a solid are obtained. The acidimetric assay with 0.1N sodium hydroxide shows that the polymer consists on average of 90% SPEKK-OH having 2 SO ₃ H functions per repeat unit and 10% PEKK-OH having 1 SO ₃ H function per unit of repetition.

Example 31 – Preparation of an Fe(II) salt of a SPEKK disulphonated , of formula II where n= 0%

200 mg of disulphonated PEKK-OH (2 SO ₃ H functions per unit of repetition), 20 mL of water 0.5 equivalent of ferrous acetate are introduced into a 50 mL flask. The reaction mixture is heated, then the water and acetic acid are distilled off. The quantity of distilled acetic acid is measured by sodium hydroxide assay. The residue obtained is the iron(II) salt of the disulphonated SPEKK-OH.

Example 32 - Results antibacterials of SPEEK-polymers Fe( II) polysulfonated and reticulated s at 10% by the propanediamine , of formula I

The polymer of Example 26 in film form is tested against Pseudomonas aeruginosa strains, the reduction in the number of bacteria is observed compared to the number inoculated at T0 (a few minutes after innoculation) and T7 (7 days after inoculation).

Essay Strain Reduction in the number of microorganisms at T0 Reduction in the number of microorganisms at T7 days Trial 32 Pseudomonas aeruginosa -0.03 logs > 5.11 logs

The reduction in the number of microorganisms is greater than 5 log after 7 days.

Example 33 - Results antibacterial polymers SPEEK- Fe( II) polysulfonated And reticle s 20% by the diphenyl ether , of formula I .

From the polymer of Example 25, the iron(II) salt is prepared according to the procedure of Example 31. The salt is dissolved in hot water then the solvent is evaporated so as to obtain a film. The antibacterial activity of the film is tested against the Pseudomonas aeruginosa strain.

Essay Strain Reduction in the number of microorganisms at T0 Reduction in the number of microorganisms at T7 days Trial 33 Pseudomonas aeruginosa 0.01log >5.11 logs

The reduction in the number of microorganisms is greater than 5 log after 7 days.

Example 34 - R antibacterial results of SPEEK-polymers Fe( II) polysulfonated at 200% , of formula I where n = 0%

The polymer of Example 29 in powder form is tested against the Pseudomonas aeruginosa strain.

Essay Strain Reduction in the number of microorganisms at T0 Reduction in the number of microorganisms at T7 days Trial 34 Pseudomonas aeruginosa 1.21 logs >5.11 logs

The reduction in the number of microorganisms greater than 1 log is observed from T0 and the reduction in the number of microorganisms greater than 5 log after 7 days.

Example 35 - Cyclization of 3- seven ene-2, 6 -diol by SPEEK( FeIII ) , made up of formula I where n = 0% , generated in situ at pa r shot of SPEEK-OH and FeCl ₃

A 20 mL flask is charged with 130 mg of 3-heptene-2,6-diol and 3 mL of dichloroethane. 40 mg of a 120% sulphonated SPEEK-OH and 40 mg of FeCl ₃ are then added. The mixture is heated at 80° C. for 6 h. After treatment and evaporation of the dichlorothane, the 5,6-dihydro-2,6-dimethyl-2H-pyran is identified by NMR. The yield of 5,6-dihydro-2,6-dimethyl-2H-pyran is 68%.

Example 36 - Cyclization with some SPEEK-Au ( I) , made up of formula I where n = 0% , as a catalyst

Preparation of the catalyst

In a 100 mL flask topped with a condenser, one equivalent of commercial AuCl (63 mg) is added to a mixture of SPEEK-OH at 110% SO ₃ H function (100 mg) in deionized water (30 mL). The reaction medium is refluxed for 12 h. After returning to room temperature, the precipitate is filtered and the aqueous solution is evaporated. A yellow colored solid is obtained 125 mg (85% yield).

Cyclohydration

This cyclohydration has been described in a homogeneous medium by C. Zhang, D.-M. Cui, L.-Y. Yao, B.-S. Wang, Y.-Z. Hu and T. Hayashi, J. Org. Chem. (2008), 73, 7811.

