WO2024062182A1 - Functionalized halogenated polymer and method for preparing same - Google Patents
Functionalized halogenated polymer and method for preparing same Download PDFInfo
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- WO2024062182A1 WO2024062182A1 PCT/FR2023/051414 FR2023051414W WO2024062182A1 WO 2024062182 A1 WO2024062182 A1 WO 2024062182A1 FR 2023051414 W FR2023051414 W FR 2023051414W WO 2024062182 A1 WO2024062182 A1 WO 2024062182A1
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- Prior art keywords
- monomeric units
- polymer
- group
- formula
- vinyl
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- 229920000642 polymer Polymers 0.000 title claims abstract description 79
- 238000000034 method Methods 0.000 title claims abstract description 21
- -1 thiolate compound Chemical class 0.000 claims abstract description 43
- 239000000178 monomer Substances 0.000 claims abstract description 36
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 29
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 23
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 17
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 14
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 14
- 125000005843 halogen group Chemical group 0.000 claims abstract description 13
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 claims abstract description 10
- 125000001188 haloalkyl group Chemical group 0.000 claims abstract description 9
- 150000002978 peroxides Chemical class 0.000 claims abstract description 9
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 claims abstract description 8
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims abstract description 7
- 125000001424 substituent group Chemical group 0.000 claims description 35
- 239000000203 mixture Substances 0.000 claims description 32
- 125000000217 alkyl group Chemical group 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000000460 chlorine Substances 0.000 claims description 20
- 125000000524 functional group Chemical group 0.000 claims description 20
- 229920001515 polyalkylene glycol Polymers 0.000 claims description 18
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 17
- 125000003118 aryl group Chemical group 0.000 claims description 16
- 125000000392 cycloalkenyl group Chemical group 0.000 claims description 14
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical compound FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 claims description 14
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 12
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 12
- FDMFUZHCIRHGRG-UHFFFAOYSA-N 3,3,3-trifluoroprop-1-ene Chemical compound FC(F)(F)C=C FDMFUZHCIRHGRG-UHFFFAOYSA-N 0.000 claims description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 11
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 10
- 125000003342 alkenyl group Chemical group 0.000 claims description 10
- 239000011737 fluorine Substances 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 9
- 238000000576 coating method Methods 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- DMUPYMORYHFFCT-UPHRSURJSA-N (z)-1,2,3,3,3-pentafluoroprop-1-ene Chemical compound F\C=C(/F)C(F)(F)F DMUPYMORYHFFCT-UPHRSURJSA-N 0.000 claims description 8
- OQISUJXQFPPARX-UHFFFAOYSA-N 2-chloro-3,3,3-trifluoroprop-1-ene Chemical compound FC(F)(F)C(Cl)=C OQISUJXQFPPARX-UHFFFAOYSA-N 0.000 claims description 8
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 8
- INLLPKCGLOXCIV-UHFFFAOYSA-N bromoethene Chemical compound BrC=C INLLPKCGLOXCIV-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- GHXZPUGJZVBLGC-UHFFFAOYSA-N iodoethene Chemical compound IC=C GHXZPUGJZVBLGC-UHFFFAOYSA-N 0.000 claims description 8
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 6
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 claims description 6
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 6
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 6
- 239000004793 Polystyrene Substances 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Chemical compound [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical group 0.000 claims description 6
- ZCSHNCUQKCANBX-UHFFFAOYSA-N lithium diisopropylamide Chemical compound [Li+].CC(C)[N-]C(C)C ZCSHNCUQKCANBX-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 229920002223 polystyrene Polymers 0.000 claims description 6
- CPRMKOQKXYSDML-UHFFFAOYSA-M rubidium hydroxide Chemical compound [OH-].[Rb+] CPRMKOQKXYSDML-UHFFFAOYSA-M 0.000 claims description 6
- UMGQVBVEWTXECF-UHFFFAOYSA-N 1,1,2,3-tetrachloroprop-1-ene Chemical compound ClCC(Cl)=C(Cl)Cl UMGQVBVEWTXECF-UHFFFAOYSA-N 0.000 claims description 5
- LIPPKMMVZOHCIF-UHFFFAOYSA-N 1,1,2-trichloroprop-1-ene Chemical compound CC(Cl)=C(Cl)Cl LIPPKMMVZOHCIF-UHFFFAOYSA-N 0.000 claims description 5
- ZAIDIVBQUMFXEC-UHFFFAOYSA-N 1,1-dichloroprop-1-ene Chemical compound CC=C(Cl)Cl ZAIDIVBQUMFXEC-UHFFFAOYSA-N 0.000 claims description 5
- YHLIEGBCOUQKHU-UHFFFAOYSA-N 1,1-difluoroprop-1-ene Chemical compound CC=C(F)F YHLIEGBCOUQKHU-UHFFFAOYSA-N 0.000 claims description 5
- VJGCZWVJDRIHNC-UHFFFAOYSA-N 1-fluoroprop-1-ene Chemical compound CC=CF VJGCZWVJDRIHNC-UHFFFAOYSA-N 0.000 claims description 5
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 claims description 5
- 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 5
- 229910003849 O-Si Inorganic materials 0.000 claims description 5
- 229910003872 O—Si Inorganic materials 0.000 claims description 5
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 claims description 5
- VFDYKPARTDCDCU-UHFFFAOYSA-N hexachloropropene Chemical compound ClC(Cl)=C(Cl)C(Cl)(Cl)Cl VFDYKPARTDCDCU-UHFFFAOYSA-N 0.000 claims description 5
- 239000011591 potassium Substances 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 229950011008 tetrachloroethylene Drugs 0.000 claims description 5
- KYVBNYUBXIEUFW-UHFFFAOYSA-N 1,1,3,3-tetramethylguanidine Chemical compound CN(C)C(=N)N(C)C KYVBNYUBXIEUFW-UHFFFAOYSA-N 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 4
- 239000000446 fuel Substances 0.000 claims description 4
- 150000002430 hydrocarbons Chemical group 0.000 claims description 4
- 150000002432 hydroperoxides Chemical class 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 150000001451 organic peroxides Chemical class 0.000 claims description 4
- WHIRALQRTSITMI-UJURSFKZSA-N (1s,5r)-6,8-dioxabicyclo[3.2.1]octan-4-one Chemical compound O1[C@@]2([H])OC[C@]1([H])CCC2=O WHIRALQRTSITMI-UJURSFKZSA-N 0.000 claims description 3
- KYRYKPLDURXJCW-UHFFFAOYSA-N 1,3,2,4-diazadiphosphetidine Chemical compound N1PNP1 KYRYKPLDURXJCW-UHFFFAOYSA-N 0.000 claims description 3
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 claims description 3
- UWKQJZCTQGMHKD-UHFFFAOYSA-N 2,6-di-tert-butylpyridine Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=N1 UWKQJZCTQGMHKD-UHFFFAOYSA-N 0.000 claims description 3
- PCYSWBQHCWWSFW-UHFFFAOYSA-N 4,6,11-trimethyl-1,4,6,11-tetraza-5-phosphabicyclo[3.3.3]undecane Chemical compound C1CN(C)P2N(C)CCN1CCN2C PCYSWBQHCWWSFW-UHFFFAOYSA-N 0.000 claims description 3
- VFYGGVGHFXHJBO-UHFFFAOYSA-N C(C)(C)[N-]C(C)C.[Rb+] Chemical compound C(C)(C)[N-]C(C)C.[Rb+] VFYGGVGHFXHJBO-UHFFFAOYSA-N 0.000 claims description 3
- WTXOBUNCXMLEOJ-UHFFFAOYSA-N C=C=C=CF.F Chemical compound C=C=C=CF.F WTXOBUNCXMLEOJ-UHFFFAOYSA-N 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 3
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- LINDOXZENKYESA-UHFFFAOYSA-N TMG Natural products CNC(N)=NC LINDOXZENKYESA-UHFFFAOYSA-N 0.000 claims description 3
- FLDQIVJIBJOWLG-UHFFFAOYSA-N bis(trimethylsilyl)azanide rubidium(1+) Chemical compound [Rb+].C[Si](C)(C)[N-][Si](C)(C)C FLDQIVJIBJOWLG-UHFFFAOYSA-N 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 235000011116 calcium hydroxide Nutrition 0.000 claims description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 3
- YBLVILVQEZRPFO-UHFFFAOYSA-N calcium;bis(trimethylsilyl)azanide Chemical compound [Ca+2].C[Si](C)(C)[N-][Si](C)(C)C.C[Si](C)(C)[N-][Si](C)(C)C YBLVILVQEZRPFO-UHFFFAOYSA-N 0.000 claims description 3
- WJBGFWVXTWSRAN-UHFFFAOYSA-N calcium;di(propan-2-yl)azanide Chemical compound [Ca+2].CC(C)[N-]C(C)C.CC(C)[N-]C(C)C WJBGFWVXTWSRAN-UHFFFAOYSA-N 0.000 claims description 3
- 229920001940 conductive polymer Polymers 0.000 claims description 3
- 238000006704 dehydrohalogenation reaction Methods 0.000 claims description 3
- 230000002209 hydrophobic effect Effects 0.000 claims description 3
- YNESATAKKCNGOF-UHFFFAOYSA-N lithium bis(trimethylsilyl)amide Chemical compound [Li+].C[Si](C)(C)[N-][Si](C)(C)C YNESATAKKCNGOF-UHFFFAOYSA-N 0.000 claims description 3
- ANYSGBYRTLOUPO-UHFFFAOYSA-N lithium tetramethylpiperidide Chemical compound [Li]N1C(C)(C)CCCC1(C)C ANYSGBYRTLOUPO-UHFFFAOYSA-N 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 3
- 239000000347 magnesium hydroxide Substances 0.000 claims description 3
- 235000012254 magnesium hydroxide Nutrition 0.000 claims description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 3
- WYPTZCBYSQFOQS-UHFFFAOYSA-N magnesium;bis(trimethylsilyl)azanide Chemical compound [Mg+2].C[Si](C)(C)[N-][Si](C)(C)C.C[Si](C)(C)[N-][Si](C)(C)C WYPTZCBYSQFOQS-UHFFFAOYSA-N 0.000 claims description 3
- XDBOBNVQEBSKFO-UHFFFAOYSA-N magnesium;di(propan-2-yl)azanide Chemical compound CC(C)N(C(C)C)[Mg]N(C(C)C)C(C)C XDBOBNVQEBSKFO-UHFFFAOYSA-N 0.000 claims description 3
- IUBQJLUDMLPAGT-UHFFFAOYSA-N potassium bis(trimethylsilyl)amide Chemical compound C[Si](C)(C)N([K])[Si](C)(C)C IUBQJLUDMLPAGT-UHFFFAOYSA-N 0.000 claims description 3
- ZMJJCODMIXQWCQ-UHFFFAOYSA-N potassium;di(propan-2-yl)azanide Chemical compound [K+].CC(C)[N-]C(C)C ZMJJCODMIXQWCQ-UHFFFAOYSA-N 0.000 claims description 3
- VBKNTGMWIPUCRF-UHFFFAOYSA-M potassium;fluoride;hydrofluoride Chemical compound F.[F-].[K+] VBKNTGMWIPUCRF-UHFFFAOYSA-M 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- SBYHFKPVCBCYGV-UHFFFAOYSA-N quinuclidine Chemical compound C1CC2CCN1CC2 SBYHFKPVCBCYGV-UHFFFAOYSA-N 0.000 claims description 3
- 229910052701 rubidium Inorganic materials 0.000 claims description 3
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 3
- WRIKHQLVHPKCJU-UHFFFAOYSA-N sodium bis(trimethylsilyl)amide Chemical compound C[Si](C)(C)N([Na])[Si](C)(C)C WRIKHQLVHPKCJU-UHFFFAOYSA-N 0.000 claims description 3
- YHOBGCSGTGDMLF-UHFFFAOYSA-N sodium;di(propan-2-yl)azanide Chemical compound [Na+].CC(C)[N-]C(C)C YHOBGCSGTGDMLF-UHFFFAOYSA-N 0.000 claims description 3
- 239000007784 solid electrolyte Substances 0.000 claims description 3
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 claims description 3
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 3
- UURSXESKOOOTOV-UHFFFAOYSA-N dec-5-ene Chemical compound CCCCC=CCCCC UURSXESKOOOTOV-UHFFFAOYSA-N 0.000 claims 3
- MGKYTFDYDXZTEM-UHFFFAOYSA-N n,n-dibutyl-2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepin-10-amine Chemical compound CCCCN(CCCC)C1CCCCN2CCCN=C12 MGKYTFDYDXZTEM-UHFFFAOYSA-N 0.000 claims 1
- 125000001153 fluoro group Chemical group F* 0.000 abstract description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 abstract 1
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 54
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 18
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 15
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 14
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 12
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 11
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 10
- FPBWSPZHCJXUBL-UHFFFAOYSA-N 1-chloro-1-fluoroethene Chemical group FC(Cl)=C FPBWSPZHCJXUBL-UHFFFAOYSA-N 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 9
- 150000002148 esters Chemical class 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 8
- 238000007306 functionalization reaction Methods 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical group FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 description 6
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 6
- LDTMPQQAWUMPKS-UHFFFAOYSA-N 1-chloro-3,3,3-trifluoroprop-1-ene Chemical compound FC(F)(F)C=CCl LDTMPQQAWUMPKS-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 6
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 6
- FFYWKOUKJFCBAM-UHFFFAOYSA-N ethenyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC=C FFYWKOUKJFCBAM-UHFFFAOYSA-N 0.000 description 6
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 6
- RQAKESSLMFZVMC-UHFFFAOYSA-N n-ethenylacetamide Chemical compound CC(=O)NC=C RQAKESSLMFZVMC-UHFFFAOYSA-N 0.000 description 6
- LVLANIHJQRZTPY-UHFFFAOYSA-N vinyl carbamate Chemical compound NC(=O)OC=C LVLANIHJQRZTPY-UHFFFAOYSA-N 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- DIBHLCJAJIKHGB-UHFFFAOYSA-N dec-5-ene Chemical compound [CH2]CCCC=CCCCC DIBHLCJAJIKHGB-UHFFFAOYSA-N 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- CDOOAUSHHFGWSA-OWOJBTEDSA-N (e)-1,3,3,3-tetrafluoroprop-1-ene Chemical compound F\C=C\C(F)(F)F CDOOAUSHHFGWSA-OWOJBTEDSA-N 0.000 description 3
- LDTMPQQAWUMPKS-OWOJBTEDSA-N (e)-1-chloro-3,3,3-trifluoroprop-1-ene Chemical compound FC(F)(F)\C=C\Cl LDTMPQQAWUMPKS-OWOJBTEDSA-N 0.000 description 3
- NDMMKOCNFSTXRU-UHFFFAOYSA-N 1,1,2,3,3-pentafluoroprop-1-ene Chemical class FC(F)C(F)=C(F)F NDMMKOCNFSTXRU-UHFFFAOYSA-N 0.000 description 3
- BLTXWCKMNMYXEA-UHFFFAOYSA-N 1,1,2-trifluoro-2-(trifluoromethoxy)ethene Chemical compound FC(F)=C(F)OC(F)(F)F BLTXWCKMNMYXEA-UHFFFAOYSA-N 0.000 description 3
- BZPCMSSQHRAJCC-UHFFFAOYSA-N 1,2,3,3,4,4,5,5,5-nonafluoro-1-(1,2,3,3,4,4,5,5,5-nonafluoropent-1-enoxy)pent-1-ene Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)=C(F)OC(F)=C(F)C(F)(F)C(F)(F)C(F)(F)F BZPCMSSQHRAJCC-UHFFFAOYSA-N 0.000 description 3
- OVGRCEFMXPHEBL-UHFFFAOYSA-N 1-ethenoxypropane Chemical compound CCCOC=C OVGRCEFMXPHEBL-UHFFFAOYSA-N 0.000 description 3
- FXRLMCRCYDHQFW-UHFFFAOYSA-N 2,3,3,3-tetrafluoropropene Chemical compound FC(=C)C(F)(F)F FXRLMCRCYDHQFW-UHFFFAOYSA-N 0.000 description 3
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 3
