EP4208500A1 - Polymeres contenant des unites de repetition avec plusieurs motifs sulfonates metalliques ou organiques, leurs procedes de preparation et leurs utilisations - Google Patents
Polymeres contenant des unites de repetition avec plusieurs motifs sulfonates metalliques ou organiques, leurs procedes de preparation et leurs utilisationsInfo
- Publication number
- EP4208500A1 EP4208500A1 EP21772651.2A EP21772651A EP4208500A1 EP 4208500 A1 EP4208500 A1 EP 4208500A1 EP 21772651 A EP21772651 A EP 21772651A EP 4208500 A1 EP4208500 A1 EP 4208500A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- polymers
- iodonium
- diamino
- formula
- percentage
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 214
- 238000000034 method Methods 0.000 title claims abstract description 25
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 22
- 239000002184 metal Substances 0.000 title claims abstract description 22
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 title abstract description 3
- 230000000844 anti-bacterial effect Effects 0.000 claims abstract description 29
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- 239000000417 fungicide Substances 0.000 claims abstract description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 54
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 37
- 239000007787 solid Substances 0.000 claims description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- -1 iodonium cation Chemical class 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 23
- 125000006850 spacer group Chemical group 0.000 claims description 23
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 238000004132 cross linking Methods 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 18
- 150000001768 cations Chemical class 0.000 claims description 17
- 150000003839 salts Chemical class 0.000 claims description 16
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- 238000007306 functionalization reaction Methods 0.000 claims description 15
- 239000010931 gold Substances 0.000 claims description 15
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- 230000015572 biosynthetic process Effects 0.000 claims description 11
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 claims description 11
- 230000000855 fungicidal effect Effects 0.000 claims description 11
- 239000000543 intermediate Substances 0.000 claims description 11
- MGFYSGNNHQQTJW-UHFFFAOYSA-N iodonium Chemical compound [IH2+] MGFYSGNNHQQTJW-UHFFFAOYSA-N 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 11
- 238000003786 synthesis reaction Methods 0.000 claims description 11
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 10
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 9
- 150000001242 acetic acid derivatives Chemical class 0.000 claims description 9
- 230000000845 anti-microbial effect Effects 0.000 claims description 9
- 230000000840 anti-viral effect Effects 0.000 claims description 9
- 229910052738 indium Inorganic materials 0.000 claims description 9
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 9
- 230000003647 oxidation Effects 0.000 claims description 9
- 238000007254 oxidation reaction Methods 0.000 claims description 9
- 229910052717 sulfur Inorganic materials 0.000 claims description 9
- 125000004434 sulfur atom Chemical group 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 9
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 8
- NLMDJJTUQPXZFG-UHFFFAOYSA-N 1,4,10,13-tetraoxa-7,16-diazacyclooctadecane Chemical compound C1COCCOCCNCCOCCOCCN1 NLMDJJTUQPXZFG-UHFFFAOYSA-N 0.000 claims description 8