In a screwed tube, under argon, 100 mg of dimethyl 2,2-di(prop-2-yn-1-yl)malonate (0.5 mmol), 2 mol% of SPEEK-Au(I) (6 mg), 50 μL of trifluoromethanesulfonic acid, 10 μL of water in MeOH (2 mL) are added and the reaction mixture is brought to 70° C. for 24 h. The reaction mixture is treated with an aqueous solution of NaHCO3. The aqueous phase is extracted with ethyl acetate (3 × 50 mL) and the organic phase is then dried over Na2SO4, filtered and then evaporated under reduced pressure. Purification is carried out by flash chromatography on silica (petroleum ether/ethyl acetate) to yield the desired product 3-methyl-5-oxocyclohex-3-ene-1,1-dicarboxylate dimethyl with 45% yield (52 mg).

Example s 3 7 - 3 8 - cycle isomerization s . Comparison of SPEEK-Au(I) and SPEEK-Au (III) as a catalyst

This cycloisomerization has been described in a homogeneous medium by: E. Genin, P. Y. Toullec, S. Antoniotti, C. Brancour, J.-P. Genet and V. Michelet, J. Am. Chem. Soc. (2006), 128, 3112.

Preparation of the catalyst

SPEEk-Au(III) is prepared in the same way as SPEEk-Au(I) by replacing AuCl with a quantity of AuCl ₃ corresponding to the stoichimetry of the SO ₃ H functions.

Cycloisomerizations

In a screwed tube, under argon, 100 mg of 2-(methoxycarbonyl)-2-(prop-2-yn-1-yl)pent-4-ynoic acid (0.51 mmol) in 1 mL of anhydrous acetonitrile are added 5 mol% of SPEEK-Au(I) or SPEEK-Au(III) (14 mg). The reaction medium is stirred for 12 h at room temperature, then filtered. The solution is then filtered through a bed of silica using a 7/3 cyclohexane/ethyl acetate mixture as eluent. After evaporation, the methyl 5-methylene-2-oxo-3-(prop-2-yn-1-yl)tetrahydrofuran-3-carboxylate lactone is obtained with the yields mentioned in the table below.

ESSAY CATALYST YIELD 37 SPEEK-Au(I) 94% 38 SPEEK-Au(III) 98%

Example 3 9 - Cycloisomerization . Influence of SPEEK-Au(I) recycling as a catalyst

This cycloisomerization has been described in a homogeneous medium by: E. Genin, P. Y. Toullec, S. Antoniotti, C. Brancour, J.-P. Genet and V. Michelet, J. Am. Chem. Soc. (2006), 128, 3112.

Cycloisomerizations

In a screwed tube, under argon, 100 mg of 2-(methoxycarbonyl)-2-(prop-2-yn-1-yl)pent-4-ynoic acid (0.51 mmol) in 1 mL of anhydrous acetonitrile are added 5 mol% recycled SPEEK-Au(I). The reaction medium is stirred for 12 h at room temperature, then filtered. The solution is then filtered through a bed of silica using a 7/3 cyclohexane/ethyl acetate mixture as eluent. After evaporation, the methyl 5-methylene-2-oxo-3-(prop-2-yn-1-yl)tetrahydrofuran-3-carboxylate lactone is obtained with the yields mentioned in the table below.

ESSAY CATALYST RECYCLING YIELD Comparative SPEEK-Au(I) 0 94% 39 SPEEK-Au(I) 1 94%

No catalyst deactivation is observed during recycling.

Example 40 - Cycloisomerization with SPEEK-Au(I) as catalyst

This cycloisomerization has been described in a homogeneous medium by: E. Genin, P. Y. Toullec, S. Antoniotti, C. Brancour, J.-P. Genet and V. Michelet, J. Am. Chem. Soc. (2006), 128, 3112.