- QMIWYOZFFSLIAK-UHFFFAOYSA-N 3,3,3-trifluoro-2-(trifluoromethyl)prop-1-ene Chemical group FC(F)(F)C(=C)C(F)(F)F QMIWYOZFFSLIAK-UHFFFAOYSA-N 0.000 description 3
- GVEUEBXMTMZVSD-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,6-nonafluorohex-1-ene Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C=C GVEUEBXMTMZVSD-UHFFFAOYSA-N 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 3
- 150000001733 carboxylic acid esters Chemical class 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 238000005796 dehydrofluorination reaction Methods 0.000 description 3
- 238000002845 discoloration Methods 0.000 description 3
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- 239000007970 homogeneous dispersion Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 235000013824 polyphenols Nutrition 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 150000003573 thiols Chemical class 0.000 description 3
- KBMBVTRWEAAZEY-UHFFFAOYSA-N trisulfane Chemical compound SSS KBMBVTRWEAAZEY-UHFFFAOYSA-N 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 2
- QAERDLQYXMEHEB-UHFFFAOYSA-N 1,1,3,3,3-pentafluoroprop-1-ene Chemical compound FC(F)=CC(F)(F)F QAERDLQYXMEHEB-UHFFFAOYSA-N 0.000 description 2
- FVKFHMNJTHKMRX-UHFFFAOYSA-N 3,4,6,7,8,9-hexahydro-2H-pyrimido[1,2-a]pyrimidine Chemical compound C1CCN2CCCNC2=N1 FVKFHMNJTHKMRX-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 125000002704 decyl 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])* 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- SNWKNPMDQONHKK-UHFFFAOYSA-N methyl 2-sulfanylpropanoate Chemical compound COC(=O)C(C)S SNWKNPMDQONHKK-UHFFFAOYSA-N 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- YFZCNXJOYHYIGC-UHFFFAOYSA-N (2,2,2-trichloroacetyl) 2,2,2-trichloroethaneperoxoate Chemical compound ClC(Cl)(Cl)C(=O)OOC(=O)C(Cl)(Cl)Cl YFZCNXJOYHYIGC-UHFFFAOYSA-N 0.000 description 1
- MSTZXMFWGUDAOI-UHFFFAOYSA-N (2,2-dichloro-2-fluoroacetyl) 2,2-dichloro-2-fluoroethaneperoxoate Chemical compound FC(Cl)(Cl)C(=O)OOC(=O)C(F)(Cl)Cl MSTZXMFWGUDAOI-UHFFFAOYSA-N 0.000 description 1
- 125000006729 (C2-C5) alkenyl group Chemical group 0.000 description 1
- AQKYLAIZOGOPAW-UHFFFAOYSA-N 2-methylbutan-2-yl 2,2-dimethylpropaneperoxoate Chemical compound CCC(C)(C)OOC(=O)C(C)(C)C AQKYLAIZOGOPAW-UHFFFAOYSA-N 0.000 description 1
- 229920007479 Kynar® 741 Polymers 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910013075 LiBF Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013131 LiN Inorganic materials 0.000 description 1
- 229910013528 LiN(SO2 CF3)2 Inorganic materials 0.000 description 1
- 229910013386 LiN(SO2C2F3)2 Inorganic materials 0.000 description 1
- 229910013385 LiN(SO2C2F5)2 Inorganic materials 0.000 description 1
- 229910013553 LiNO Inorganic materials 0.000 description 1
- 229910013884 LiPF3 Inorganic materials 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- BHDAXLOEFWJKTL-UHFFFAOYSA-L dipotassium;carboxylatooxy carbonate Chemical compound [K+].[K+].[O-]C(=O)OOC([O-])=O BHDAXLOEFWJKTL-UHFFFAOYSA-L 0.000 description 1
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000011883 electrode binding agent Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- ACFSQHQYDZIPRL-UHFFFAOYSA-N lithium;bis(1,1,2,2,2-pentafluoroethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)C(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)C(F)(F)F ACFSQHQYDZIPRL-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 1
- YPVDWEHVCUBACK-UHFFFAOYSA-N propoxycarbonyloxy propyl carbonate Chemical compound CCCOC(=O)OOC(=O)OCCC YPVDWEHVCUBACK-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229960001922 sodium perborate Drugs 0.000 description 1
- 229940045872 sodium percarbonate Drugs 0.000 description 1
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 description 1
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/34—Introducing sulfur atoms or sulfur-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/26—Removing halogen atoms or halogen-containing groups from the molecule
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
- H01M4/623—Binders being polymers fluorinated polymers
Definitions
- the present invention relates to a process for preparing a functionalized halogenated polymer.
- the present invention also relates to the use of the functionalized halogenated polymer thus prepared in the field of batteries or fuel cells.
- Halogenated polymers are widely used in many technical fields given their unique properties in terms of thermal stability, chemical inertness and mechanical properties. They can thus be used in the fields of aeronautics, engineering, the automobile or chemical industry or in insulating materials.
- PVDF Poly(vinylidene fluoride)
- a PVDF Poly(vinylidene fluoride)
- a different molecular structure and different reactivity towards other monomers may have a significant impact for the targeted technological applications.
- Emulsion polymerization is characterized by its high productivity and results in branched products and the incorporation of functional monomers can be complex.
- Functionalization of PVDF can also be achieved by plasma processing and electron beam irradiation approaches.
- some technical limitations such as industrialization and repeatability can be difficult.
- the halogenated polymer Al is obtained by a dehydrohalogenation reaction of a halogenated polymer A comprising monomers Ml comprising at least one halogen atom, preferably fluorine, and monomeric units M4 of formula - CH(R 1 )-C(R 2 )(X)- in which X is halogen and R 1 and R 2 are as defined in the present invention.
- the thiolate compound B of formula R-S- is obtained by reaction between a compound of formula R-S-H and a base.
- the base is selected from the group consisting of LiOH, NaOH, KOH, CsOH, RbOH, Mg(OH)2, Ca(OH)2, N(C n H 2 n + i) 3 with n being an integer from 1 to 10, N,N-Diisopropylethylamine, morpholine, pyridine, pyrrolidine, Piperidine, piperazine, 4- Methylmorpholine, N,N-Diisopropylethylamine, l,8-Diazabicyclo(5.4.0)undec-7-ene , 6-(Dibutylamino)-l,8-diazabicyclo[5.4.0]undec-7-ene, l,8-Diazabicyclo[5.4.0]undec-7-ene linked to polystyrene, l,5,7-Triazabicyclo [4.4.0]dec-5-ene, 7-Methyl-l,5,7-triazabic
- the peroxide compound C is selected from organic peroxides, percarbonates, perborates and hydroperoxides.
- the thiolate compound B is of formula RS in which R is selected from the group of substituents consisting of Ci.Cis alkyl, C2-C18 alkenyl, C4.C18 cycloalkenyl, C 3.Cis cycloalkyl, Cg- Cis aryl, polyalkylene glycol, said substituent optionally carrying one or more functional groups of formula -F, -OR', -O- C(O)R', -CN, -NR' 2 , -O-Si( OR') 3 , -Si(R') 3 , -SO 3 R', -OP(O)(OR') 2 , -P(O)(OR) 2 , -C(O)OR', -C (O)R', -C(O)- S-R', -C(O)-NR'2, -NR' 3 + in which R' is independently selected for each substituent of the functional group from the group consisting of Ci.Cis
- said monomeric units Ml come from a monomer selected from the group consisting of vinyl bromide, vinyl iodide, vinyl chloride, vinylidene chloride, tetrachloroethylene, hexachloropropene, tetrachloropropene, trichloropropene, dichloropropene, difluoropropene , fluoropropene, vinylidene fluoride, vinyl fluoride, hexafluoropropene, tetrafluoroethylene, chlorotrifluoroethylene, trifluoroethylene, 2,3,3,3-tetrafluoropropene, E/Z-l, 3,3,3-tetrafluoropropene, 3,3,3-trifluoropropene, ( E/Z)-l-chloro-2,3,3,3-tetrafluoropropene, 1,2,3,3,3-pentafluoropropene, (E/Z)-l-chloro-2,
- step b) is carried out in the presence of a solvent selected from the group consisting of water, acetone, dimethylsulfoxide, dimethylformamide, N,N-dimethylacetamide, l-methyl-2-pyrrolidone, isobutyl methyl ketone and dihydrolevoglucosenone.
- a solvent selected from the group consisting of water, acetone, dimethylsulfoxide, dimethylformamide, N,N-dimethylacetamide, l-methyl-2-pyrrolidone, isobutyl methyl ketone and dihydrolevoglucosenone.
- the present invention provides a functionalized halogenated polymer comprising monomeric units M3 of formula -CH(R 1 )-C(R 2 ) (SR)- and monomeric units Ml comprising at least one halogen atom, preferably fluorine, with R, R 1 and R 2 as defined in the present application.
- the molar content of the monomeric units M3 is between 0.01 and 5%, preferably between 0.05 and 2%, in particular between 0.1 and 1% in said polymer.
- the present invention provides an electrode binder comprising said functionalized halogenated polymer according to the present invention.
- the present invention provides an electrode comprising said functionalized halogenated polymer according to the present invention.
- the present invention provides a battery comprising said electrode according to the present invention.
- Said battery may also comprise an electrolyte salt selected from the group consisting of LiCF 3 SO 3 , LiPFg, LiCIO 4 , LiBF 4 , LiB(C 2 O 4 ) 2 , LiN(SO 2 F) 2 , LiN(SO 2 CF 3 ) 2 , LiN(SO 2 C 2 F 3 ) 2 , LiN(SO 2 C 2 F 5 ) 2 , LiN(SO 2 F)(SO 2 CF 3 ), LiN(SO 2 F)(SO 2 C 2 F 5 ), LiN(SO 2 CF 3 )(SO 2 C 2 F 5 ),LiAsF 6 , LiBF 2 C 2 O 4 , LiNO 3 , LiPF3(CF 2 CF 3 ) 3 , LiBETI, LiTDI, or a mixture of these.
- the present invention relates to the use of said functionalized halogenated polymer according to the present invention in the preparation of a conductive polymer, of a solid electrolyte for fuel cells, of a hydrophilic coating, of a hydrophobic coating or a UV-absorbing coating.
- the present invention relates to a process for preparing a functionalized halogenated polymer.
- the substituents R 1 and R 2 are independently of each other selected from the group consisting of H, Ci-C 5 alkyl, Ci-C 5 (per)haloalkyl , F, Br, I and CL
- the substituents R 1 and R 2 are independently of each other selected from the group consisting of F, CF 3 , Cl and H.
- the monomeric units Ml are of formula -C(Y 1 )(Y 2 )- C(Y 3 )(Y 4 )- in which Y 1 , Y 2 , Y 3 and Y 4 are independently each other selected from the group consisting of H, Ci-C 5 alkyl, Ci-C 5 (per)haloalkyl, F, Br, I and Cl; of preferably independently of each other selected from the group consisting of F, CF3, Br, I, Cl and H, provided that the substituents Y 1 , Y 2 , Y 3 and Y 4 are not simultaneously H or C1-C5 alkyl .
- the term C1-C5 (per)haloalkyl refers to alkyl compounds comprising 1 to 5 carbon atoms and at least one halogen atom.
- the monomeric units Ml come from a monomer selected from the group consisting of vinyl bromide, vinyl iodide, vinyl chloride, vinylidene chloride, tetrachloroethylene, hexachloropropene, tetrachloropropene, trichloropropene, dichloropropene, difluoropropene, fluoropropene, fluoride vinylidene, vinyl fluoride, hexafluoropropene, tetrafluoroethylene, chlorotrifluoroethylene, trifluoroethylene, 2, 3,3,3- tetrafluoropropene, E/Z-l,3,3,3-tetrafluoropropene, 3,3,3-trifluoropropene, (E/Z)- l-chloro-
- the monomeric units Ml come from a monomer selected from the group consisting of vinylidene fluoride, vinyl fluoride, tetrafluoroethylene, chlorotrifluoroethylene, trifluoroethylene and mixtures thereof.
- the monomeric units Ml come from a monomer selected from the group consisting of vinylidene fluoride, tetrafluoroethylene, hexafluoropropene, chlorotrifluoroethylene and mixtures thereof.
- the monomeric units Ml come from vinylidene fluoride.
- the halogenated polymer Al can also comprise monomeric units Ml' originating from a comonomer compatible with vinylidene fluoride.
- Comonomers compatible with vinylidene fluoride can be halogenated (fluorinated, chlorinated, brominated or iodized) or non-halogenated.
- Suitable comonomers are for example vinyl chloride, vinyl iodide, vinyl bromide, vinyl fluoride, tetrafluoroethylene, trifluoroethylene, hexafluoropropene, trifluoropropenes and in particular 3,3,3-trifluoropropene, tetrafluoropropenes and in particular 2, 3,3,3-tetrafluoropropene or 1,3,3,3-tetrafluoropropene, hexafluoroisobutylene, perfluorobutylethylene, pentafluoropropenes and in particular
- the comonomer compatible with vinylidene fluoride may contain a chlorine, bromine or iodine atom. It may in particular be chosen from bromotrifluoroethylene, chlorofluoroethylene, chlorotrifluoroethylene and chlorotrifluoropropene.
- Chlorofluoroethylene can refer to either 1-chloro-l-fluoroethylene or l-chloro-2-fluoroethylene. The 1-chloro-1-fluoroethylene isomer is preferred.
- the chlorotrifluoropropene is preferably 1-chloro-3,3,3-trifluoropropene or 2-chloro-3,3,3-trifluoropropene.
- the halogenated polymer Al may also comprise monomeric units carrying at least one of the following functions: carboxylic acid, carboxylic acid anhydride, carboxylic acid esters, epoxy groups (such as glycidyl), amide, hydroxyl, carbonyl, mercapto, sulfide, oxazoline, phenolics, ester, ether, siloxane, sulfonic, sulfuric, phosphoric, phosphonic.
- carboxylic acid carboxylic acid anhydride
- carboxylic acid esters include epoxy groups (such as glycidyl), amide, hydroxyl, carbonyl, mercapto, sulfide, oxazoline, phenolics, ester, ether, siloxane, sulfonic, sulfuric, phosphoric, phosphonic.
- the function is introduced by a chemical reaction which may be grafting, or a copolymerization of the vinylidene fluoride (VDF) monomer with a monomer bearing at least one of said functional groups and a vinyl function capable of copolymerizing with the VDF monomer, according to techniques well known to those skilled in the art.
- the units carrying the carboxylic acid function further comprise a heteroatom chosen from oxygen, sulfur, nitrogen and phosphorus.
- the content of functional groups in said halogenated polymer Al may preferably be at least 0.01 mole%, preferably at least 0.1 mole%, and at most 15 mole%, preferably at most 10 mole%. .
- the halogenated polymer Al may also comprise monomeric units Ml" derived from (meth)acrylic acid selected from the group consisting of acrylic acid, methacrylic acid, hydroxyethyl(meth)acrylate, hydroxypropyl(meth) acrylate, hydroxyethylhexyl(meth)acrylate, styrene, vinylene carbonate, vinyl carbamate, N-vinyl acetamide, vinyl methacrylate, l-vinyl-2-pyrrolidone and methyl methacrylate, Ci-Cis esters of the acid acrylic or methacrylic acid; or a mixture thereof.