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 8
- GXVUZYLYWKWJIM-UHFFFAOYSA-N 2-(2-aminoethoxy)ethanamine Chemical compound NCCOCCN GXVUZYLYWKWJIM-UHFFFAOYSA-N 0.000 claims description 8
- NIQFAJBKEHPUAM-UHFFFAOYSA-N 2-[2-[2-(2-aminoethoxy)ethoxy]ethoxy]ethanamine Chemical compound NCCOCCOCCOCCN NIQFAJBKEHPUAM-UHFFFAOYSA-N 0.000 claims description 8
- IFZOPNLVYZYSMQ-UHFFFAOYSA-N 2-[2-[2-[2-(2-aminoethoxy)ethoxy]ethoxy]ethoxy]ethanamine Chemical compound NCCOCCOCCOCCOCCN IFZOPNLVYZYSMQ-UHFFFAOYSA-N 0.000 claims description 8
- JCRRFJIVUPSNTA-UHFFFAOYSA-N 4-[4-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC(C=C1)=CC=C1OC1=CC=C(N)C=C1 JCRRFJIVUPSNTA-UHFFFAOYSA-N 0.000 claims description 8
- 239000002841 Lewis acid Substances 0.000 claims description 8
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 8
- IWBOPFCKHIJFMS-UHFFFAOYSA-N ethylene glycol bis(2-aminoethyl) ether Chemical compound NCCOCCOCCN IWBOPFCKHIJFMS-UHFFFAOYSA-N 0.000 claims description 8
- 150000007517 lewis acids Chemical class 0.000 claims description 8
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 claims description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- 150000004985 diamines Chemical class 0.000 claims description 7
- 230000007062 hydrolysis Effects 0.000 claims description 7
- 238000006460 hydrolysis reaction Methods 0.000 claims description 7
- 229910052744 lithium Inorganic materials 0.000 claims description 7
- NPAQDGBOEJUXOX-UHFFFAOYSA-N (2-methylphenyl)-(2,4,6-trimethylphenyl)iodanium Chemical compound CC1=CC(C)=CC(C)=C1[I+]C1=CC=CC=C1C NPAQDGBOEJUXOX-UHFFFAOYSA-N 0.000 claims description 6
- IMAYFPJJNJKXKL-UHFFFAOYSA-N (3-bromophenyl)-(2,4,6-trimethylphenyl)iodanium Chemical compound CC1=CC(C)=CC(C)=C1[I+]C1=CC=CC(Br)=C1 IMAYFPJJNJKXKL-UHFFFAOYSA-N 0.000 claims description 6
- BWZVCCNYKMEVEX-UHFFFAOYSA-N 2,4,6-Trimethylpyridine Chemical compound CC1=CC(C)=NC(C)=C1 BWZVCCNYKMEVEX-UHFFFAOYSA-N 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Chemical class CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 6
- 241000589517 Pseudomonas aeruginosa Species 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 150000001408 amides Chemical class 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 150000001558 benzoic acid derivatives Chemical class 0.000 claims description 6
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 claims description 6
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 claims description 6
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 238000002604 ultrasonography Methods 0.000 claims description 6
- 241000894006 Bacteria Species 0.000 claims description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 5
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 5
- 229910052797 bismuth Inorganic materials 0.000 claims description 5
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- 239000012312 sodium hydride Substances 0.000 claims description 5
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 5
- JTNRGGLCSLZOOQ-UHFFFAOYSA-N 1,3-diphenoxybenzene Chemical compound C=1C=CC(OC=2C=CC=CC=2)=CC=1OC1=CC=CC=C1 JTNRGGLCSLZOOQ-UHFFFAOYSA-N 0.000 claims description 4
- UVGPELGZPWDPFP-UHFFFAOYSA-N 1,4-diphenoxybenzene Chemical compound C=1C=C(OC=2C=CC=CC=2)C=CC=1OC1=CC=CC=C1 UVGPELGZPWDPFP-UHFFFAOYSA-N 0.000 claims description 4
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 4
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- ZCSHNCUQKCANBX-UHFFFAOYSA-N lithium diisopropylamide Chemical compound [Li+].CC(C)[N-]C(C)C ZCSHNCUQKCANBX-UHFFFAOYSA-N 0.000 claims description 4