Cycloisomerizations

In a screwed tube, under argon, to 100 mg of 2-(ethoxycarbonyl)-2-(prop-2-yn-1-yl)hexanoic acid (0.44 mmol) in 1 mL of anhydrous acetonitrile are added 5 mol% of SPEEK-Au(I) (12 mg). The reaction medium is stirred for 12 h at room temperature, then filtered. The solution is then filtered on a bed of silica using a 7/3 cyclohexane/ethyl acetate mixture as eluent. After evaporation, methyl lactone ( Z )-3-butyl-2-oxo-5-propylidenetetrahydrofuran-3-carboxylate is obtained with 98% yield (96 mg).

Claims (19)

Polymers of the family of polyaryl ether ketones or polyether sulfonated polymers corresponding to formulas I, II, III, IV, V, VI, and VII







in which :
- M ^{z +} represents one or more cations corresponding to an oxidized form of the elements of columns IA, IB, IIA, IIB, IIIA, IIIB, IVA, IVB, VA, VB, VIB, VIIB and VIII of the periodic table of the elements or an ammonium, phosphonium or iodonium cation;
- z represents an integer from 1 to 6 corresponding to the degree of oxidation of the cation;
- y represents an integer or fractional number equal to 1/z so as to ensure neutrality between the negative and positive charges;
- a, b, c, d, e, f, g represent whole or decimal numbers whose sum a+b+c+d+e+f+g is greater than 1 and less than or equal to 4, preferably the sum a+b+c+d+e+f+g is greater than 1 and less than or equal to 3;
- W represents a spacer in which the sulfur atom and the spacer are linked by carbon or nitrogen atoms;
- m represents the percentage of unbridged repeat units having an oxoaryl or dioxoaryl motif possessing several sulfonyl functions; this percentage varies between 60% and 100%, preferably between 80% and 100%;
- n represents the percentage of repeating units bridged by a motif W and possessing one or more sulfonyl functions; this percentage varies between 0% and 40%, preferably between 0% and 20%;
- the sum m + n represents 100%;
- q represents the number of repeating units of the polymer; q varies from 40 to 300, preferably between 60 and 200. Polymers according to Claim 1, characterized in that:
- M is chosen from the cations of hydrogen, titanium, zirconium, vanadium, chromium, molybdenum, tungsten, manganese, iron, ruthenium, osmium, cobalt, nickel, palladium, platinum, copper, silver, gold, zinc, aluminum, gallium, indium, tin, bismuth, magnesium, sodium, potassium, calcium, lithium, or when M is an ammonium or a phosphonium, M is preferably chosen from the cations N,N,N,N-tetramethylammonium, N,N,N,N-tetraethylammonium, N,N,N ,N-tetrapropylammonium, N,N,N,N-tetrabutylammonium, N-methyl-N,N,N-tributylammonium, N-ethyl-N,N,N-tributylammonium, N,N,N,N-tetrapentylammonium, N ,N,N,N-tetrahexylammonium, N,N,N,N-tetraoctylammonium, N,N,N,N-tetraphenylammonium, N,N,N-trimethyl-N-hydroxyethylammonium, N,N,N-trimethyl-N -phenylammonium, N,N,N-triethyl-N-phenylammonium, N-methyl-N,N,N-tridodecylammonium, pentamethylguanidinium, pentaethylguanidinium, tetramethylphosphonium, tet