- (meth)acrylic acid selected from the group consisting of acrylic acid, methacrylic acid, hydroxyethyl(meth)acrylate, hydroxypropyl(meth) acrylate, hydroxyethylhexyl(meth)acrylate, styrene, vinylene carbonate, vinyl carbamate, N-viny
- said halogenated polymer Al is obtained by a dehydrohalogenation reaction of a halogenated polymer A.
- Said halogenated polymer A thus comprises Ml monomers as defined above and M4 monomeric units of formula -CH( R 1 )-C(R 2 )(X)- in which X is a halogen and R 1 and R 2 are as defined above.
- X is F or Cl, in particular
- the monomeric units Ml are of formula -C(Y 1 )(Y 2 )-C(Y 3 )(Y 4 )- in which Y 1 , Y 2 , Y 3 and Y 4 are independently selected from the group consisting of H, C1-C5 alkyl, C1-C5 (per)haloalkyl, F, Br, I and Cl; preferably independently of each other selected from the group consisting of F, CF3, Br, I, Cl and H, provided that the substituents Y 1 , Y 2 , Y 3 and Y 4 are not simultaneously H or C1-C5 alkyl.
- the monomeric units Ml come from a monomer selected from the group consisting of vinyl bromide, vinyl iodide, vinyl chloride, vinylidene chloride, tetrachloroethylene, hexachloropropene, tetrachloropropene, trichloropropene, dichloropropene, difluoropropene, fluoropropene, vinylidene fluoride, vinyl fluoride, hexafluoropropene, tetrafluoroethylene, chlorotrifluoroethylene, trifluoroethylene, 2, 3,3,3- tetrafluoropropene, E/Zl,3,3,3-tetrafluoropropene, 3,3,3- trifluoropropene, (E/Z)-l-chloro-2,3,3,3-tetrafluoropropene, 1,2,3,3,3-pentafluoropropene, (E/Z)-l-chloro-3
- the monomeric units Ml come from a monomer selected from the group consisting of vinylidene fluoride, vinyl fluoride, tetrafluoroethylene, chlorotrifluoroethylene, trifluoroethylene and mixtures thereof.
- the monomeric units Ml come from a monomer selected from the group consisting of vinylidene fluoride, tetrafluoroethylene, hexafluoropropene, chlorotrifluoroethylene and mixtures thereof.
- the monomeric units Ml come from vinylidene fluoride.
- the halogenated polymer A comprises monomeric units Ml derived from vinylidene fluoride and monomeric units M4 of formula -CH(R 1 )-C(R 2 ) (X)- in which X is a halogen and R 1 and R 2 are as defined above.
- the halogenated polymer A may also comprise monomeric units Ml' originating from a comonomer compatible with vinylidene fluoride.
- Comonomers compatible with vinylidene fluoride can be halogenated (fluorinated, chlorinated, brominated or iodized) or non-halogenated.
- the comonomer compatible with vinylidene fluoride may contain a chlorine, bromine or iodine atom. It can in particular be chosen from bromotrifluoroethylene, chlorofluoroethylene, chlorotrifluoroethylene and chlorotrifluoropropene.
- Chlorofluoroethylene can refer to either 1-chloro-l-fluoroethylene or l-chloro-2-fluoroethylene.
- the 1-chloro-1-fluoroethylene isomer is preferred.
- the chlorotrifluoropropene is preferably 1-chloro-3,3,3-trifluoropropene or 2-chloro-3,3,3-trifluoropropene.
- the halogenated polymer A may also comprise monomeric units carrying at least one of the following functions: carboxylic acid, carboxylic acid anhydride, carboxylic acid esters, epoxy groups (such as glycidyl), amide, hydroxyl, carbonyl, mercapto, sulfide, oxazoline, phenolics, ester, ether, siloxane, sulfonic, sulfuric, phosphoric, phosphonic.
- carboxylic acid carboxylic acid anhydride
- carboxylic acid esters include epoxy groups (such as glycidyl), amide, hydroxyl, carbonyl, mercapto, sulfide, oxazoline, phenolics, ester, ether, siloxane, sulfonic, sulfuric, phosphoric, phosphonic.
- the function is introduced by a chemical reaction which may be grafting, or a copolymerization of the vinylidene fluoride (VDF) monomer with a monomer bearing at least one of said functional groups and a vinyl function capable of copolymerizing with the VDF monomer, according to techniques well known to those skilled in the art.
- the units carrying the carboxylic acid function further comprise a heteroatom chosen from oxygen, sulfur, nitrogen and phosphorus.
- the content of functional groups in said halogenated polymer A may preferably be at least 0.01 mole%, preferably at least 0.1 mole%, and at most 15 mole%, preferably at most 10 mole%. .
- the halogenated polymer A may also comprise monomeric units Ml" derived from (meth)acrylic acid selected from the group consisting of acrylic acid, methacrylic acid, hydroxyethyl(meth)acrylate, hydroxypropyl(meth) acrylate, hydroxyethylhexyl(meth)acrylate, styrene, vinylene carbonate, vinyl carbamate, N-vinyl acetamide, vinyl methacrylate, l-vinyl-2-pyrrolidone and methyl methacrylate, Ci-Cis esters of the acid acrylic or methacrylic acid; or a mixture thereof.
- (meth)acrylic acid selected from the group consisting of acrylic acid, methacrylic acid, hydroxyethyl(meth)acrylate, hydroxypropyl(meth) acrylate, hydroxyethylhexyl(meth)acrylate, styrene, vinylene carbonate, vinyl carbamate, N-viny
- the halogenated polymer A comprises monomeric units Ml derived from vinylidene fluoride, monomeric units M4 of formula -CH(R 1 )-C(R 2 )(X)- in which a halogen and R 1 and R 2 are as defined above and optionally monomeric units Ml' as defined above, monomeric units Ml" as defined above; or a mixture of the two.
- the halogenated polymer A comprises monomeric units Ml derived from vinylidene fluoride, monomeric units M4 of formula -CH(R 1 )-C(R 2 )(X)- in which X is a halogen and R 1 and R 2 are as defined above and optionally monomeric units Ml' originating from a monomer selected from the group consisting of tetrafluoroethylene, trifluoroethylene, vinyl acetate, methyl vinyl ether, chlorotrifluoroethylene and hexafluoropropene or a mixture thereof, and monomeric units Ml" derived from a monomer selected from the group consisting of acrylic acid, methacrylic acid, hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate, hydroxyethylhexyl(meth)acrylate, styrene, vinylene carbonate, vinyl carbamate, N-vinyl acetamide, vinyl methacrylate, l
- X is preferably F or Cl, in particular X is F.
- the polymer Al is preferably prepared by dehydrofluorination of the polymer A.
- the dehydrofluorination step is carried out in the presence of a base of the alkaline hydroxide or alkaline earth hydroxide type; for example NaOH or KOH according to techniques known to those skilled in the art.
- the base can be used in the form of an aqueous solution with a concentration of 10 to 80% by weight based on the total weight of the solution.
- This step is preferably carried out at a temperature of 15°C to 80°C.
- This step can also be carried out in the presence of a solvent, for example an alcohol or water or a mixture of the two.
- step b) of the present process said halogenated polymer Al is brought into contact with a thiolate compound B of formula RS- in the presence of a peroxide compound C.
- said peroxide compound C is selected from organic peroxides, percarbonates, perborates and hydroperoxides.
- perborates we can cite sodium perborate, potassium perborate or lithium perborate.
- percarbonates we can cite sodium percarbonate, potassium percarbonate or lithium percarbonate.
- H2O2 bis-acylperoxides of formula (Rf-C(O)- 0)2 with Rf being C1-C10 (per)haloalkyl, C1-C10 (per)fluoropolyoxyalkylene in particular bis-trichloroacetyl peroxide and bis-dichlorofluoroacetylperoxide; dialkylperoxides of formula (RH- 0)2 with RH being C1-C10 alkyl, in particular diterbutylperoxide (DTBP); sodium or potassium persulfate; sodium or potassium perphosphate; dialkylperoxydicarbonates in which the alkyl group contains from 1 to 8 carbon atoms such as di-n-propyl-peroxydicarbonate or diisopropylperoxydicarbonate; alkyl peroxyesters such as tert-amylperoxypivalate or ter
- the peroxide compound C is H2O2.
- the use of hydrogen peroxide makes it possible to avoid the presence of organic impurities or additional processing steps such as precipitation or extractions in the presence of organic solvents which consume energy. This type of impurity can affect performance in certain applications in the electronic field.
- the use of hydrogen peroxide also makes it possible to avoid the presence of potentially toxic or flammable organic solvents.
- the thiolate compound B has the formula R-S-.
- this is obtained by reaction between a compound of formula R-S-H and a base.
- said base may be selected from the group consisting of LiOH, NaOH, KOH, CsOH, RbOH, Mg(OH)2, Ca(OH)2, N(CnH2n+l)3 with n being an integer from 1 to 10, N,N- Diisopropylethylamine, morpholine, pyridine, pyrrolidine, Piperidine, piperazine, 4- Methylmorpholine, N,N-Diisopropylethylamine, l,8-Diazabicyclo(5.4.0)undec-7-ene, 6- (Dibutylamino)- l,8-diazabicyclo[5.4.0]undec-7-ene, l,8-Diazabicyclo[5.4.0]undec-7-ene bonded to polystyrene, l,5,7-Triazabicyclo[4.4.0]dec- 5-ene, 7-Methyl-l,5,7-triazabicyclo[4.4.0]dec
- the substituent R is a hydrocarbon.
- hydrocarbon refers to a substituent comprising from 1 to 150 carbon atoms, preferably from 1 to 75 carbon atoms, in particular from 1 to 30 carbon atoms.
- the substituent R is selected from the group of substituents consisting of Ci-Cis alkyl, C2-C18 alkenyl, C4-C18 cycloalkenyl, C3-C18 cycloalkyl, Cg-Cis aryl, polyalkylene glycol, said substituent optionally carrying a or several functional groups of formula -F, -OR', -OC(O)R', -CN, -NR' 2 , -0-Si(0R')3, -Si(R')s, -SO3R' , -OP(O)(OR') 2 , -P(O)(OR) 2 , -C(O)OR', -C(O)R', -C(O)-S-R', - C(O)-NR' 2 , -NR' 3 + in which R' is independently selected for each substituent of the functional group from the group consisting of H, C1.C18 alkyl, C 2.
- the substituent R is selected from the group of substituents consisting of Ci.C15 alkyl, C 2 .Ci 5 alkenyl, C4-C15 cycloalkenyl, C3-C15 cycloalkyl, Cg-Cis aryl, polyalkylene glycol, said substituent optionally being a carrier one or more functional groups of formula -F, -OR', -OC(O)R', -CN, -NR' 2 , -O-Si(OR') 3 , -Si(R') 3 , -SO3R', -OP(O)(OR') 2 , -P(O)(OR) 2 , - C(O)OR', -C(O)R', -C(O)-S-R ', -C(O)-NR' 2 , -NR' 3 + in which R' is independently selected for each substituent of the functional group from the group consisting of H, C
- the substituent R is selected from the group of substituents consisting of C1.C10 alkyl, C 2.Cio alkenyl, C4-C10 cycloalkenyl, C3-C10 cycloalkyl, Cg-Cio aryl, polyalkylene glycol, said substituent optionally carrying 'one or more functional groups of formula -F, -OR', -OC(O)R', -CN, -NR' 2 , -0-Si(0R')3, -Si(R')s, - SO3R', -OP(O)(OR') 2 , -P(O)(OR) 2 , -C(O)OR', -C(O)R', -C(O)-S-R' , -C(O)-NR' 2 , -NR' 3 + in which R' is independently selected for each substituent of the functional group from the group consisting of H, C1.C10 alkyl, C
- the substituent R is selected from the group of substituents consisting of Ci.C 5 alkyl, C 2 .C 5 alkenyl, C4-C5 cycloalkenyl, C3-C5 cycloalkyl, Cg aryl, polyalkylene glycol, said substituent optionally carrying 'one or more functional groups of formula -F, -OR', -OC(O)R', -CN, -NR' 2 , -O-Si(OR') 3 , -Si(R') 3 , - SO3R', -OP(O)(OR') 2 , -P(O)(OR) 2 , - C(O)OR', -C(O)R', -C(O)-S-R' , -C(O)-NR' 2 , -NR' 3 + in which R' is independently selected for each substituent of the functional group from the group consisting of H, C1.C5 alkyl
- the substituent R is selected from the group of substituents consisting of C1.C5 alkyl, Cg aryl, polyalkylene glycol, said substituent optionally carrying one or more functional groups of formula -F, -OR', -OC( O)R', -CN, -NR'2, -O-Si(OR') 3 , -S ⁇ (R') 3 , -SO3R', -OP(O)(OR') 2 , -P(O )(OR) 2 , -C(O)OR', -C(O)R', -C(O)-S-R', -C(O)-NR' 2 , - NR' 3 + in which R' is independently selected for each functional group substituent from the group consisting of H, C1-C5 alkyl, C 2 -C 5 alkenyl, C4 -C5 cycloalkenyl, C 3 -C 5 cycloalkyl, C
- the substituent R is selected from the group of substituents consisting of C1.C5 alkyl, Cg aryl, polyalkylene glycol, said substituent optionally carrying one or more functional groups of formula -F, -OR', -OC (O)R', -CN, -NR' 2 , -C(O)OR', -C(O)R', -C(O)-NR' 2 , -NR' 3 + in which R' is independently selected for each functional group substituent from the group consisting of H, C1.C5 alkyl, C 2 . C 5 alkenyl, C4-C5 cycloalkenyl, C 3 .C 5 cycloalkyl, Cg aryl and polyalkylene glycol.
- polyalkylene glycol refers in particular to compounds of formula -CH 2 CH 2 (OCH 2 CH 2 ) n -OCH 3 or -CH 2 CH 2 O(CH 2 CH 2 O) n -CH 3 or -CH 2 CH 2 C(O)NH- CH 2 CH 2 O-(CH 2 CH 2 O)CH 3 OR -(CH 2 CH 2 O) n -CH 2 CO 2 H or -CH 2 CH 2 ( OCH 2 CH 2 ) n -OCH 2 CH 2 SH or - (CH 2 CH 2 O) n -CH 2 CH 2 CO 2 H or to compounds comprising polyethylene glycol units - (CH 2 CH 2 O) n and/ or polypropylene glycol (OCH(CH 3 )CH 2 ) n distributed randomly or in bulk; or any of the above formulas in which one or more hydrogen atoms are substituted by a fluorine atom; with n an integer from 1 to 100, advantageously from 1 to 75, preferably from 1
- R 8 , R 9 and R 10 are independently of each other selected from the group consisting of H, F, Cl, C1-C5 alkyl.
- R 8 , R 9 and R 10 are independently of each other selected from the group consisting of H, F and Ci-C 3 alkyl.
- step b) of the present process is carried out in the presence of a solvent.
- Said solvent may be an organic solvent capable of solubilizing compounds B and C.
- said solvent may be water.
- said solvent can be selected from the group consisting of water, acetone, dimethylsulfoxide, dimethylformamide, N,N-dimethylacetamide, l-methyl-2-pyrrolidone, isobutyl methyl ketone and dihydrolevoglucosenone.
- the solvent is water. This makes it possible to avoid organic impurities which would require the implementation of additional purification steps.
- step b) is carried out at a temperature of 10°C to 80°C, preferably 10°C to 50°C.
- step b) is carried out in the presence of a thiolate compound B as described above in the presence of hydrogen peroxide H2O2 and water.
- the thiolate compound B and hydrogen peroxide being soluble in water, this makes it possible to combine additional advantages, even if the process can be carried out with good yields with other peroxide compounds C or in another solvent .