- 229920006260 polyaryletherketone Polymers 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 4
- 150000003512 tertiary amines Chemical class 0.000 claims description 4
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims description 4
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 claims description 4
- PJHQBPICSCJGPI-UHFFFAOYSA-N (3,5-dichlorophenyl)-(2,4,6-trimethoxyphenyl)iodanium Chemical compound COC1=CC(OC)=C([I+]C2=CC(Cl)=CC(Cl)=C2)C(OC)=C1 PJHQBPICSCJGPI-UHFFFAOYSA-N 0.000 claims description 3
- BFWFMKWUGSIILS-UHFFFAOYSA-N (3-methylphenyl)-(2,4,6-trimethylphenyl)iodanium Chemical compound CC1=CC=CC([I+]C=2C(=CC(C)=CC=2C)C)=C1 BFWFMKWUGSIILS-UHFFFAOYSA-N 0.000 claims description 3
- JTJRJICKRHIFRR-UHFFFAOYSA-N (4-methylphenyl)-(2,4,6-trimethylphenyl)iodanium Chemical compound C1=CC(C)=CC=C1[I+]C1=C(C)C=C(C)C=C1C JTJRJICKRHIFRR-UHFFFAOYSA-N 0.000 claims description 3
- QNAGMLXZAQIBOU-UHFFFAOYSA-N (4-nitrophenyl)-(2,4,6-trimethylphenyl)iodanium Chemical compound CC1=CC(C)=CC(C)=C1[I+]C1=CC=C([N+]([O-])=O)C=C1 QNAGMLXZAQIBOU-UHFFFAOYSA-N 0.000 claims description 3
- OPSOSRFTIUMCJF-UHFFFAOYSA-M (4-nitrophenyl)-phenyliodanium;trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.C1=CC([N+](=O)[O-])=CC=C1[I+]C1=CC=CC=C1 OPSOSRFTIUMCJF-UHFFFAOYSA-M 0.000 claims description 3
- MFKRCEFIAPLZCY-UHFFFAOYSA-N (4-phenylphenyl)-(2,4,6-trimethoxyphenyl)iodanium Chemical compound COc1cc(OC)c([I+]c2ccc(cc2)-c2ccccc2)c(OC)c1 MFKRCEFIAPLZCY-UHFFFAOYSA-N 0.000 claims description 3
- SUUXOKIQOYRLBK-UHFFFAOYSA-N (5-fluoro-2-nitrophenyl)-(2,4,6-trimethoxyphenyl)iodanium Chemical compound COC1=CC(OC)=C([I+]C2=C(C=CC(F)=C2)[N+]([O-])=O)C(OC)=C1 SUUXOKIQOYRLBK-UHFFFAOYSA-N 0.000 claims description 3
- ZXSQEZNORDWBGZ-UHFFFAOYSA-N 1,3-dihydropyrrolo[2,3-b]pyridin-2-one Chemical compound C1=CN=C2NC(=O)CC2=C1 ZXSQEZNORDWBGZ-UHFFFAOYSA-N 0.000 claims description 3
- OCZIZUGXOJUBMO-UHFFFAOYSA-N 1-adamantyl-tris(hydroxymethyl)phosphanium Chemical compound C1C(C2)CC3CC2CC1([P+](CO)(CO)CO)C3 OCZIZUGXOJUBMO-UHFFFAOYSA-N 0.000 claims description 3
- 125000006276 2-bromophenyl group Chemical group [H]C1=C([H])C(Br)=C(*)C([H])=C1[H] 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- 239000004952 Polyamide Substances 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- 241000191967 Staphylococcus aureus Species 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- HYGCUEYOKGLJQZ-UHFFFAOYSA-N [4-(2-hydroxytetradecoxy)phenyl]-phenyliodanium Chemical compound C1=CC(OCC(O)CCCCCCCCCCCC)=CC=C1[I+]C1=CC=CC=C1 HYGCUEYOKGLJQZ-UHFFFAOYSA-N 0.000 claims description 3
- FLBLHNVZAXVSJH-UHFFFAOYSA-N [4-(bromomethyl)phenyl]-(2,4,6-trimethoxyphenyl)iodanium Chemical compound COC1=CC(OC)=CC(OC)=C1[I+]C1=CC=C(CBr)C=C1 FLBLHNVZAXVSJH-UHFFFAOYSA-N 0.000 claims description 3
- JHYBNSWWQNFERC-UHFFFAOYSA-N [4-fluoro-3-(trifluoromethyl)phenyl]-(2,4,6-trimethoxyphenyl)iodanium Chemical compound COC1=CC(OC)=C([I+]C2=CC(=C(F)C=C2)C(F)(F)F)C(OC)=C1 JHYBNSWWQNFERC-UHFFFAOYSA-N 0.000 claims description 3
- NRGWEQLAXOTOPB-UHFFFAOYSA-O [diethylamino(ethylamino)methylidene]-diethylazanium Chemical compound CCNC(N(CC)CC)=[N+](CC)CC NRGWEQLAXOTOPB-UHFFFAOYSA-O 0.000 claims description 3
- 150000007513 acids Chemical class 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 3
- WOUBWJAJSXAOIV-UHFFFAOYSA-N benzene-1,4-disulfonamide Chemical compound NS(=O)(=O)C1=CC=C(S(N)(=O)=O)C=C1 WOUBWJAJSXAOIV-UHFFFAOYSA-N 0.000 claims description 3
- FGLZFXDJHLJUIA-UHFFFAOYSA-N bis(2,4,6-trimethylphenyl)iodanium Chemical compound CC1=CC(C)=CC(C)=C1[I+]C1=C(C)C=C(C)C=C1C FGLZFXDJHLJUIA-UHFFFAOYSA-N 0.000 claims description 3