raethylphosphonium, tetrapentylphosphonium, tetrahexylphosphonium, methyltriphenylphosphonium, tetraphenylphosphonium, 1,1,2,2,3,4,4-heptamethylphosphonium, tetradecylphosphonium, isopropyltriphenylphosphonium, 1-adamantyl[tris(hydroxymethyl)]phosphonium, bis(4-bromophenyl)iodonium, bis (4-tert-butylphenyl)iodonium, bis(4-fluorophenyl)iodonium, bis(4-methylphenyl)iodonium,(2-bromophenyl)(2,4,6-trimethylphenyl)iodonium, (3-bromophenyl)(2,4 ,6-trimethylphenyl)iodonium, (2-methylphenyl)(2,4,6-trimethylphenyl)iodonium, (3-methylphenyl)(2,4,6-trimethylphenyl)iodonium, (4-methylphenyl)(2,4,6 -trimethylphenyl)iodonium, (4-nitrophenyl)phenyliodonium triflate, (4-nitrophenyl)(2,4,6-trimethylphenyl)iodonium, phenyl[3-(trifluoromethyl)phenyl]iodonium, 4-biphenylyl(2,4,6- trimethoxyphenyl)iodonium, bis(pyridine)iodonium, bis(2,4,6-trimethylphenyl)iodonium, Bis(2,4,6-trimethylpyridine)iodonium, [4-(bromomethyl)phenyl](2,4,6-trimethoxyphenyl )iodonium, (3-bromophenyl)(mesityl)iodonium, (3,5-dichlorophenyl l)(2,4,6-trimethoxyphenyl)iodonium, (5-fluoro-2-nitrophenyl)(2,4,6-trimethoxyphenyl)iodonium, ethynyl(phenyl)iodonium, [4-fluoro-3-(trifluoromethyl)phenyl ](2,4,6-trimethoxyphenyl)iodonium, [4-[(2-hydroxytetradecyl)oxy]phenyl]phenyliodonium, 4-isopropyl-4'-methyldiphenyliodonium, (2-methylphenyl)(2,4,6-trimethylphenyl) iodonium;
- a, b, c, d, e, f, g represent whole or decimal numbers whose sum a+b+c+d+e+f+g is greater than 1 and less than or equal to 3;
- m varies between 80% and 100%, preferably between 90% and 100%;
- n varies between 0% and 20%, preferably between 0 and 10%;
- the sum m + n represents 100%. Polymers according to one of Claims 1 or 2, characterized in that:
the spacer W is chosen from the groups ethyl-1,2-diamino, propyl-1,3-diamino, butyl-1,4-diamino, pentyl-1,5-diamino, 4-methylpentyl-1,5-diamino , hexyl-1,6-diamino, dodecyl-1,12-diamino, N,N'-dimethylethyl-1,2-diamino, N,N'-dimethylpropyl-1,3-diamino, N,N'-dimethylbutyl- 1,4-diamino, N,N'-dimethylpentyl-1,5-diamino, N,N'-piperazinediyl, N,N'-dimethylhexyl-1,6-diamino, N,N'-dimethyldodecyl-1,12- diamino, 1,3-diaminobenzene, 1,4-diaminobenzene, 1,5-diamino-3-oxapentane, 1,8-diamino-3,6-dioxaoctane, 1,11-diamino-3,6,9-trioxaundecane, 1,14-diamino-3,6,9,12-tetraoxatetradecane, 4,13-diaza-18-crown-6-ether, 4,4'-diaminodiphenylether, 1,4-bis(4-aminophenoxy)benzene, 1 ,3-benzenedisulphonylamido, 1,4-diphenyletherdiyl, 1,4-bis(1-phenoxy-4-yl)benzene, a polyamide in which the end groups are amino groups such as 1,3-benzenedisulphonylamide or 1, 4-benzenedisulfonamide. Process for the synthesis of polymers I, II, III, IV, V, VI and VII as defined in any one of Claims 1 to 3, characterized in that it comprises the following stages:
- polychlorosulphonation of polymers of formula VIII, XIX, X, XI, XII, XIII and XIV with a mixture of chlorosulphonic acid, thionyl chloride and an amide