- the particularly preferred use of H2O2 and water makes it possible to carry out the process at a temperature of 10°C to 50°C with good yields without the use of potentially flammable or toxic organic solvents, in conditions respectful of the environment and not requiring excessive energy consumption.
- step b) of the thiolate compound B rather than its thiol precursor (RSH) makes it possible to facilitate the functionalization reaction of the polymer. Indeed, it was surprisingly observed that the thiolate compound B was very easily activated by the peroxide compound C, in particular H2O2, compared to the thiol precursor. The functionalization of the halogenated polymer Al is thus facilitated by implementing step b) of the present process compared to a step using a thiol derivative.
- step b) allows the formation of a halogenated polymer A2.
- Said polymer A2 comprises monomeric units M3 of formula -CHfR 1 )- C(R 2 ) (SR)- and said monomeric units Ml comprising at least one halogen atom, preferably fluorine; R, R 1 and R 2 being as defined above.
- the monomeric units Ml are of formula -C(Y 1 )(Y 2 )- C(Y 3 )(Y 4 )- in which Y 1 , Y 2 , Y 3 and Y 4 are independently each other selected from the group consisting of H, C1-C5 alkyl, C1-C5 (per)haloalkyl, F, Br, I and Cl; preferably independently of each other selected from the group consisting of F, CF 3 , Cl, Br, I and H; provided that the Y 1 , Y 2 , Y 3 and Y 4 substituents are not simultaneously H or Ci-C 5 alkyl.
- the monomeric units Ml come from a monomer selected from the group consisting of vinyl bromide, vinyl iodide, vinyl chloride, vinylidene chloride, tetrachloroethylene, hexachloropropene, tetrachloropropene, trichloropropene, dichloropropene, difluoropropene, fluoropropene, fluoride vinylidene, vinyl fluoride, hexafluoropropene, tetrafluoroethylene, chlorotrifluoroethylene, trifluoroethylene, 2, 3,3,3- tetrafluoropropene, E/Z-l,3,3,3-tetrafluoropropene, 3,3,3-trifluoropropene, (E/Z)- l-chloro-2,3,3,3-tetrafluoropropene, 1,2,3,3,3-pentafluoropropene, (E/Z)-l-chloro-2
- the monomeric units Ml come from a monomer selected from the group consisting of vinylidene fluoride, vinyl fluoride, tetrafluoroethylene, chlorotrifluoroethylene, trifluoroethylene and mixtures thereof.
- the monomeric units Ml come from a monomer selected from the group consisting of vinylidene fluoride, tetrafluoroethylene, hexafluoropropene, chlorotrifluoroethylene and mixtures thereof.
- the monomeric units Ml come from vinylidene fluoride.
- the halogenated polymer A2 comprises monomeric units Ml derived from vinylidene fluoride and monomeric units M3 of formula -CH(R 1 )-C(R 2 ) (SR)- with R, R 1 and R 2 as defined above in this application.
- the halogenated polymer A2 can also comprise monomeric units Ml' derived from a comonomer compatible with vinylidene fluoride.
- Comonomers compatible with vinylidene fluoride can be halogenated (fluorinated, chlorinated, brominated or iodized) or non-halogenated.
- the comonomer compatible with vinylidene fluoride may contain a chlorine, bromine or iodine atom. It may in particular be chosen from bromotrifluoroethylene, chlorofluoroethylene, chlorotrifluoroethylene and chlorotrifluoropropene.
- Chlorofluoroethylene can refer to either 1-chloro-l-fluoroethylene or l-chloro-2-fluoroethylene. The 1-chloro-1-fluoroethylene isomer is preferred.
- the chlorotrifluoropropene is preferably 1-chloro-3,3,3-trifluoropropene or 2-chloro-3,3,3-trifluoropropene.
- the halogenated polymer A2 may also comprise monomeric units carrying at least one of the following functions: carboxylic acid, carboxylic acid anhydride, carboxylic acid esters, epoxy groups (such as glycidyl), amide, hydroxyl, carbonyl, mercapto, sulfide, oxazoline, phenolics, ester, ether, siloxane, sulfonic, sulfuric, phosphoric, phosphonic.
- carboxylic acid carboxylic acid anhydride
- carboxylic acid esters include epoxy groups (such as glycidyl), amide, hydroxyl, carbonyl, mercapto, sulfide, oxazoline, phenolics, ester, ether, siloxane, sulfonic, sulfuric, phosphoric, phosphonic.
- the function is introduced by a chemical reaction which may be grafting, or a copolymerization of the vinylidene fluoride (VDF) monomer with a monomer bearing at least one of said functional groups and a vinyl function capable of copolymerizing with the VDF monomer, according to techniques well known to those skilled in the art.
- the units carrying the carboxylic acid function further comprise a heteroatom chosen from oxygen, sulfur, nitrogen and phosphorus.
- the content of functional groups in said halogenated polymer A2 may preferably be at least 0.01 mol%, preferably at least 0.1 mol%, and at most 15 mol%, preferably at most 10 mol%. .
- the halogenated polymer A2 may also comprise monomeric units Ml" derived from (meth)acrylic acid selected from the group consisting of acrylic acid, methacrylic acid, hydroxyethyl(meth)acrylate, hydroxypropyl(meth) acrylate, hydroxyethylhexyl(meth)acrylate, styrene, vinylene carbonate, vinyl carbamate, N-vinyl acetamide, vinyl methacrylate, l-vinyl-2-pyrrolidone and methyl methacrylate, Ci-Cis esters of the acid acrylic or methacrylic acid; or a mixture thereof.
- (meth)acrylic acid selected from the group consisting of acrylic acid, methacrylic acid, hydroxyethyl(meth)acrylate, hydroxypropyl(meth) acrylate, hydroxyethylhexyl(meth)acrylate, styrene, vinylene carbonate, vinyl carbamate, N-vin
- the halogenated polymer A2 comprises monomeric units Ml derived from vinylidene fluoride, monomeric units M3 of formula -CH(R 1 )-C(R 2 )(SR)- with R, R 1 and R 2 as defined above and optionally monomeric units Ml' as defined above, monomeric units Ml" as defined above; or a mixture of the two.
- the halogenated polymer A2 comprises monomeric units Ml derived from vinylidene fluoride, monomeric units M3 of formula -CH(R 1 )-C(R 2 ) (SR)- with R, R 1 and R 2 such that defined above and optionally monomeric units Ml' derived from a monomer selected from the group consisting of tetrafluoroethylene, trifluoroethylene, vinyl acetate, methyl vinyl ether, chlorotrifluoroethylene and hexafluoropropene or a mixture thereof, and monomeric units Ml" derived of a monomer selected from the group consisting of acrylic acid, methacrylic acid, hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate, hydroxyethylhexyl(meth)acrylate, styrene, vinylene carbonate, vinyl carbamate, N- vinyl acetamide, vinyl methacrylate, l-vinyl-2-pyrroli
- the molar content of the monomeric units M3 in said polymer A2 is between 0.01 and 5%, preferably between 0.05 and 2%, in particular between 0.1 and 1%.
- a molar content of the monomeric units M3 in said polymer A2 between 0.01 and 1%, in particular between 0.1 and 1% is particularly preferred when the polymer A2 is used as a binder in a battery. In this molar content range, the M3 monomeric units have an impact on the performance of batteries using said A2 polymer as a binder.
- Polymer A2 as described in the present application can be used in numerous applications.
- said polymer A2 can be used as a binder for an electrode (cathode or anode).
- an electrode comprising said polymer A2 is provided.
- a battery comprising said electrode is also provided.
- said polymer A2 can be used in the preparation of a conductive polymer, a solid electrolyte for fuel cells, a hydrophilic coating, a hydrophobic coating or a UV absorbing coating .
- Example 1 5g of Kynar® 741 PVDF powder are stirred in 55 ml of a 10% ethanol solution in water. To this mixture, 2.5 ml of a NaOH solution (50% by weight in water) are added and the reaction medium is stirred for 24 hours at room temperature. A discoloration of the powder is observed indicating that the dehydrofluorination reaction has taken place (from white to brown or black). The dehydrofluorinated PVDF is isolated by filtration and washed with water until a colorless filtrate is obtained. The dehydrofluorinated PVDF is then dried at 50°C for 24 h.
- Example 1 is reproduced using 18 ml of a 50% NaOH solution in water.
- Example 2 is reproduced with the addition of 0.05 g of sodium dodecyl sulfate in addition to 18 ml of a 50% NaOH solution in water.
- PVDF a dehydrofluorinated PVDF is obtained.
- the powder is characterized by 1 H NMR (Bruker Avance III 400 with a BBFO+ 5mm probe).
- the sample is dissolved in (CDshCO or (CDshSO.
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Abstract
The present invention relates to a method for preparing a functionalized halogenated polymer, comprising the steps of: a) providing a halogenated polymer A1 comprising monomer units M1 comprising at least one halogen atom, preferably fluorine atom, and monomer units M2 comprising at least one carbon-carbon double bond –C(R1)=C(R2)-; b) bringing said halogenated polymer A1 into contact with a thiolate compound B of formula R-S- in the presence of a peroxide compound C to form a polymer A2 comprising monomer units M3 of formula –CH(R1)-C(R2)(SR)- and said monomer units M1 comprising at least one halogen atom, preferably fluorine atom; R1 and R2 being independently of one another selected from the group consisting of H, C1-C5 alkyl, C1-C5 haloalkyl, F, Br, I and Cl; R being an optionally functionalized hydrocarbon substituent.
Description
Titre :
éné fonctionnalisé et
édé de
de celui-ci Title : functionalized ene and ed of of this one
Domaine technique de l'invention Technical field of the invention
La présente invention concerne un procédé de préparation d'un polymère halogéné fonctionnalisé. La présente invention concerne également l'utilisation du polymère halogéné fonctionnalisé ainsi préparé dans le domaine des batteries ou des piles à combustibles. The present invention relates to a process for preparing a functionalized halogenated polymer. The present invention also relates to the use of the functionalized halogenated polymer thus prepared in the field of batteries or fuel cells.
Arrière-plan technologique de l'invention Technological background of the invention
Les polymères halogénés sont largement utilisés dans de nombreux domaines techniques compte tenu de leurs propriétés uniques en terme de stabilité thermique, d'inertie chimique et de propriétés mécaniques. Ils peuvent ainsi être utilisés dans les domaines de l'aéronautique, de l'ingénierie, de l'industrie automobile ou chimique ou dans les matériaux isolants. Halogenated polymers are widely used in many technical fields given their unique properties in terms of thermal stability, chemical inertness and mechanical properties. They can thus be used in the fields of aeronautics, engineering, the automobile or chemical industry or in insulating materials.
Le poly(fluorure de vinylidène) (PVDF) est notamment préféré dans de nombreux domaines d'applications tels que les matériaux piézoélectriques, le stockage de l'énergie ou le traitement de l'eau. Le PVDF peut être préparé par des procédés en suspension ou en émulsion. Suivant le procédé utilisé, le PVDF peut présenter une structure moléculaire différente et une réactivité différente vis-à-vis d'autres monomères. La différence de structure ainsi que la fonctionnalisation éventuelle de la chaîne polymérique peuvent avoir un impact important pour les applications technologique visées. Poly(vinylidene fluoride) (PVDF) is particularly preferred in many fields of application such as piezoelectric materials, energy storage or water treatment. PVDF can be prepared by suspension or emulsion processes. Depending on the process used, PVDF may have a different molecular structure and different reactivity towards other monomers. The difference in structure as well as the possible functionalization of the polymer chain can have a significant impact for the targeted technological applications.
La polymérisation en émulsion se caractérise par sa productivité élevée et donne des produits ramifiés et l’incorporation de monomères fonctionnels peut s'avérer complexe. La fonctionnalisation du PVDF peut également être réalisée par des approches de traitement plasma et d’irradiation par faisceau d’électrons. Cependant, certaines limitations techniques telles que l’industrialisation et la répétabilité peuvent être difficiles. Emulsion polymerization is characterized by its high productivity and results in branched products and the incorporation of functional monomers can be complex. Functionalization of PVDF can also be achieved by plasma processing and electron beam irradiation approaches. However, some technical limitations such as industrialization and repeatability can be difficult.
Il existe donc un besoin pour une nouvelle méthode de préparation de polymère halogéné simple, efficace et avec un impact environnemental limité. There is therefore a need for a new method of preparing halogenated polymer that is simple, effective and with limited environmental impact.
Résumé de l'invention Summary of the invention
Selon un premier aspect, la présente invention fournit un procédé de préparation d'un polymère halogéné fonctionnalisé comprenant les étapes de : a) Fourniture d'un polymère halogéné Al comprenant des unités monomériques Ml comprenant au moins un atome d'halogène, de préférence de fluor, et des unités
monomériques M2 comprenant au moins une double liaison carbone-carbone - C(R1)=C(R2)- ; b) Mise en contact dudit polymère halogéné Al avec un composé thiolate B de formule R-S- en présence d'un composé peroxyde C pour former un polymère A2 comprenant des unités monomériques M3 de formule -CH(R1)-C(R2)(SR)- et lesdites unités monomériques Ml comprenant au moins un atome d'halogène, de préférence de fluor; R1 et R2 étant indépendamment l'un de l'autre sélectionné parmi le groupe consistant en H, Ci-C5 alkyle, Ci-C5 (per)halogénoalkyle, F, Br, I et Cl ; R étant un substituant hydrocarbure optionnellement fonctionnalisé.According to a first aspect, the present invention provides a process for preparing a functionalized halogenated polymer comprising the steps of: a) Providing a halogenated polymer Al comprising monomeric units Ml comprising at least one halogen atom, preferably fluorine, and units M2 monomers comprising at least one carbon-carbon double bond - C(R 1 )=C(R 2 )-; b) Bringing said halogenated polymer Al into contact with a thiolate compound B of formula RS- in the presence of a peroxide compound C to form a polymer A2 comprising monomeric units M3 of formula -CH(R 1 )-C(R 2 ) (SR)- and said monomeric units Ml comprising at least one halogen atom, preferably fluorine; R 1 and R 2 being independently selected from the group consisting of H, Ci-C 5 alkyl, Ci-C 5 (per)haloalkyl, F, Br, I and Cl; R being an optionally functionalized hydrocarbon substituent.
Il a été observé de manière surprenante qu'un polymère halogéné pouvait être facilement fonctionnalisé dans des conditions opératoires douces avec un bon rendement d'incorporation de la fonctionnalisation. It was surprisingly observed that a halogenated polymer could be easily functionalized under mild operating conditions with a good efficiency of incorporation of the functionalization.
Selon un mode de réalisation préféré, le polymère halogéné Al est obtenu par une réaction de déshydrohalogénation d'un polymère halogéné A comprenant des monomériques Ml comprenant au moins un atome d'halogène, de préférence de fluor, et des unités monomériques M4 de formule -CH(R1)-C(R2)(X)- dans laquelle X est un halogène et R1 et R2 sont tels que définis dans la présente invention. According to a preferred embodiment, the halogenated polymer Al is obtained by a dehydrohalogenation reaction of a halogenated polymer A comprising monomers Ml comprising at least one halogen atom, preferably fluorine, and monomeric units M4 of formula - CH(R 1 )-C(R 2 )(X)- in which X is halogen and R 1 and R 2 are as defined in the present invention.
Selon un mode de réalisation préféré, le composé thiolate B de formule R-S- est obtenu par réaction entre un composé de formule R-S-H et une base. According to a preferred embodiment, the thiolate compound B of formula R-S- is obtained by reaction between a compound of formula R-S-H and a base.