- RKJMYAKRQZRZCW-UHFFFAOYSA-N bis(4-bromophenyl)iodanium Chemical compound C1=CC(Br)=CC=C1[I+]C1=CC=C(Br)C=C1 RKJMYAKRQZRZCW-UHFFFAOYSA-N 0.000 claims description 3
- PHVCCRNHUOHRPC-UHFFFAOYSA-N bis(4-fluorophenyl)iodanium Chemical compound C1=CC(F)=CC=C1[I+]C1=CC=C(F)C=C1 PHVCCRNHUOHRPC-UHFFFAOYSA-N 0.000 claims description 3
- HKWWDSQUZURFQR-UHFFFAOYSA-N bis(4-methylphenyl)iodanium Chemical compound C1=CC(C)=CC=C1[I+]C1=CC=C(C)C=C1 HKWWDSQUZURFQR-UHFFFAOYSA-N 0.000 claims description 3
- DNFSNYQTQMVTOK-UHFFFAOYSA-N bis(4-tert-butylphenyl)iodanium Chemical compound C1=CC(C(C)(C)C)=CC=C1[I+]C1=CC=C(C(C)(C)C)C=C1 DNFSNYQTQMVTOK-UHFFFAOYSA-N 0.000 claims description 3
- NYENCOMLZDQKNH-UHFFFAOYSA-K bis(trifluoromethylsulfonyloxy)bismuthanyl trifluoromethanesulfonate Chemical compound [Bi+3].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F NYENCOMLZDQKNH-UHFFFAOYSA-K 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 150000007942 carboxylates Chemical class 0.000 claims description 3
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229940116318 copper carbonate Drugs 0.000 claims description 3
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 claims description 3
- MBRLRPLNYSOMCQ-UHFFFAOYSA-N ethynyl(phenyl)iodanium Chemical compound C#C[I+]C1=CC=CC=C1 MBRLRPLNYSOMCQ-UHFFFAOYSA-N 0.000 claims description 3
- RAQDACVRFCEPDA-UHFFFAOYSA-L ferrous carbonate Chemical compound [Fe+2].[O-]C([O-])=O RAQDACVRFCEPDA-UHFFFAOYSA-L 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- ISNICOKBNZOJQG-UHFFFAOYSA-O guanidinium ion Chemical compound C[NH+]=C(N(C)C)N(C)C ISNICOKBNZOJQG-UHFFFAOYSA-O 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
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- DTIFFPXSSXFQCJ-UHFFFAOYSA-N tetrahexylazanium Chemical compound CCCCCC[N+](CCCCCC)(CCCCCC)CCCCCC DTIFFPXSSXFQCJ-UHFFFAOYSA-N 0.000 claims description 3
- AGWJLDNNUJKAHP-UHFFFAOYSA-N tetrahexylphosphanium Chemical compound CCCCCC[P+](CCCCCC)(CCCCCC)CCCCCC AGWJLDNNUJKAHP-UHFFFAOYSA-N 0.000 claims description 3
- BXYHVFRRNNWPMB-UHFFFAOYSA-N tetramethylphosphanium Chemical compound C[P+](C)(C)C BXYHVFRRNNWPMB-UHFFFAOYSA-N 0.000 claims description 3
- CHYBTAZWINMGHA-UHFFFAOYSA-N tetraoctylazanium Chemical compound CCCCCCCC[N+](CCCCCCCC)(CCCCCCCC)CCCCCCCC CHYBTAZWINMGHA-UHFFFAOYSA-N 0.000 claims description 3
- GJSGYPDDPQRWPK-UHFFFAOYSA-N tetrapentylammonium Chemical compound CCCCC[N+](CCCCC)(CCCCC)CCCCC GJSGYPDDPQRWPK-UHFFFAOYSA-N 0.000 claims description 3
- LRPOXSSMNVVCMT-UHFFFAOYSA-N tetrapentylphosphanium Chemical compound CCCCC[P+](CCCCC)(CCCCC)CCCCC LRPOXSSMNVVCMT-UHFFFAOYSA-N 0.000 claims description 3
- CZMILNXHOAKSBR-UHFFFAOYSA-N tetraphenylazanium Chemical compound C1=CC=CC=C1[N+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 CZMILNXHOAKSBR-UHFFFAOYSA-N 0.000 claims description 3
- USFPINLPPFWTJW-UHFFFAOYSA-N tetraphenylphosphonium Chemical compound C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 USFPINLPPFWTJW-UHFFFAOYSA-N 0.000 claims description 3
- OSBSFAARYOCBHB-UHFFFAOYSA-N tetrapropylammonium Chemical compound CCC[N+](CCC)(CCC)CCC OSBSFAARYOCBHB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
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- 239000010936 titanium Substances 0.000 claims description 3
- GFVKHYGXCQWRON-UHFFFAOYSA-N tributyl(ethyl)azanium Chemical compound CCCC[N+](CC)(CCCC)CCCC GFVKHYGXCQWRON-UHFFFAOYSA-N 0.000 claims description 3
- HJHUXWBTVVFLQI-UHFFFAOYSA-N tributyl(methyl)azanium Chemical compound CCCC[N+](C)(CCCC)CCCC HJHUXWBTVVFLQI-UHFFFAOYSA-N 0.000 claims description 3