wherein
▪ q represents the number of polymeric units of the polymer; q varies from 40 to 300, preferably between 60 and 200;
to obtain the polymers of formula XV, XVI, XVII, XVIII, XIX, XX and XXI







in which
▪ a, b, c, d, e, f, g represent whole or decimal numbers whose sum a+b+c+d+e+f+g is greater than 1 and less than or equal to 4, and preferably greater than at 1 less than or equal to 3; And
▪ m and n represent the percentage of repeating units having an oxoaryl or dioxoaryl motif;
- optional crosslinking of the polymers of formula XV, XVI, XVII, XVIII, XIX, XX and XXI to obtain the polymers of formula XXII, XXIII, XXIV, XXV, XXVI, XXVII and XXVIII







in which
▪ W represents a spacer in which the sulfur atom and the spacer are linked by carbon or nitrogen atoms;
▪ m represents the percentage of unbridged repeat units having an oxoaryl or dioxoaryl motif possessing several sulfonyl functions; this percentage varies between 60% and 100%, preferably between 80% and 100%;
▪ n represents the percentage of repeat units bridged by a motif W and possessing one or more sulfonyl functions; this percentage varies between 0% and 40%, preferably between 0% and 20%; And
▪ the sum m + n represents 100%;
- functionalization of the polymers of formula XXII, XXIII, XXIV, XXV, XXVI, XXVII and XXVIII to obtain the polymers of formula I, II, III, IV, V, VI and VII. Process according to Claim 4, characterized in that it comprises the step of crosslinking the polymers of formula XV, XVI, XVII, XVIII, XIX, XX and XXI to obtain the polymers of formula XXII, XXIII, XXIV, XXV, XXVI , XXVII and XXVIII in which
▪ m represents the percentage of unbridged repeat units having an oxoaryl or dioxoaryl motif possessing several sulfonyl functions; this percentage varies between 60% and 99.99%, preferably between 80% and 99.99%;
▪ n represents the percentage of repeat units bridged by a motif W and possessing one or more sulfonyl functions; this percentage varies between 0.01% and 40%, preferably between 0.01% and 20%; And
▪ the sum m + n represents 100%. 6. Method according to any one of claims 4 or 5, in which the crosslinking step is:
- implementation, at a temperature between 10 and 40°C, in a solvent such as THF or water, in the presence of a tertiary amine such as triethylamine, diisopropylamine, diisopropylethylamine, tripropylamine, tributylamine , N,N-dimethylaniline or N,N-diethylaniline and the group W is a diamine chosen from ethyl-1,2-diamine, propyl-1,3-diamine, butyl-1,4-diamine , pentyl-1,5-diamine, 4-methylpentyl-1,5-diamine, hexyl-1,6-diamine, dodecyl-1,12-diamine, N,N'-ethyl-1, 2-diamine, N,N'-dimethylpropyl-1,3-diamine, N,N'-dimethylbutyl-1,4-diamine, N,N'-dimethylpentyl-1,5-diamine, piperazine, N,N'-dimethylhexyl-1,6-diamine, N,N'-dimethyldodecyl-1,12-diamine, 1,3-diaminobenzene, 1,4-diaminobenzene, 1,5-diamino-3- oxapentane, 1,8-diamino-3,6-dioxaoctane, 1,11-diamino-3,6,9-trioxaundecane, 1,14-diamino-3,6,9,12-tetraoxatetradecane, 4, 13-diaza-18-crown-6-ether, N,N'-4,4'-diaminodiphenyl ether, and 1,4-bis (4-aminophenoxy)benzene; Or
- implementation, at a temperature between 10 and 40°C, in a solvent such as THF or 2-methyltetrahydrofuran, in the presence of a strong base such as lithin, sodium hydroxide, lithium methoxide, methylate sodium, lithium ethoxide, sodium ethoxide, lithium isopropoxide, sodium isopropoxide, lithium tert-butoxide, sodium tert-butoxide, lithium hydride, sodium hydride, n-butyllithium, n-butylsodium, s-butyllithium, lithium diisopropylamide, tert-butyllithium, methyllithium phenyllithium, phenylsodium, benzyllithium, benzylsodium, lithium dimsylate, sodium dimesylate, carbonate lithium, sodium carbonate, lithium acetate or sodium acetate, preferably sodium hydride or butyllithium, and the group W is a disulfonamide such as 1,3-benzenedisulfonylamide or 1, 4-benzensulfonamide; Or
- implementation, at a temperature between 10 and 40°C, in the presence of a Lewis acid such as bismuth triflate, and the W group is an aromatic derivative such as 1,4-diphenyl ether, 1 ,4-bis(phenoxy)benzene or 1,3-bis(phenoxy)benzene; the Lewis acid being introduced in an amount varying from 2 to 10%. Process according to one of Claims 4 to 6, in which the functionalization comprises a reaction of the polymers of formulas XXII, XXIII, XXIV, XXV, XXVI, XXVII and XXVIII with:
- a metal hydroxide such as soda, lithium, potash, magnesium hydroxide; Or
- a metallic carbonate such as zinc carbonate, iron carbonate, silver carbonate, copper carbonate, sodium carbonate, potassium carbonate; Or
- a metal carboxylate, such as metal acetates, metal propionates; Or
- a metal in the oxidation state (0), under ultrasound;
to obtain the polymers of formulas I, II, III, IV, V, VI and VII. Process according to any one of Claims 4 to 6, in which the functionalization comprises hydrolysis of the polymers of structure XXII, XXIII, XXIV, XXV, XXVI, XXVII, XXVIII, with water, at a temperature of between 60 and 130°C, to obtain the polymers of formula XXIX, XXX, XXXI, XXXII, XXXIII, XXXIV and XXXV