Selon un mode de réalisation préféré, la base est sélectionnée parmi le groupe consistant en LiOH, NaOH, KOH, CsOH, RbOH, Mg(OH)2, Ca(OH)2, N(CnH2n+i)3 avec n étant un entier de 1 à 10, N,N-Diisopropylethylamine, morpholine, pyridine, pyrrolidine, Piperidine, piperazine, 4- Methylmorpholine, N,N-Diisopropylethylamine, l,8-Diazabicyclo(5.4.0)undec-7-ene, 6- (Dibutylamino)-l,8-diazabicyclo[5.4.0]undec-7-ene, l,8-Diazabicyclo[5.4.0]undec-7-ene lié à du polystyrène, l,5,7-Triazabicyclo[4.4.0]dec-5-ene, 7-Methyl-l,5,7-triazabicyclo[4.4.0]dec-5-ene, 1,1,3,3-Tetramethylguanidine, 2-tert-Butyl-l,l,3,3-tetramethylguanidine, 1,5,7- Triazabicyclo[4.4.0]dec-5-ene lié à du polystyrène, 1,4-Diazabicyclo[2.2.2]octane, Quinuclidine, l,5-Diazabicyclo(4.3.0)non-5-ene, 2,6-Di-tert-butylpyridine, 2,8,9-Trimethyl-2,5,8,9-tetraza-l- phosphabicyclo[3.3.3]undecane, Cyclodiphosphazane, Lithium diisopropylamide, sodium diisopropylamide, potassium diisopropylamide, magnesium diisopropylamide, calcium diisopropylamide, rubidium diisopropylamide, lithium bis(trimethylsilyl)amide, sodium bis(trimethylsilyl)amide, potassium bis(trimethylsilyl)amide, magnesium bis(trimethylsilyl)amide, calcium bis(trimethylsilyl)amide, rubidium bis(trimethylsilyl)amide,
lithium tetramethylpiperidide, sodium tetramethylpiperidide, potassium tetramethylpiperidide, magnesium tetramethylpiperidide, calcium tetramethylpiperidide, rubidium tetramethylpiperidide, [18-crown-6]-KHF2, KHF2, N,N'-diisopropylimidazonium, bifluorure, tetrabutylammonium, N(CnH2n+i)4 OH- avec n étant un entier de 1 à 10. According to a preferred embodiment, the base is selected from the group consisting of LiOH, NaOH, KOH, CsOH, RbOH, Mg(OH)2, Ca(OH)2, N(C n H 2 n + i) 3 with n being an integer from 1 to 10, N,N-Diisopropylethylamine, morpholine, pyridine, pyrrolidine, Piperidine, piperazine, 4- Methylmorpholine, N,N-Diisopropylethylamine, l,8-Diazabicyclo(5.4.0)undec-7-ene , 6-(Dibutylamino)-l,8-diazabicyclo[5.4.0]undec-7-ene, l,8-Diazabicyclo[5.4.0]undec-7-ene linked to polystyrene, l,5,7-Triazabicyclo [4.4.0]dec-5-ene, 7-Methyl-l,5,7-triazabicyclo[4.4.0]dec-5-ene, 1,1,3,3-Tetramethylguanidine, 2-tert-Butyl-l ,l,3,3-tetramethylguanidine, 1,5,7-Triazabicyclo[4.4.0]dec-5-ene linked to polystyrene, 1,4-Diazabicyclo[2.2.2]octane, Quinuclidine, l,5-Diazabicyclo (4.3.0)non-5-ene, 2,6-Di-tert-butylpyridine, 2,8,9-Trimethyl-2,5,8,9-tetraza-l-phosphabicyclo[3.3.3]undecane, Cyclodiphosphazane , Lithium diisopropylamide, sodium diisopropylamide, potassium diisopropylamide, magnesium diisopropylamide, calcium diisopropylamide, rubidium diisopropylamide, lithium bis(trimethylsilyl)amide, sodium bis(trimethylsilyl)amide, potassium bis(trimethylsilyl)amide, magnesium bis(trimethylsilyl)amide, calcium bis( trimethylsilyl)amide, rubidium bis(trimethylsilyl)amide, lithium tetramethylpiperidide, sodium tetramethylpiperidide, potassium tetramethylpiperidide, magnesium tetramethylpiperidide, calcium tetramethylpiperidide, rubidium tetramethylpiperidide, [18-crown-6]-KHF2, KHF2, N,N'-diisopropylimidazonium, bifluoride, tetrabutylammonium, N(C n H2n+i)4 OH- with n being an integer from 1 to 10.
Selon un mode de réalisation préféré, le composé peroxyde C est sélectionné parmi les peroxydes organiques, percarbonates, perborates et hydroperoxydes. According to a preferred embodiment, the peroxide compound C is selected from organic peroxides, percarbonates, perborates and hydroperoxides.
Selon un mode de réalisation préféré, le composé thiolate B est de formule R-S dans laquelle R est sélectionné parmi le groupe de substituants consistant en Ci.Cis alkyle, C2-C18 alkényle, C4.C18 cycloalkényle, C3.Cis cycloalkyle, Cg-Cis aryle, polyalkylene glycol, ledit substituant étant optionnellement porteur d'un ou plusieurs groupements fonctionnels de formule -F, -OR', -O- C(O)R', -CN, -NR'2, -O-Si(OR')3, -Si(R')3, -SO3R', -O-P(O)(OR')2, -P(O)(OR)2, -C(O)OR', -C(O)R', -C(O)- S-R', -C(O)-NR'2, -NR'3 + dans laquelle R' est indépendamment sélectionné pour chaque substituant du groupement fonctionnel parmi le groupe consistant en H, Ci-Cis alkyle, C2-C18 alkényle, C4-C18 cycloalkényle, C3.Cis cycloalkyle, Cg-Cis aryle, polyalkylene glycol. According to a preferred embodiment, the thiolate compound B is of formula RS in which R is selected from the group of substituents consisting of Ci.Cis alkyl, C2-C18 alkenyl, C4.C18 cycloalkenyl, C 3.Cis cycloalkyl, Cg- Cis aryl, polyalkylene glycol, said substituent optionally carrying one or more functional groups of formula -F, -OR', -O- C(O)R', -CN, -NR' 2 , -O-Si( OR') 3 , -Si(R') 3 , -SO 3 R', -OP(O)(OR') 2 , -P(O)(OR) 2 , -C(O)OR', -C (O)R', -C(O)- S-R', -C(O)-NR'2, -NR' 3 + in which R' is independently selected for each substituent of the functional group from the group consisting of H, Ci-Cis alkyl, C2-C18 alkenyl, C4-C18 cycloalkenyl, C 3 .Cis cycloalkyl, Cg-Cis aryl, polyalkylene glycol.
Selon un mode de réalisation préféré, lesdites unités monomériques Ml sont issues d'un monomère sélectionné parmi le groupe consistant en bromure de vinyle, iodure de vinyle, chlorure de vinyle, chlorure de vinylidène, tétrachloroéthylène, hexachloropropène, tétrachloropropène, trichloropropène, dichloropropène, difluoropropène, fluoropropène, fluorure de vinylidène, fluorure de vinyle, hexafluoropropène, tétrafluoroéthylène, chlorotrifluoroéthylène, trifluoroéthylène, 2,3,3,3-tétrafluoropropène, E/Z-l, 3,3,3- tétrafluoropropène, 3,3,3-trifluoropropène, (E/Z)-l-chloro-2,3,3,3-tétrafluoropropène, 1,2,3,3,3-pentafluoropropène, (E/Z)-l-chloro-3,3,3-trifluoropropène, 2-chloro-3,3,3- trifluoropropène, et les mélanges de ceux-ci. According to a preferred embodiment, said monomeric units Ml come from a monomer selected from the group consisting of vinyl bromide, vinyl iodide, vinyl chloride, vinylidene chloride, tetrachloroethylene, hexachloropropene, tetrachloropropene, trichloropropene, dichloropropene, difluoropropene , fluoropropene, vinylidene fluoride, vinyl fluoride, hexafluoropropene, tetrafluoroethylene, chlorotrifluoroethylene, trifluoroethylene, 2,3,3,3-tetrafluoropropene, E/Z-l, 3,3,3-tetrafluoropropene, 3,3,3-trifluoropropene, ( E/Z)-l-chloro-2,3,3,3-tetrafluoropropene, 1,2,3,3,3-pentafluoropropene, (E/Z)-l-chloro-3,3,3-trifluoropropene, 2 -chloro-3,3,3-trifluoropropene, and mixtures thereof.
Selon un mode de réalisation préféré, l'étape b) est mise en oeuvre en présence d'un solvant sélectionné parmi le groupe consistant en eau, acétone, diméthylsulfoxide, diméthylformamide, N,N-diméthylacétamide, l-methyl-2-pyrrolidone, isobutyle méthyle cétone et dihydrolévoglucosénone. According to a preferred embodiment, step b) is carried out in the presence of a solvent selected from the group consisting of water, acetone, dimethylsulfoxide, dimethylformamide, N,N-dimethylacetamide, l-methyl-2-pyrrolidone, isobutyl methyl ketone and dihydrolevoglucosenone.
Selon un autre aspect, la présente invention fournit un polymère halogéné fonctionnalisé comprenant des unités monomériques M3 de formule -CH(R1)-C(R2)(SR)- et des unités monomériques Ml comprenant au moins un atome d'halogène, de préférence de fluor, avec R, R1 et R2 tel que défini dans la présente demande.
Selon un mode de réalisation préféré, la teneur molaire des unités monomériques M3 est comprise entre 0,01 et 5%, de préférence entre 0,05 et 2%, en particulier entre 0,1 et 1% dans ledit polymère. According to another aspect, the present invention provides a functionalized halogenated polymer comprising monomeric units M3 of formula -CH(R 1 )-C(R 2 ) (SR)- and monomeric units Ml comprising at least one halogen atom, preferably fluorine, with R, R 1 and R 2 as defined in the present application. According to a preferred embodiment, the molar content of the monomeric units M3 is between 0.01 and 5%, preferably between 0.05 and 2%, in particular between 0.1 and 1% in said polymer.
Selon un autre aspect, la présente invention fournit un liant pour électrode comprenant ledit polymère halogéné fonctionnalisé selon la présente invention. According to another aspect, the present invention provides an electrode binder comprising said functionalized halogenated polymer according to the present invention.
Selon un autre aspect, la présente invention fournit une électrode comprenant ledit polymère halogéné fonctionnalisé selon la présente invention. According to another aspect, the present invention provides an electrode comprising said functionalized halogenated polymer according to the present invention.
Selon un autre aspect, la présente invention fournit une batterie comprenant ladite électrode selon la présente invention. Ladite batterie peut également comprendre un sel d'électrolyte sélectionné parmi le groupe consistant en LiCF3SO3, LiPFg, LiCIO4, LiBF4, LiB(C2O4)2, LiN(SO2F)2, LiN(SO2CF3)2, LiN(SO2C2F3)2, LiN(SO2C2F5)2, LiN(SO2F)(SO2CF3), LiN(SO2F)(SO2C2F5), LiN(SO2CF3)(SO2C2F5),LiAsF6, LiBF2C2O4, LiNO3, LiPF3(CF2CF3)3, LiBETI, LiTDI, ou un mélange de ceux-ci. According to another aspect, the present invention provides a battery comprising said electrode according to the present invention. Said battery may also comprise an electrolyte salt selected from the group consisting of LiCF 3 SO 3 , LiPFg, LiCIO 4 , LiBF 4 , LiB(C 2 O 4 ) 2 , LiN(SO 2 F) 2 , LiN(SO 2 CF 3 ) 2 , LiN(SO 2 C 2 F 3 ) 2 , LiN(SO 2 C 2 F 5 ) 2 , LiN(SO 2 F)(SO 2 CF 3 ), LiN(SO 2 F)(SO 2 C 2 F 5 ), LiN(SO 2 CF 3 )(SO 2 C 2 F 5 ),LiAsF 6 , LiBF 2 C 2 O 4 , LiNO 3 , LiPF3(CF 2 CF 3 ) 3 , LiBETI, LiTDI, or a mixture of these.
Selon un autre aspect, la présente invention concerne l'utilisation dudit polymère halogéné fonctionnalisé selon la présente invention dans la préparation d'un polymère conducteur, d'un électrolyte solide pour piles à combustibles, d'un revêtement hydrophile, d'un revêtement hydrophobe ou d'un revêtement absorbant l'UV. According to another aspect, the present invention relates to the use of said functionalized halogenated polymer according to the present invention in the preparation of a conductive polymer, of a solid electrolyte for fuel cells, of a hydrophilic coating, of a hydrophobic coating or a UV-absorbing coating.
Description détaillée de l'invention
Detailed description of the invention
Selon un premier aspect, la présente invention concerne un procédé de préparation d'un polymère halogéné fonctionnalisé. Ledit procédé comprend une étape a) de fourniture d'un polymère halogéné Al comprenant des unités monomériques Ml comprenant au moins un atome d'halogène, de préférence de fluor, et des unités monomériques M2 comprenant au moins une double liaison carbone-carbone -C(R1)=C(R2)-. According to a first aspect, the present invention relates to a process for preparing a functionalized halogenated polymer. Said method comprises a step a) of providing a halogenated polymer Al comprising monomeric units Ml comprising at least one halogen atom, preferably fluorine, and monomeric units M2 comprising at least one carbon-carbon double bond -C (R 1 )=C(R 2 )-.
Selon un mode de réalisation préféré, dans les unités monomériques M2 les substituants R1 et R2 sont indépendamment l'un de l'autre sélectionnés parmi le groupe consistant en H, Ci-C5 alkyle, Ci-C5 (per)halogénoalkyle, F, Br, I et CL De préférence, les substituants R1 et R2 sont indépendamment l'un de l'autre sélectionnés parmi le groupe consistant en F, CF3, Cl et H.According to a preferred embodiment, in the monomeric units M2 the substituents R 1 and R 2 are independently of each other selected from the group consisting of H, Ci-C 5 alkyl, Ci-C 5 (per)haloalkyl , F, Br, I and CL Preferably, the substituents R 1 and R 2 are independently of each other selected from the group consisting of F, CF 3 , Cl and H.
Selon un mode de réalisation préféré, les unités monomériques Ml sont de formule -C(Y1)(Y2)- C(Y3)(Y4)- dans laquelle Y1, Y2, Y3 et Y4 sont indépendamment les uns des autres sélectionnés parmi le groupe consistant en H, Ci-C5 alkyle, Ci-C5 (per)halogénoalkyle, F, Br, I et Cl ; de
préférence indépendamment les uns des autres sélectionnés parmi le groupe consistant en F, CF3, Br, I, Cl et H, à condition que les substituants Y1, Y2, Y3 et Y4 ne soient pas simultanément H ou C1-C5 alkyle. Le terme C1-C5 (per)halogénoalkyle se réfère à des composés alkyles comprenant de 1 à 5 atomes de carbone et au moins un atome d'halogène. According to a preferred embodiment, the monomeric units Ml are of formula -C(Y 1 )(Y 2 )- C(Y 3 )(Y 4 )- in which Y 1 , Y 2 , Y 3 and Y 4 are independently each other selected from the group consisting of H, Ci-C 5 alkyl, Ci-C 5 (per)haloalkyl, F, Br, I and Cl; of preferably independently of each other selected from the group consisting of F, CF3, Br, I, Cl and H, provided that the substituents Y 1 , Y 2 , Y 3 and Y 4 are not simultaneously H or C1-C5 alkyl . The term C1-C5 (per)haloalkyl refers to alkyl compounds comprising 1 to 5 carbon atoms and at least one halogen atom.