- JJPVWQWOOQYHCB-UHFFFAOYSA-N triethyl(phenyl)azanium Chemical compound CC[N+](CC)(CC)C1=CC=CC=C1 JJPVWQWOOQYHCB-UHFFFAOYSA-N 0.000 claims description 3
- ZNEOHLHCKGUAEB-UHFFFAOYSA-N trimethylphenylammonium Chemical compound C[N+](C)(C)C1=CC=CC=C1 ZNEOHLHCKGUAEB-UHFFFAOYSA-N 0.000 claims description 3
- PXIMQGSMXJFQOF-UHFFFAOYSA-N triphenyl(propan-2-yl)phosphanium Chemical compound C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C(C)C)C1=CC=CC=C1 PXIMQGSMXJFQOF-UHFFFAOYSA-N 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
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- IRDQNLLVRXMERV-UHFFFAOYSA-N CCCC[Na] Chemical compound CCCC[Na] IRDQNLLVRXMERV-UHFFFAOYSA-N 0.000 claims description 2
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- QNKHVIRRKIYHNN-UHFFFAOYSA-L disodium methanesulfonate Chemical compound [Na+].[Na+].CS([O-])(=O)=O.CS([O-])(=O)=O QNKHVIRRKIYHNN-UHFFFAOYSA-L 0.000 claims description 2
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- 239000003599 detergent Substances 0.000 description 1
- AKISDSWMEPTCRL-UHFFFAOYSA-N dimethyl 2,2-bis(prop-2-ynyl)propanedioate Chemical compound COC(=O)C(CC#C)(CC#C)C(=O)OC AKISDSWMEPTCRL-UHFFFAOYSA-N 0.000 description 1
- QKIUAMUSENSFQQ-UHFFFAOYSA-N dimethylazanide Chemical compound C[N-]C QKIUAMUSENSFQQ-UHFFFAOYSA-N 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000003818 flash chromatography Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000012737 fresh medium Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008233 hard water Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 230000002458 infectious effect Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000002054 inoculum Substances 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000012669 liquid formulation Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- DBYQHFPBWKKZAT-UHFFFAOYSA-N lithium;benzene Chemical compound [Li+].C1=CC=[C-]C=C1 DBYQHFPBWKKZAT-UHFFFAOYSA-N 0.000 description 1
- IHLVCKWPAMTVTG-UHFFFAOYSA-N lithium;carbanide Chemical compound [Li+].[CH3-] IHLVCKWPAMTVTG-UHFFFAOYSA-N 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- 230000035479 physiological effects, processes and functions Effects 0.000 description 1
- 238000001637 plasma atomic emission spectroscopy Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003208 poly(ethylene sulfide) Polymers 0.000 description 1
- 239000013641 positive control Substances 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- GGHDAUPFEBTORZ-UHFFFAOYSA-N propane-1,1-diamine Chemical compound CCC(N)N GGHDAUPFEBTORZ-UHFFFAOYSA-N 0.000 description 1
- ZNZJJSYHZBXQSM-UHFFFAOYSA-N propane-2,2-diamine Chemical compound CC(C)(N)N ZNZJJSYHZBXQSM-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical group OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 229960003500 triclosan Drugs 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/48—Polymers modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
- C08G65/4012—Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones
- C08G65/4056—(I) or (II) containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/20—Polysulfones
- C08G75/23—Polyethersulfones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2371/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08J2371/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2381/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
- C08J2381/06—Polysulfones; Polyethersulfones
Definitions
- 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.