in which
▪ a, b, c, d, e, f, g represent whole or decimal numbers whose sum a+b+c+d+e+f+g is greater than 1 and less than or equal to 4, preferably greater than 1 and less than or equal to 3;
▪ W represents a spacer in which the sulfur atom and the spacer are linked by carbon or nitrogen atoms;
▪ m represents the percentage of unbridged repeat units having an oxoaryl or dioxoaryl motif possessing several sulfonyl functions; this percentage varies between 60% and 100%, preferably between 80% and 100%;
▪ n represents the percentage of repeat units bridged by a motif W and possessing one or more sulfonyl functions; this percentage varies between 0% and 40%, preferably between 0% and 20%;
▪ the sum m + n represents 100%;
▪ q represents the number of repeating units of the polymer; q varies from 40 to 300, preferably between 60 and 200. Process according to Claim 8, characterized in that the functionalization further comprises a reaction of the polymers of formula XXIX, XXX, XXXI, XXXII, XXXIII, XXXIV and XXXV with salts chosen from carbonates, hydroxides, acetates, propionates , or benzoates of an element of columns IA, IB, IIA, IIB, IIIA, IIIB, IVA, IVB, VA, VB, VIB, VIIB or VIII to obtain the polymers of formulas I, II, III, IV, V , VI and VII. 10. Method according to claim 9, characterized in that the salts are salts of weak acids, the pKa of which is greater than 0, such as carbonates, acetates, or benzoates. 11. Method according to claim 8, characterized in that the functionalization further comprises a reaction of the polymers of formula XXIX, XXX, XXXI, XXXII, XXXIII, XXXIV and XXXV with a metal in oxidation state 0 such as indium , iron, or copper, under ultrasound. 12. Synthetic intermediates for the preparation of the polymers described in any one of claims 1 to 3, characterized in that they correspond to formulas XV, XVI, XVII, XVIII, XIX, XX, XXI, XXII, XXIII, XXIV , XXV, XXVI, XXVII, XXVIII, XXIX, XXX, XXXI, XXXII, XXXIII, XXXIV or XXXV. 3Use of the polymers described in any one of claims 1 to 3, to form films with a thickness of between 10 and 200 µm. 4Use of the polymers of formula I, II, III, IV, V, VI, and VII described in any one of claims 1 to 3, or films of these polymers, as antibacterial, fungicide, antimicrobial or catalyst. 5Antibacterial characterized in that it comprises a polymer of formula I, II, III, IV, V, VI or VII described in any one of claims 1 to 3, or a film of one of these polymers, in solution or in the solid state. 6Antibacterial according to the preceding claim, exhibiting bactericidal activity against a bacterium chosen from Staphylococcus Aureus and Pseudomonas Aeruginosa . 17. Fungicide characterized in that it comprises a polymer of formula I, II, III, IV, V, VI or VII described in any one of claims 1 to 3, or a film of one of these polymers, in solution or in the solid state. 18. Antiviral characterized in that it comprises a polymer of formula I, II, III, IV, V, VI or VII described in any one of claims 1 to 3, or a film of one of these polymers, in solution or in the solid state. 19. Catalyst characterized in that it comprises a polymer of formula I, II, III, IV, V, VI or VII described in any one of claims 1 to 3, or a film of one of these polymers, in solution or in the solid state.