Avantageusement, les unités monomériques Ml sont issues d'un monomère sélectionné parmi le groupe consistant en bromure de vinyle, iodure de vinyle, chlorure de vinyle, chlorure de vinylidène, tétrachloroéthylène, hexachloropropène, tétrachloropropène, trichloropropène, dichloropropène, difluoropropène, fluoropropène, fluorure de vinylidène, fluorure de vinyle, hexafluoropropène, tétrafluoroéthylène, chlorotrifluoroéthylène, trifluoroéthylène, 2, 3,3,3- tétrafluoropropène, E/Z-l,3,3,3-tétrafluoropropène, 3,3,3-trifluoropropène, (E/Z)-l-chloro-Advantageously, the monomeric units Ml come from a monomer selected from the group consisting of vinyl bromide, vinyl iodide, vinyl chloride, vinylidene chloride, tetrachloroethylene, hexachloropropene, tetrachloropropene, trichloropropene, dichloropropene, difluoropropene, fluoropropene, fluoride vinylidene, vinyl fluoride, hexafluoropropene, tetrafluoroethylene, chlorotrifluoroethylene, trifluoroethylene, 2, 3,3,3- tetrafluoropropene, E/Z-l,3,3,3-tetrafluoropropene, 3,3,3-trifluoropropene, (E/Z)- l-chloro-
2.3.3.3-tétrafluoropropène, 1,2,3,3,3-pentafluoropropène, (E/Z)-l-chloro-3,3,3- trifluoropropène, 2-chloro-3,3,3-trifluoropropène, et les mélanges de ceux-ci. 2.3.3.3-tetrafluoropropene, 1,2,3,3,3-pentafluoropropene, (E/Z)-l-chloro-3,3,3-trifluoropropene, 2-chloro-3,3,3-trifluoropropene, and mixtures of these.
De préférence, les unités monomériques Ml sont issues d'un monomère sélectionné parmi le groupe consistant en fluorure de vinylidène, fluorure de vinyle, tétrafluoroéthylène, chlorotrifluoroéthylène, trifluoroéthylène et les mélanges de ceux-ci. De préférence, les unités monomériques Ml sont issues d'un monomère sélectionné parmi le groupe consistant en fluorure de vinylidène, tétrafluoroéthylène, hexafluoropropène, chlorotrifluoroéthylène et les mélanges de ceux-ci. En particulier, les unités monomériques Ml sont issues du fluorure de vinylidène. Preferably, the monomeric units Ml come from a monomer selected from the group consisting of vinylidene fluoride, vinyl fluoride, tetrafluoroethylene, chlorotrifluoroethylene, trifluoroethylene and mixtures thereof. Preferably, the monomeric units Ml come from a monomer selected from the group consisting of vinylidene fluoride, tetrafluoroethylene, hexafluoropropene, chlorotrifluoroethylene and mixtures thereof. In particular, the monomeric units Ml come from vinylidene fluoride.
Dans un mode de réalisation préféré, le polymère halogéné Al comprend des unités monomériques Ml issues du fluorure de vinylidène et des unités monomériques M2 comprenant au moins une double liaison carbone-carbone -C(R1)=C(R2)- avec R1 et R2 tels que définis ci-dessus. Dans ce mode de réalisation, le polymère halogéné Al peut également comprendre des unités monomériques Ml' issues d'un comonomère compatible avec le fluorure de vinylidène. Les comonomères compatibles avec le fluorure de vinylidène peuvent être halogénés (fluorés, chlorés, bromés ou iodés) ou non-halogénés. Des exemples de comonomères appropriés sont par exemple chlorure de vinyle, iodure de vinyle, bromure de vinyle, fluorure de vinyle, tétrafluoroéthylène, trifluoroéthylène, hexafluoropropène, les trifluoropropènes et notamment le 3,3,3-trifluoropropène, les tétrafluoropropènes et notamment le 2,3,3,3-tétrafluoropropène ou le 1,3,3,3-tétrafluoropropène, l'hexafluoroisobutylène, le perfluorobutyléthylène, les pentafluoropropènes et notamment leIn a preferred embodiment, the halogenated polymer Al comprises monomeric units Ml derived from vinylidene fluoride and monomeric units M2 comprising at least one carbon-carbon double bond -C(R 1 )=C(R 2 )- with R 1 and R 2 as defined above. In this embodiment, the halogenated polymer Al can also comprise monomeric units Ml' originating from a comonomer compatible with vinylidene fluoride. Comonomers compatible with vinylidene fluoride can be halogenated (fluorinated, chlorinated, brominated or iodized) or non-halogenated. Examples of suitable comonomers are for example vinyl chloride, vinyl iodide, vinyl bromide, vinyl fluoride, tetrafluoroethylene, trifluoroethylene, hexafluoropropene, trifluoropropenes and in particular 3,3,3-trifluoropropene, tetrafluoropropenes and in particular 2, 3,3,3-tetrafluoropropene or 1,3,3,3-tetrafluoropropene, hexafluoroisobutylene, perfluorobutylethylene, pentafluoropropenes and in particular
1.1.3.3.3-pentafluoropropène ou le 1,2,3,3,3-pentafluoropropène, les perfluoroalkylvinyléthers et notamment ceux de formule générale Rf-0-CF=CF2, Rf étant un groupement alkyle, de
préférence en Cl à C4 (des exemples préférés étant le perfluoropropylvinyléther et le perfluorométhylvinyléther), les alkylvinyléthers et notamment ceux de formule générale Rf-O- CH=CH2, Rf étant un groupement alkyle, de préférence en Cl à C4 (des exemples préférés étant le propylvinyléther et le méthylvinyléther), les alkanolates de vinyle et notamment ceux de formule générale Rf-C(O)-O-CH=CH2, Rf étant un groupement alkyle, de préférence en Cl à C4, en particulier l'acétate de vinyle. Le comonomère compatible avec le fluorure de vinylidène peut comporter un atome de chlore, de brome ou d'iode. Il peut en particulier être choisi parmi le bromotrifluoroéthylène, le chlorofluoroethylène, le chlorotrifluoroéthylène et le chlorotrifluoropropène. Le chlorofluoroéthylène peut désigner soit le 1-chloro-l- fluoroéthylène, soit le l-chloro-2-fluoroéthylène. L'isomère 1-chloro-l-fluoroéthylène est préféré. Le chlorotrifluoropropène est de préférence le l-chloro-3,3,3-trifluoropropène ou le 2- chloro-3,3,3-trifluoropropène. 1.1.3.3.3-pentafluoropropene or 1,2,3,3,3-pentafluoropropene, perfluoroalkyl vinyl ethers and in particular those of general formula Rf-0-CF=CF2, Rf being an alkyl group, of preferably from Cl to C4 (preferred examples being perfluoropropyl vinyl ether and perfluoromethyl vinyl ether), alkyl vinyl ethers and in particular those of general formula Rf-O- CH=CH2, Rf being an alkyl group, preferably from Cl to C4 (preferred examples being propyl vinyl ether and methyl vinyl ether), vinyl alkanolates and in particular those of general formula Rf-C(O)-O-CH=CH2, Rf being an alkyl group, preferably C to C4, in particular vinyl acetate . The comonomer compatible with vinylidene fluoride may contain a chlorine, bromine or iodine atom. It may in particular be chosen from bromotrifluoroethylene, chlorofluoroethylene, chlorotrifluoroethylene and chlorotrifluoropropene. Chlorofluoroethylene can refer to either 1-chloro-l-fluoroethylene or l-chloro-2-fluoroethylene. The 1-chloro-1-fluoroethylene isomer is preferred. The chlorotrifluoropropene is preferably 1-chloro-3,3,3-trifluoropropene or 2-chloro-3,3,3-trifluoropropene.
Le polymère halogéné Al peut également comprendre des unités monomériques portant au moins l'une des fonctions suivantes: acide carboxylique, anhydride d'acide carboxylique, esters d'acide carboxylique, groupes époxy (tel que le glycidyle), amide, hydroxyle, carbonyle, mercapto, sulfure, oxazoline, phénoliques, ester, éther, siloxane, sulfonique, sulfurique, phosphorique, phosphonique. La fonction est introduite par une réaction chimique qui peut être du greffage, ou une copolymérisation du monomère fluorure de vinylidène (VDF) avec un monomère portant au moins un desdits groupes fonctionnels et une fonction vinylique capable de copolymériser avec le monomère VDF, selon des techniques bien connues par l'homme du métier. Selon un mode de réalisation, les unités portant la fonction acide carboxylique comprennent en outre un hétéroatome choisi parmi l'oxygène, le soufre, l'azote et le phosphore. La teneur en groupes fonctionnels dudit polymère halogéné Al peut être de préférence d'au moins 0,01% molaire, de préférence d'au moins 0,1 % molaire, et au plus de 15% molaire, de préférence au plus 10% molaire. The halogenated polymer Al may also comprise monomeric units carrying at least one of the following functions: carboxylic acid, carboxylic acid anhydride, carboxylic acid esters, epoxy groups (such as glycidyl), amide, hydroxyl, carbonyl, mercapto, sulfide, oxazoline, phenolics, ester, ether, siloxane, sulfonic, sulfuric, phosphoric, phosphonic. The function is introduced by a chemical reaction which may be grafting, or a copolymerization of the vinylidene fluoride (VDF) monomer with a monomer bearing at least one of said functional groups and a vinyl function capable of copolymerizing with the VDF monomer, according to techniques well known to those skilled in the art. According to one embodiment, the units carrying the carboxylic acid function further comprise a heteroatom chosen from oxygen, sulfur, nitrogen and phosphorus. The content of functional groups in said halogenated polymer Al may preferably be at least 0.01 mole%, preferably at least 0.1 mole%, and at most 15 mole%, preferably at most 10 mole%. .
En particulier, le polymère halogéné Al peut également comprendre des unités monomériques Ml" issues de l'acide (méth)acrylique sélectionné parmi le groupe consistant en l'acide acrylique, l'acide méthacrylique, hydroxyéthyl(méth)acrylate, hydroxypropyl(méth)acrylate, hydroxyéthylhexyl(méth)acrylate, styrène, carbonate de vinylène, carbamate de vinyle, N-vinyle acétamide, méthacrylate de vinyle, l-vinyl-2-pyrrolidone et le méthacrylate de méthyle, les esters en Ci-Cis de l'acide acrylique ou l'acide méthacrylique ; ou un mélange de ceux-ci. In particular, the halogenated polymer Al may also comprise monomeric units Ml" derived from (meth)acrylic acid selected from the group consisting of acrylic acid, methacrylic acid, hydroxyethyl(meth)acrylate, hydroxypropyl(meth) acrylate, hydroxyethylhexyl(meth)acrylate, styrene, vinylene carbonate, vinyl carbamate, N-vinyl acetamide, vinyl methacrylate, l-vinyl-2-pyrrolidone and methyl methacrylate, Ci-Cis esters of the acid acrylic or methacrylic acid; or a mixture thereof.
Ainsi, dans un mode de réalisation particulier, le polymère halogéné Al comprend des unités monomériques Ml issues du fluorure de vinylidène, des unités monomériques M2 comprenant
au moins une double liaison carbone-carbone -C(R1)=C(R2)- avec R1 et R2 tels que définis ci- dessus et optionnellement des unités monomériques Ml' telles que définies ci-dessus, des unités monomériques Ml" telles que définies ci-dessus ou un mélange des deux. Plus particulièrement, le polymère halogéné Al comprend des unités monomériques Ml issues du fluorure de vinylidène, des unités monomériques M2 comprenant au moins une double liaison carbone-carbone -C(R1)=C(R2)- avec R1 et R2 tels que définis ci-dessus et optionnellement des unités monomériques Ml' issues d'un monomère sélectionné parmi le groupe consistant en tétrafluoroéthylène, trifluoroéthylène, acétate de vinyle, méthylvinyléther, chlorotrifluoroéthylène et hexafluoropropène ou un mélange de ceux-ci, et des unités monomériques Ml" issues d'un monomère sélectionné parmi le groupe consistant en l'acide acrylique, l'acide méthacrylique, hydroxyéthyl(méth)acrylate, hydroxypropyl(méth)acrylate, hydroxyéthylhexyl(méth)acrylate, styrène, carbonate de vinylène, carbamate de vinyle, N-vinyle acétamide, méthacrylate de vinyle, l-vinyl-2-pyrrolidone et le méthacrylate de méthyle, les esters en Ci-Cis de l'acide acrylique ou l'acide méthacrylique, ou un mélange de ceux-ci ; ou un mélange des unités monomériques Ml' et Ml". Thus, in a particular embodiment, the halogenated polymer Al comprises monomeric units Ml derived from vinylidene fluoride, monomeric units M2 comprising at least one carbon-carbon double bond -C(R 1 )=C(R 2 )- with R 1 and R 2 as defined above and optionally monomeric units Ml' as defined above, monomeric units Ml" as defined above or a mixture of the two. More particularly, the halogenated polymer Al comprises monomeric units Ml derived from vinylidene fluoride, monomeric units M2 comprising at least one carbon-carbon double bond -C(R 1 )=C(R 2 )- with R 1 and R 2 as defined above and optionally monomeric units Ml' from a monomer selected from the group consisting of tetrafluoroethylene, trifluoroethylene, vinyl acetate, methyl vinyl ether, chlorotrifluoroethylene and hexafluoropropene or a mixture thereof, and monomeric units Ml" originating from a monomer selected from the group consisting of acrylic acid, methacrylic acid, hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate, hydroxyethylhexyl( meth)acrylate, styrene, vinylene carbonate, vinyl carbamate, N-vinyl acetamide, vinyl methacrylate, l-vinyl-2-pyrrolidone and methyl methacrylate, Ci-Cis esters of acrylic acid or methacrylic acid, or a mixture thereof; or a mixture of the monomeric units Ml' and Ml".
Selon un mode de réalisation préféré, ledit polymère halogéné Al est obtenu par une réaction de déshydrohalogénation d'un polymère halogéné A. Ledit polymère halogéné A comprend ainsi des monomériques Ml telles que définies ci-dessus et des unités monomériques M4 de formule -CH(R1)-C(R2)(X)- dans laquelle X est un halogène et R1 et R2 sont tels que définis ci-dessus. De préférence X est F ou Cl, en particulier X est F. La réaction de déshydrohalogénation permet d'éliminer un composé HX issu des unités monomériques M4 pour former les unités monomériques M2 telles que décrites ci-dessus. According to a preferred embodiment, said halogenated polymer Al is obtained by a dehydrohalogenation reaction of a halogenated polymer A. Said halogenated polymer A thus comprises Ml monomers as defined above and M4 monomeric units of formula -CH( R 1 )-C(R 2 )(X)- in which X is a halogen and R 1 and R 2 are as defined above. Preferably X is F or Cl, in particular
Comme dans le polymère Al ci-dessus, dans le polymère A, les unités monomériques Ml sont de formule -C(Y1)(Y2)-C(Y3)(Y4)- dans laquelle Y1, Y2, Y3 et Y4 sont indépendamment les uns des autres sélectionnés parmi le groupe consistant en H, C1-C5 alkyle, C1-C5 (per)halogénoalkyle, F, Br, I et Cl ; de préférence indépendamment les uns des autres sélectionnés parmi le groupe consistant en F, CF3, Br, I, Cl et H, à condition que les substituants Y1, Y2, Y3 et Y4 ne soient pas simultanément H ou C1-C5 alkyle. As in the polymer Al above, in the polymer A, the monomeric units Ml are of formula -C(Y 1 )(Y 2 )-C(Y 3 )(Y 4 )- in which Y 1 , Y 2 , Y 3 and Y 4 are independently selected from the group consisting of H, C1-C5 alkyl, C1-C5 (per)haloalkyl, F, Br, I and Cl; preferably independently of each other selected from the group consisting of F, CF3, Br, I, Cl and H, provided that the substituents Y 1 , Y 2 , Y 3 and Y 4 are not simultaneously H or C1-C5 alkyl.