- 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.
- quaternary ammonium salts used in many fields such as cleaning products, cosmetics.
- these compounds have several disadvantages.
- the antimicrobial dispersed in the medium 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.
- 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.
- 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 Applicant has developed polymers having several sulphonate functions per repeating unit, which, a priori, was not obvious due to the deactivating nature of the sulphonic functions.
- the first subject of the invention is 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 a or 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; - 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
- - ⁇ 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 N,N,N,N-tetramethylammonium cations , 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-tribut
- 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 at 1 and less than or equal to 4, and preferably greater than 1 less than or equal to
- 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 motif W 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
- 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, XXIII, XXIV, XXV, XXVI, XXVII, XXVIII, XXIX, XXX, XXXI, XXIII, XXXIV or XXXXV.
- 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 ⁇ m.
- 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.
- 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.
- - M z+ represents a cation corresponding to an oxidized form of iron; and – the polymer is of formula I.
- the 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.
- - 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 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 space
- 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 repeating units bridged by a motif W 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%.
- 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.
- the polymers of the invention correspond to formulas I, II, III, IV, V, VI and VII in which: - m represents the percentage of unbridged repeating units having an oxoaryl or dioxoaryl unit possessing several sulfonyl functions; this percentage varies between 60% and 99.99%, preferably between 80% and 99.99%; - n represents the percentage of repeating 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%; - the sum m + n represents 100%.
- the polymers of formula I, II, III, IV, V, VI, VII and VIII are crosslinked.
- 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 N,N,N,N-tetramethylammonium, N,N,N,N-tetraethylammonium, N,N,N,N-tetrapropylammonium, N,N,N,N- tetrabuty
- 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
- 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-
- the spacer W is chosen from propyl-1,3-diamino, N,N'-piperazinediyl, 1,4-diphenyletherdiyl groups.
- 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 sulfonyl functions per repeat unit, that is to say a statistical distribution of sulfonyl functions resulting, on average, in several sulfonyl functions per repeat unit.
- 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
- q represents the number of polymer 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.
- the polychlorosulphonation is carried out at a temperature between 60° C. and 150° C., preferably between 80° C.
- 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.
- 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.
- 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.
- the chlorosulfonic acid can be generated in situ, for example from sulfuric acid and thionyl chloride (C.
- 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.
- polychlorosulfonated polymers XV, XVI, XVII, XVIII, XIX, XX and XXI are given by way of example. Other isomers can 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 .
- - 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.
- 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%.
- the crosslinking step is optional only for the polymers of formula XV, XVI, XVII and XVIII.
- the intermediate polymers, of formula XXII, XXIII, XXIV and XXV are not necessarily crosslinked and n may be equal to 0%.
- the step of crosslinking the polymers of formula XV, XVI, XVII, XVIII, XIX, XX and XXI makes it possible to obtain the polymers of formula XXII, XXIII, XXIV, XXV, 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%.
- the intermediate polymers of formula XXII, XXIII, XXIV, XXV, XXVI, XXVII and XXVIII are necessarily crosslinked and n cannot be equal to 0%.
- 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'-d
- 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'-di
- 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.
- 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.
- 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.
- 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,
- - 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.
- 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 step of functionalizing the polymers of formula XXII, XXIII, XXIV, XXV, XXVI, XXVII and XXVIII makes it possible to obtain the polymers of formula XXIX, XXX, XXXI, XXXII, 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%.
- 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.
- 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, XXIII, 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.
- 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 quite conceivable to use mixtures of metals or salts or else a sub-stoichiometry in salts.
- 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 + .
- 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 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 -
- a metal hydroxide such as soda, lithin, potash, magnesium hydroxide
- a metal carbonate such as zinc carbonate, iron carbonate, silver carbonate, copper carbonate, sodium carbonate, potassium carbonate
- a metal carboxylate such as metal acetates, metal propionates
- - by reaction of a metal in the oxidation state (0), under ultrasound By reaction with a metal hydroxide such as soda, lithin, potash, magnesium hydroxide; or - by reaction with a metal carbonate such as zinc carbonate, iron carbonate, silver carbonate, copper carbonate, sodium carbonate, potassium carbonate; or - by reaction with a metal carb
- 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, XX, XXI, XXII, XXIII, XXXIV, XXXV.