Avantageusement, les unités monomériques Ml sont issues d'un monomère sélectionné parmi le groupe consistant en bromure de vinyle, iodure de vinyle, chlorure de vinyle, chlorure de vinylidène, tétrachloroéthylène, hexachloropropène, tétrachloropropène, trichloropropène,
dichloropropène, difluoropropène, fluoropropène, fluorure de vinylidène, fluorure de vinyle, hexafluoropropène, tétrafluoroéthylène, chlorotrifluoroéthylène, trifluoroéthylène, 2, 3,3,3- tétrafluoropropène, E/Z-l,3,3,3-tétrafluoropropène, 3,3,3-trifluoropropène, (E/Z)-l-chloro- 2,3,3,3-tétrafluoropropène, 1,2,3,3,3-pentafluoropropène, (E/Z)-l-chloro-3,3,3- trifluoropropène, 2-chloro-3,3,3-trifluoropropène, et les mélanges de ceux-ci. Advantageously, the monomeric units Ml come from a monomer selected from the group consisting of vinyl bromide, vinyl iodide, vinyl chloride, vinylidene chloride, tetrachloroethylene, hexachloropropene, tetrachloropropene, trichloropropene, dichloropropene, difluoropropene, fluoropropene, vinylidene fluoride, vinyl fluoride, hexafluoropropene, tetrafluoroethylene, chlorotrifluoroethylene, trifluoroethylene, 2, 3,3,3- tetrafluoropropene, E/Zl,3,3,3-tetrafluoropropene, 3,3,3- trifluoropropene, (E/Z)-l-chloro-2,3,3,3-tetrafluoropropene, 1,2,3,3,3-pentafluoropropene, (E/Z)-l-chloro-3,3,3- trifluoropropene, 2-chloro-3,3,3-trifluoropropene, and mixtures thereof.
De préférence, les unités monomériques Ml sont issues d'un monomère sélectionné parmi le groupe consistant en fluorure de vinylidène, fluorure de vinyle, tétrafluoroéthylène, chlorotrifluoroéthylène, trifluoroéthylène et les mélanges de ceux-ci. De préférence, les unités monomériques Ml sont issues d'un monomère sélectionné parmi le groupe consistant en fluorure de vinylidène, tétrafluoroéthylène, hexafluoropropène, chlorotrifluoroéthylène et les mélanges de ceux-ci. En particulier, les unités monomériques Ml sont issues du fluorure de vinylidène. Preferably, the monomeric units Ml come from a monomer selected from the group consisting of vinylidene fluoride, vinyl fluoride, tetrafluoroethylene, chlorotrifluoroethylene, trifluoroethylene and mixtures thereof. Preferably, the monomeric units Ml come from a monomer selected from the group consisting of vinylidene fluoride, tetrafluoroethylene, hexafluoropropene, chlorotrifluoroethylene and mixtures thereof. In particular, the monomeric units Ml come from vinylidene fluoride.
Dans un mode de réalisation préféré, le polymère halogéné A comprend des unités monomériques Ml issues du fluorure de vinylidène et des unités monomériques M4 de formule -CH(R1)-C(R2)(X)- dans laquelle X est un halogène et R1 et R2 sont tels que définis ci-dessus. Dans ce mode de réalisation, le polymère halogéné A peut également comprendre des unités monomériques Ml' issues d'un comonomère compatible avec le fluorure de vinylidène. Les comonomères compatibles avec le fluorure de vinylidène peuvent être halogénés (fluorés, chlorés, bromés ou iodés) ou non-halogénés. Des exemples de comonomères appropriés sont par exemple chlorure de vinyle, iodure de vinyle, bromure de vinyle, fluorure de vinyle, tétrafluoroéthylène, trifluoroéthylène, hexafluoropropène, les trifluoropropènes et notamment le 3,3,3-trifluoropropène, les tétrafluoropropènes et notamment le 2,3,3,3-tétrafluoropropène ou le 1,3,3,3-tétrafluoropropène, l'hexafluoroisobutylène, le perfluorobutyléthylène, les pentafluoropropènes et notamment le 1,1,3,3,3-pentafluoropropène ou le 1,2,3,3,3- pentafluoropropène, les perfluoroalkylvinyléthers et notamment ceux de formule générale Rf- 0-CF=CF2, Rf étant un groupement alkyle, de préférence en Cl à C4 (des exemples préférés étant le perfluoropropylvinyléther et le perfluorométhylvinyléther), les alkylvinyléthers et notamment ceux de formule générale Rf-O-CH=CH2, Rf étant un groupement alkyle, de préférence en Cl à C4 (des exemples préférés étant le propylvinyléther et le méthylvinyléther), les alkanolates de vinyle et notamment ceux de formule générale Rf-C(O)-O-CH=CH2, Rf étant un groupement alkyle, de préférence en Cl à C4, en particulier l'acétate de vinyle. Le comonomère compatible avec le fluorure de vinylidène peut comporter un atome de chlore, de brome ou d'iode. Il peut en particulier être choisi parmi le bromotrifluoroéthylène, le
chlorofluoroethylène, le chlorotrifluoroéthylène et le chlorotrifluoropropène. Le chlorofluoroéthylène peut désigner soit le 1-chloro-l-fluoroéthylène, soit le l-chloro-2- fluoroéthylène. L'isomère 1-chloro-l-fluoroéthylène est préféré. Le chlorotrifluoropropène est de préférence le l-chloro-3,3,3-trifluoropropène ou le 2-chloro-3,3,3-trifluoropropène. In a preferred embodiment, the halogenated polymer A comprises monomeric units Ml derived from vinylidene fluoride and monomeric units M4 of formula -CH(R 1 )-C(R 2 ) (X)- in which X is a halogen and R 1 and R 2 are as defined above. In this embodiment, the halogenated polymer A may also comprise monomeric units Ml' originating from a comonomer compatible with vinylidene fluoride. Comonomers compatible with vinylidene fluoride can be halogenated (fluorinated, chlorinated, brominated or iodized) or non-halogenated. Examples of suitable comonomers are for example vinyl chloride, vinyl iodide, vinyl bromide, vinyl fluoride, tetrafluoroethylene, trifluoroethylene, hexafluoropropene, trifluoropropenes and in particular 3,3,3-trifluoropropene, tetrafluoropropenes and in particular 2, 3,3,3-tetrafluoropropene or 1,3,3,3-tetrafluoropropene, hexafluoroisobutylene, perfluorobutylethylene, pentafluoropropenes and in particular 1,1,3,3,3-pentafluoropropene or 1,2,3, 3,3-pentafluoropropene, perfluoroalkyl vinyl ethers and in particular those of general formula Rf- 0-CF=CF2, Rf being an alkyl group, preferably C to C4 (preferred examples being perfluoropropyl vinyl ether and perfluoromethyl vinyl ether), alkyl vinyl ethers and in particular those of general formula Rf-O-CH=CH2, Rf being an alkyl group, preferably C to C4 (preferred examples being propyl vinyl ether and methyl vinyl ether), vinyl alkanolates and in particular those of general formula Rf-C( O)-O-CH=CH2, Rf being an alkyl group, preferably C1 to C4, in particular vinyl acetate. The comonomer compatible with vinylidene fluoride may contain a chlorine, bromine or iodine atom. It can in particular be chosen from bromotrifluoroethylene, chlorofluoroethylene, chlorotrifluoroethylene and chlorotrifluoropropene. Chlorofluoroethylene can refer to either 1-chloro-l-fluoroethylene or l-chloro-2-fluoroethylene. The 1-chloro-1-fluoroethylene isomer is preferred. The chlorotrifluoropropene is preferably 1-chloro-3,3,3-trifluoropropene or 2-chloro-3,3,3-trifluoropropene.
Le polymère halogéné A peut également comprendre des unités monomériques portant au moins l'une des fonctions suivantes: acide carboxylique, anhydride d'acide carboxylique, esters d'acide carboxylique, groupes époxy (tel que le glycidyle), amide, hydroxyle, carbonyle, mercapto, sulfure, oxazoline, phénoliques, ester, éther, siloxane, sulfonique, sulfurique, phosphorique, phosphonique. La fonction est introduite par une réaction chimique qui peut être du greffage, ou une copolymérisation du monomère fluorure de vinylidène (VDF) avec un monomère portant au moins un desdits groupes fonctionnels et une fonction vinylique capable de copolymériser avec le monomère VDF, selon des techniques bien connues par l'homme du métier. Selon un mode de réalisation, les unités portant la fonction acide carboxylique comprennent en outre un hétéroatome choisi parmi l'oxygène, le soufre, l'azote et le phosphore. La teneur en groupes fonctionnels dudit polymère halogéné A peut être de préférence d'au moins 0,01% molaire, de préférence d'au moins 0,1 % molaire, et au plus de 15% molaire, de préférence au plus 10% molaire. The halogenated polymer A may also comprise monomeric units carrying at least one of the following functions: carboxylic acid, carboxylic acid anhydride, carboxylic acid esters, epoxy groups (such as glycidyl), amide, hydroxyl, carbonyl, mercapto, sulfide, oxazoline, phenolics, ester, ether, siloxane, sulfonic, sulfuric, phosphoric, phosphonic. The function is introduced by a chemical reaction which may be grafting, or a copolymerization of the vinylidene fluoride (VDF) monomer with a monomer bearing at least one of said functional groups and a vinyl function capable of copolymerizing with the VDF monomer, according to techniques well known to those skilled in the art. According to one embodiment, the units carrying the carboxylic acid function further comprise a heteroatom chosen from oxygen, sulfur, nitrogen and phosphorus. The content of functional groups in said halogenated polymer A may preferably be at least 0.01 mole%, preferably at least 0.1 mole%, and at most 15 mole%, preferably at most 10 mole%. .
En particulier, le polymère halogéné A peut également comprendre des unités monomériques Ml" issues de l'acide (méth)acrylique sélectionné parmi le groupe consistant en l'acide acrylique, l'acide méthacrylique, hydroxyéthyl(méth)acrylate, hydroxypropyl(méth)acrylate, hydroxyéthylhexyl(méth)acrylate, styrène, carbonate de vinylène, carbamate de vinyle, N-vinyle acétamide, méthacrylate de vinyle, l-vinyl-2-pyrrolidone et le méthacrylate de méthyle, les esters en Ci-Cis de l'acide acrylique ou l'acide méthacrylique ; ou un mélange de ceux-ci. In particular, the halogenated polymer A may also comprise monomeric units Ml" derived from (meth)acrylic acid selected from the group consisting of acrylic acid, methacrylic acid, hydroxyethyl(meth)acrylate, hydroxypropyl(meth) acrylate, hydroxyethylhexyl(meth)acrylate, styrene, vinylene carbonate, vinyl carbamate, N-vinyl acetamide, vinyl methacrylate, l-vinyl-2-pyrrolidone and methyl methacrylate, Ci-Cis esters of the acid acrylic or methacrylic acid; or a mixture thereof.
Ainsi, dans un mode de réalisation particulier, le polymère halogéné A comprend des unités monomériques Ml issues du fluorure de vinylidène, des unités monomériques M4 de formule -CH(R1)-C(R2)(X)- dans laquelle X est un halogène et R1 et R2 sont tels que définis ci-dessus et optionnellement des unités monomériques Ml' telles que définies ci-dessus, des unités monomériques Ml" telles que définies ci-dessus ; ou un mélange des deux. Thus, in a particular embodiment, the halogenated polymer A comprises monomeric units Ml derived from vinylidene fluoride, monomeric units M4 of formula -CH(R 1 )-C(R 2 )(X)- in which a halogen and R 1 and R 2 are as defined above and optionally monomeric units Ml' as defined above, monomeric units Ml" as defined above; or a mixture of the two.
Plus particulièrement, le polymère halogéné A comprend des unités monomériques Ml issues du fluorure de vinylidène, des unités monomériques M4 de formule -CH(R1)-C(R2)(X)- dans laquelle X est un halogène et R1 et R2 sont tels que définis ci-dessus et optionnellement des unités monomériques Ml' issues d'un monomère sélectionné parmi le groupe consistant en tétrafluoroéthylène, trifluoroéthylène, acétate de vinyle, méthylvinyléther,
chlorotrifluoroéthylène et hexafluoropropène ou un mélange de ceux-ci, et des unités monomériques Ml" issues d'un monomère sélectionné parmi le groupe consistant en l'acide acrylique, l'acide méthacrylique, hydroxyéthyl(méth)acrylate, hydroxypropyl(méth)acrylate, hydroxyéthylhexyl(méth)acrylate, styrène, carbonate de vinylène, carbamate de vinyle, N-vinyle acétamide, méthacrylate de vinyle, l-vinyl-2-pyrrolidone et le méthacrylate de méthyle, les esters en Ci-Cis de l'acide acrylique ou l'acide méthacrylique, ou un mélange de ceux-ci ; ou un mélange des unités monomériques Ml' et Ml". More particularly, the halogenated polymer A comprises monomeric units Ml derived from vinylidene fluoride, monomeric units M4 of formula -CH(R 1 )-C(R 2 )(X)- in which X is a halogen and R 1 and R 2 are as defined above and optionally monomeric units Ml' originating from a monomer selected from the group consisting of tetrafluoroethylene, trifluoroethylene, vinyl acetate, methyl vinyl ether, chlorotrifluoroethylene and hexafluoropropene or a mixture thereof, and monomeric units Ml" derived from a monomer selected from the group consisting of acrylic acid, methacrylic acid, hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate, hydroxyethylhexyl(meth)acrylate, styrene, vinylene carbonate, vinyl carbamate, N-vinyl acetamide, vinyl methacrylate, l-vinyl-2-pyrrolidone and methyl methacrylate, Ci-Cis esters of acrylic acid or methacrylic acid, or a mixture thereof; or a mixture of the monomeric units Ml' and Ml".
Dans ces différents modes de réalisation particuliers, X est de préférence F ou Cl, en particulier X est F. In these different particular embodiments, X is preferably F or Cl, in particular X is F.
Le polymère Al est de préférence préparé par déshydrofluoration du polymère A. L'étape de déshydrofluoration est mise en oeuvre en présence d'une base de type hydroxyde alcalin ou hydroxyde d'alcalino-terreux ; par exemple NaOH ou KOH selon les techniques connues de l'homme du métier. La base peut être utilisée sous la forme d'une solution aqueuse d'une concentration de 10 à 80% en poids sur base du poids total de la solution. Cette étape est de préférence mise en oeuvre à une température de 15°C à 80°C. Cette étape peut également être mise en oeuvre en présence d'un solvant, par exemple un alcool ou de l'eau ou un mélange des deux. The polymer Al is preferably prepared by dehydrofluorination of the polymer A. The dehydrofluorination step is carried out in the presence of a base of the alkaline hydroxide or alkaline earth hydroxide type; for example NaOH or KOH according to techniques known to those skilled in the art. The base can be used in the form of an aqueous solution with a concentration of 10 to 80% by weight based on the total weight of the solution. This step is preferably carried out at a temperature of 15°C to 80°C. This step can also be carried out in the presence of a solvent, for example an alcohol or water or a mixture of the two.
Dans l'étape b) du présent procédé, ledit polymère halogéné Al est mis en contact avec un composé thiolate B de formule R-S- en présence d'un composé peroxyde C.
In step b) of the present process, said halogenated polymer Al is brought into contact with a thiolate compound B of formula RS- in the presence of a peroxide compound C.