- These synthesis intermediates are as defined above. In particular, these synthesis intermediates are polysulfonated polymers.
- each repeat unit statistically comprises several SO 2 Cl functions.
- a unit of non-bridged repeat that is to say a non-bridged repeat unit having an oxoaryl or dioxoaryl unit, the percentage of which is defined by m, statistically comprises several sulfonyl 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.
- 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 ⁇ m and 200 ⁇ m, preferably between 50 to 150 ⁇ m.
- 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 ⁇ m and 200 ⁇ m, preferably between 50 and 150 ⁇ m.
- the polymer films according to the invention can be used in a temperature range of 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.
- 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.
- 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 the 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.
- 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 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.
- 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 polymer of formula I, II, III, IV, V, VI or VII, or the film of one of these polymers is as defined above, and M z+ represents a cation corresponding to an oxidized form of iron.
- the antiviral material comprises a polymer of formula I, or a polymer film of formula I, and M z+ represents a cation corresponding to an oxidized form of iron.
- 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.
- 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.
- S-Cl represents the following polymers
- D-Cl represent all of the following compounds:
- 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.
- DCE dichloroethane
- Example 2 Polychlorosulfonation of PEEK. Influence of the reaction time
- the operation is carried out under the conditions of example 1 by varying the reaction time Increasing the reaction time favors the formation of the trichlorosulfonated polymer.
- Examples 3 to 5 Polychlorosulfonation of PEEK. Influence of the reaction temperature
- the operation is carried out under the conditions of example 1 by varying the reaction temperature. A rise in temperature promotes polychlorosulfonation.
- Examples 6 to 10 Polychlorosulfonation of PEEK. Influence of the Solvent and of the Reaction Time The operation is carried out under the conditions of Example 1 by varying the solvent, and consequently the reaction temperature and the time.
- Examples 11 to 16 Polychlorosulfonation of PEEK in the absence of solvent. Influence of the solvent The operation is carried out under the conditions of example 1, in the absence of solvent, and by increasing the temperature: Examples 17 to 19 - Polychlorosulphonation of SPEEK-Cl to obtain a polymer of formula XV Into a dry flask, equipped with a magnetic bar and conditioned under an inert atmosphere, 200 mg of SPEEK-Cl of type S-Cl chlorosulphonated at 100 % (0.51mmol) 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.
- Example 23 Crosslinking of dichlorosulfonated SPEEKs with piperazine to obtain a polymer of formula XXII
- the operation is carried out under the conditions of Examples 27 to 29, replacing 1,3-diaminopropane with piperazine (15% molar relative to the SO functions 2Cl ). During the reaction, an insoluble polymer is formed.
- Example 25 Hydrolysis of a SPEEK-Cl crosslinked with diphenyl ether, to obtain a polymer of formula XXIX
- a 100 mL flask 550 mg of disulphonated SPEEK-Cl (2 SO 2 Cl functions per repeating unit) are introduced, of which 40% of the SO 2 Cl functions were 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.
- Example 26 Hydrolysis of a SPEEK-Cl disulphonated at 200% and crosslinked at 10% with 1,3-diaminopropane, to obtain a polymer of formula XXIX
- a polymer of formula XXIX Into a 100 mL flask, 550 mg of disulphonated SPEEK-Cl are introduced (2 SO 2 Cl functions per repeat unit) of which 20% of the SO 2 Cl functions were crosslinked 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.
- Example 27 Hydrolysis of a crosslinked SPEEK-Cl by 1,3-diaminopropane with lithine, to obtain a polymer of formula I
- a crosslinked SPEEK-Cl by 1,3-diaminopropane with lithine to obtain a polymer of formula I
- 83 mg of disulphonated SPEEK-Cl (2 SO 2 Cl functions per repeat unit) are introduced, 40% of the SO2Cl functions of which have been cross-linked with 1,3-diaminopropane and 50 mL of water containing 0.01mM LiOH.
- the reaction mixture is heated under reflux for 18 h.
- the acidimetric assay with 0.1N sodium hydroxide shows that the polymer consists on average of 90% SPEKK-OH with 2 SO3H functions per repeat unit and 10% PEKK-OH with 1 SO 3 H function per repeat unit .
- Example 32 Antibacterial Results of Polysulfonated SPEEK-Fe(II) Polymers Crosslinked to 10% with 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 compared to the number inoculated at T0 (a few minutes after inoculation) and T7 (7 days after inoculation). The reduction in the number of microorganisms is greater than 5 log after 7 days.
- Example 33 Antibacterial results of polysulphonated SPEEK-Fe(II) polymers crosslinked at 20% with diphenyl ether, of formula I.
- 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.
- 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 SO3H 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.
- Example 39 Cycloisomerization. Influence of SPEEK-Au(I) recycling as a catalyst This cycloisomerization has been described in a homogeneous medium by: E. Genin, PY Toullec, S. Antoniotti, C. Brancour, J.-P. Genet and V. Michelet, J. Am.
- Example 40 Cycloisomerization with SPEEK-Au(I) as Catalyst This cycloisomerization has been described in a homogeneous medium by: E. Genin, PY Toullec, S. Antoniotti, C. Brancour, J.-P. Genêt and V. Michelet, J. Am. Chem. Soc. (2006), 128, 3112.
- a cytotoxicity test is carried out on a culture of Vero E6 cells.
- a drop of 200 ⁇ L of culture medium is placed in a well of a 6-well plate containing the polymer film.
- the samples are then left in contact for 15 minutes or 1 hour.
- the pure samples diluted to dilutions 10 -1 and 10 -2 are then brought into contact with the cells for 1 hour before being removed to be replaced with fresh medium.
- the cells are incubated for 2 days at 37° C. then the cytotoxicity is observed using a microscope.
- the results show an absence of cytotoxicity for the culture media brought into contact, at both times, with the polymer SPEEK-Fe(II) diluted to dilutions 10 -1 and 10 -2 , or with the reference polymer (PEEK), pure or diluted.
- Plaque Forming Unit PFU
- the cell monolayer is stained purple, the holes remain white.
- a viral titer is then calculated in PFU/mL taking into account the dilution factor and the volume of the inoculum.
- a drop of 200 ⁇ L of SARS-CoV2 viral stock is deposited in wells of a 6-well plate which is empty (control) or contains the PEEK film or the SPEEK-Fe(II) polymer film. The samples are then left in contact for 15 minutes or 1 hour. The positive control corresponds to the virus deposited in an empty well.
- the viral titration results show a reduction in the viral titer of 0.5 log10 at 15 minutes of contact and of 1.24 log10 after one hour of contact.
Abstract
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PCT/EP2021/074349 WO2022049236A1 (fr) | 2020-09-03 | 2021-09-03 | Polymeres contenant des unites de repetition avec plusieurs motifs sulfonates metalliques ou organiques, leurs procedes de preparation et leurs utilisations |
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US5030706A (en) * | 1988-10-11 | 1991-07-09 | The Dow Chemical Company | Copolymers containing polybenzoxazole, polybenzothiazole and polybenzimidazole moieties |
US6090895A (en) * | 1998-05-22 | 2000-07-18 | 3M Innovative Properties Co., | Crosslinked ion conductive membranes |
WO2001094450A2 (fr) * | 2000-06-02 | 2001-12-13 | Sri International | Composition polymerique |
JP2005154578A (ja) * | 2003-11-26 | 2005-06-16 | Jsr Corp | 架橋型高分子電解質およびプロトン伝導膜 |
JP2010100705A (ja) * | 2008-10-22 | 2010-05-06 | Toyota Motor Corp | 高分子電解質合成方法、高分子電解質膜、及び固体高分子型燃料電池 |
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FR3024146B1 (fr) * | 2014-07-23 | 2018-02-16 | Cdp Innovation | Nouveaux polymeres contenant des sels de lithium ou de sodium de bis(sulfonyl)imides greffes, leurs procedes de preparation et leurs utilisations comme electrolytes pour batteries |
FR3030534B1 (fr) | 2014-12-22 | 2016-12-30 | Cdp Innovation | Nouveaux polymeres contenant des fonctions sulfonates metalliques, leurs procedes de preparation et leurs utilisations comme catalyseurs |
FR3030533B1 (fr) * | 2014-12-22 | 2017-05-12 | Cdp Innovation | Nouveaux polymeres contenant des fonctions sulfonates metalliques, leurs procedes de preparation et leurs utilisations comme antibacteriens, fongicides et antimicrobiens |
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