Selon un mode de réalisation préféré, ledit composé peroxyde C est sélectionné parmi les peroxydes organiques, percarbonates, perborates et hydroperoxydes. Par exemple, parmi les perborates, on peut citer le perborate de sodium, le perborate de potassium ou le perborate de lithium. Par exemple, parmi les percarbonates, on peut citer le percarbonate de sodium, le percarbonate de potassium ou le percarbonate de lithium. Par exemple, parmi les peroxydes organiques et les hydroperoxydes, on peut citer H2O2 ; bis-acylperoxydes de formule (Rf-C(O)- 0)2 avec Rf étant C1-C10 (per)haloalkyle, C1-C10 (per)fluoropolyoxyalkylène en particulier bis- trichloroacetyl peroxyde et bis-dichlorofluoroacétylperoxyde ; dialkylperoxydes de formule (RH- 0)2 avec RH étant C1-C10 alkyle, en particulier le diterbutylperoxyde (DTBP) ; le persulfate de sodium ou de potassium ; le perphospate de sodium ou de potassium ;
dialkylperoxydicarbonates dans lesquels le groupement alkyle comporte de 1 à 8 atomes de carbone tel que di-n-propyl-peroxydicarbonate ou le diisopropylperoxydicarbonate ; les peroxyesters d'alkyle tels que le tert-amylperoxypivalate ou le tert-butylperoxyisobutirate.According to a preferred embodiment, said peroxide compound C is selected from organic peroxides, percarbonates, perborates and hydroperoxides. For example, among perborates, we can cite sodium perborate, potassium perborate or lithium perborate. For example, among the percarbonates, we can cite sodium percarbonate, potassium percarbonate or lithium percarbonate. For example, among organic peroxides and hydroperoxides, we can cite H2O2; bis-acylperoxides of formula (Rf-C(O)- 0)2 with Rf being C1-C10 (per)haloalkyl, C1-C10 (per)fluoropolyoxyalkylene in particular bis-trichloroacetyl peroxide and bis-dichlorofluoroacetylperoxide; dialkylperoxides of formula (RH- 0)2 with RH being C1-C10 alkyl, in particular diterbutylperoxide (DTBP); sodium or potassium persulfate; sodium or potassium perphosphate; dialkylperoxydicarbonates in which the alkyl group contains from 1 to 8 carbon atoms such as di-n-propyl-peroxydicarbonate or diisopropylperoxydicarbonate; alkyl peroxyesters such as tert-amylperoxypivalate or tert-butylperoxyisobutirate.
En particulier, le composé peroxyde C est H2O2. En effet, l'utilisation du peroxyde d'hydrogène permet d'éviter la présence d'impuretés organiques ou des étapes supplémentaires de traitement telles que la précipitation ou des extractions en présence de solvants organiques qui sont consommatrices d'énergie. Ce type d'impuretés peut affecter les performances dans certaines applications dans le domaine électronique. L'emploi du peroxyde d'hydrogène permet d'éviter également la présence de solvant organique potentiellement toxiques ou inflammables. In particular, the peroxide compound C is H2O2. Indeed, the use of hydrogen peroxide makes it possible to avoid the presence of organic impurities or additional processing steps such as precipitation or extractions in the presence of organic solvents which consume energy. This type of impurity can affect performance in certain applications in the electronic field. The use of hydrogen peroxide also makes it possible to avoid the presence of potentially toxic or flammable organic solvents.
Composé thiolate B Thiolate compound B
Comme mentionné ci-dessus, le composé thiolate B est de formule R-S-. De préférence, celui-ci est obtenu par réaction entre un composé de formule R-S-H et une base. As mentioned above, the thiolate compound B has the formula R-S-. Preferably, this is obtained by reaction between a compound of formula R-S-H and a base.
De préférence, ladite base peut être sélectionnée parmi le groupe consistant en LiOH, NaOH, KOH, CsOH, RbOH, Mg(OH)2, Ca(OH)2, N(CnH2n+l)3 avec n étant un entier de 1 à 10, N,N- Diisopropylethylamine, morpholine, pyridine, pyrrolidine, Piperidine, piperazine, 4- Methylmorpholine, N,N-Diisopropylethylamine, l,8-Diazabicyclo(5.4.0)undec-7-ene, 6- (Dibutylamino)-l,8-diazabicyclo[5.4.0]undec-7-ene, l,8-Diazabicyclo[5.4.0]undec-7-ene lié à du polystyrène, l,5,7-Triazabicyclo[4.4.0]dec-5-ene, 7-Methyl-l,5,7-triazabicyclo[4.4.0]dec-5-ene, 1,1,3,3-Tetramethylguanidine, 2-tert-Butyl-l,l,3,3-tetramethylguanidine, 1,5,7- Triazabicyclo[4.4.0]dec-5-ene lié à du polystyrène, 1,4-Diazabicyclo[2.2.2]octane, Quinuclidine, l,5-Diazabicyclo(4.3.0)non-5-ene, 2,6-Di-tert-butylpyridine, 2,8,9-Trimethyl-2,5,8,9-tetraza-l- phosphabicyclo[3.3.3]undecane, Cyclodiphosphazane, Lithium diisopropylamide, sodium diisopropylamide, potassium diisopropylamide, magnesium diisopropylamide, calcium diisopropylamide, rubidium diisopropylamide, lithium bis(trimethylsilyl)amide, sodium bis(trimethylsilyl)amide, potassium bis(trimethylsilyl)amide, magnesium bis(trimethylsilyl)amide, calcium bis(trimethylsilyl)amide, rubidium bis(trimethylsilyl)amide, lithium tetramethylpiperidide, sodium tetramethylpiperidide, potassium tetramethylpiperidide, magnesium tetramethylpiperidide, calcium tetramethylpiperidide, rubidium tetramethylpiperidide, [18-crown-6]-KHF2, KHF2, N,N'-diisopropylimidazonium, bifluorure, tetrabutylammonium, N(CnH2n+l)4 OH- avec n étant un entier de 1 à 10. Preferably, said base may be selected from the group consisting of LiOH, NaOH, KOH, CsOH, RbOH, Mg(OH)2, Ca(OH)2, N(CnH2n+l)3 with n being an integer from 1 to 10, N,N- Diisopropylethylamine, morpholine, pyridine, pyrrolidine, Piperidine, piperazine, 4- Methylmorpholine, N,N-Diisopropylethylamine, l,8-Diazabicyclo(5.4.0)undec-7-ene, 6- (Dibutylamino)- l,8-diazabicyclo[5.4.0]undec-7-ene, l,8-Diazabicyclo[5.4.0]undec-7-ene bonded to polystyrene, l,5,7-Triazabicyclo[4.4.0]dec- 5-ene, 7-Methyl-l,5,7-triazabicyclo[4.4.0]dec-5-ene, 1,1,3,3-Tetramethylguanidine, 2-tert-Butyl-l,l,3,3- tetramethylguanidine, 1,5,7- Triazabicyclo[4.4.0]dec-5-ene linked to polystyrene, 1,4-Diazabicyclo[2.2.2]octane, Quinuclidine, l,5-Diazabicyclo(4.3.0)non- 5-ene, 2,6-Di-tert-butylpyridine, 2,8,9-Trimethyl-2,5,8,9-tetraza-l-phosphabicyclo[3.3.3]undecane, Cyclodiphosphazane, Lithium diisopropylamide, sodium diisopropylamide, potassium diisopropylamide, magnesium diisopropylamide, calcium diisopropylamide, rubidium diisopropylamide, lithium bis(trimethylsilyl)amide, sodium bis(trimethylsilyl)amide, potassium bis(trimethylsilyl)amide, magnesium bis(trimethylsilyl)amide, calcium bis(trimethylsilyl)amide, rubidium bis( trimethylsilyl)amide, lithium tetramethylpiperidide, sodium tetramethylpiperidide, potassium tetramethylpiperidide, magnesium tetramethylpiperidide, calcium tetramethylpiperidide, rubidium tetramethylpiperidide, [18-crown-6]-KHF2, KHF2, N,N'-diisopropylimidazonium, bifluoride, tetrabutylammonium, N(CnH2n+l )4 OH- with n being an integer from 1 to 10.
Dans le composé thiolate B, comme dans le composé de formule RSH dont il est issu, le substituant R est un hydrocarbure. Le terme hydrocarbure se réfère à un substituant
comprenant de 1 à 150 atomes de carbone, de préférence de 1 à 75 atomes de carbone, en particulier de 1 à 30 atomes de carbone. In the thiolate compound B, as in the compound of formula RSH from which it is derived, the substituent R is a hydrocarbon. The term hydrocarbon refers to a substituent comprising from 1 to 150 carbon atoms, preferably from 1 to 75 carbon atoms, in particular from 1 to 30 carbon atoms.
Avantageusement, le substituant R est sélectionné parmi le groupe de substituants consistant en Ci-Cis alkyle, C2-C18 alkényle, C4-C18 cycloalkényle, C3-C18 cycloalkyle, Cg-Cis aryle, polyalkylene glycol, ledit substituant étant optionnellement porteur d'un ou plusieurs groupements fonctionnels de formule -F, -OR', -O-C(O)R', -CN, -NR'2, -0-Si(0R')3, -Si( R')s, -SO3R', -O-P(O)(OR')2, -P(O)(OR)2, -C(O)OR', -C(O)R', -C(O)-S-R', -C(O)-NR'2, -NR'3 + dans laquelle R' est indépendamment sélectionné pour chaque substituant du groupement fonctionnel parmi le groupe consistant en H, C1.C18 alkyle, C2.Cis alkényle, C4-C18 cycloalkényle, C3-C18 cycloalkyle, Cg-Cis aryle et polyalkylene glycol. Advantageously, the substituent R is selected from the group of substituents consisting of Ci-Cis alkyl, C2-C18 alkenyl, C4-C18 cycloalkenyl, C3-C18 cycloalkyl, Cg-Cis aryl, polyalkylene glycol, said substituent optionally carrying a or several functional groups of formula -F, -OR', -OC(O)R', -CN, -NR' 2 , -0-Si(0R')3, -Si(R')s, -SO3R' , -OP(O)(OR') 2 , -P(O)(OR) 2 , -C(O)OR', -C(O)R', -C(O)-S-R', - C(O)-NR' 2 , -NR' 3 + in which R' is independently selected for each substituent of the functional group from the group consisting of H, C1.C18 alkyl, C 2.Cis alkenyl, C4-C18 cycloalkenyl, C3-C18 cycloalkyl, Cg-Cis aryl and polyalkylene glycol.
De préférence, le substituant R est sélectionné parmi le groupe de substituants consistant en Ci. C15 alkyle, C2.Ci5 alkényle, C4-C15 cycloalkényle, C3-C15 cycloalkyle, Cg-Cis aryle, polyalkylene glycol, ledit substituant étant optionnellement porteur d'un ou plusieurs groupements fonctionnels de formule -F, -OR', -O-C(O)R', -CN, -NR'2, -O-Si(OR')3, -Si(R')3, -SO3R', -O-P(O)(OR')2, -P(O)(OR)2, - C(O)OR', -C(O)R', -C(O)-S-R', -C(O)-NR'2, -NR'3 + dans laquelle R' est indépendamment sélectionné pour chaque substituant du groupement fonctionnel parmi le groupe consistant en H, C1.C15 alkyle, C2.Ci5 alkényle, C4-C15 cycloalkényle, C3-C15 cycloalkyle, Cg-Ci5 aryle et polyalkylene glycol. Plus préférentiellement, le substituant R est sélectionné parmi le groupe de substituants consistant en C1.C10 alkyle, C2.Cio alkényle, C4-C10 cycloalkényle, C3-C10 cycloalkyle, Cg-Cio aryle, polyalkylene glycol, ledit substituant étant optionnellement porteur d'un ou plusieurs groupements fonctionnels de formule -F, -OR', -O-C(O)R', -CN, -NR'2, -0-Si(0R')3, -Si(R')s, -SO3R', -O-P(O)(OR')2, -P(O)(OR)2, -C(O)OR', -C(O)R', -C(O)-S-R', -C(O)-NR'2, -NR'3 + dans laquelle R' est indépendamment sélectionné pour chaque substituant du groupement fonctionnel parmi le groupe consistant en H, C1.C10 alkyle, C2.Cio alkényle, C4-C10 cycloalkényle, C3-C10 cycloalkyle, Cg- C10 aryle et polyalkylene glycol. Preferably, the substituent R is selected from the group of substituents consisting of Ci.C15 alkyl, C 2 .Ci 5 alkenyl, C4-C15 cycloalkenyl, C3-C15 cycloalkyl, Cg-Cis aryl, polyalkylene glycol, said substituent optionally being a carrier one or more functional groups of formula -F, -OR', -OC(O)R', -CN, -NR' 2 , -O-Si(OR') 3 , -Si(R') 3 , -SO3R', -OP(O)(OR') 2 , -P(O)(OR) 2 , - C(O)OR', -C(O)R', -C(O)-S-R ', -C(O)-NR' 2 , -NR' 3 + in which R' is independently selected for each substituent of the functional group from the group consisting of H, C1.C15 alkyl, C 2 .Ci 5 alkenyl, C4 -C15 cycloalkenyl, C3-C15 cycloalkyl, Cg-Ci 5 aryl and polyalkylene glycol. More preferably, the substituent R is selected from the group of substituents consisting of C1.C10 alkyl, C 2.Cio alkenyl, C4-C10 cycloalkenyl, C3-C10 cycloalkyl, Cg-Cio aryl, polyalkylene glycol, said substituent optionally carrying 'one or more functional groups of formula -F, -OR', -OC(O)R', -CN, -NR' 2 , -0-Si(0R')3, -Si(R')s, - SO3R', -OP(O)(OR') 2 , -P(O)(OR) 2 , -C(O)OR', -C(O)R', -C(O)-S-R' , -C(O)-NR' 2 , -NR' 3 + in which R' is independently selected for each substituent of the functional group from the group consisting of H, C1.C10 alkyl, C 2 .Cio alkenyl, C4-C10 cycloalkenyl, C3-C10 cycloalkyl, Cg-C10 aryl and polyalkylene glycol.
En particulier, le substituant R est sélectionné parmi le groupe de substituants consistant en Ci. C5 alkyle, C2.C5 alkényle, C4-C5 cycloalkényle, C3-C5 cycloalkyle, Cg aryle, polyalkylene glycol, ledit substituant étant optionnellement porteur d'un ou plusieurs groupements fonctionnels de formule -F, -OR', -O-C(O)R', -CN, -NR'2, -O-Si(OR')3, -Si(R')3, -SO3R', -O-P(O)(OR')2, -P(O)(OR)2, - C(O)OR', -C(O)R', -C(O)-S-R', -C(O)-NR'2, -NR'3 + dans laquelle R' est indépendamment sélectionné pour chaque substituant du groupement fonctionnel parmi le groupe consistant en H, C1.C5 alkyle, C2.C5 alkényle, C4-C5 cycloalkényle, C3-C5 cycloalkyle, Cg aryle et polyalkylene glycol.
Plus particulièrement, le substituant R est sélectionné parmi le groupe de substituants consistant en C1.C5 alkyle, Cg aryle, polyalkylene glycol, ledit substituant étant optionnellement porteur d'un ou plusieurs groupements fonctionnels de formule -F, -OR', -O-C(O)R', -CN, -NR'2, -O-Si(OR')3, -Sï(R')3, -SO3R', -O-P(O)(OR')2, -P(O)(OR)2, -C(O)OR', -C(O)R', -C(O)-S-R', -C(O)-NR'2, - NR'3 + dans laquelle R' est indépendamment sélectionné pour chaque substituant du groupement fonctionnel parmi le groupe consistant en H, C1.C5 alkyle, C2.C5 alkényle, C4.C5 cycloalkényle, C3.C5 cycloalkyle, Cg aryle et polyalkylene glycol. In particular, the substituent R is selected from the group of substituents consisting of Ci.C 5 alkyl, C 2 .C 5 alkenyl, C4-C5 cycloalkenyl, C3-C5 cycloalkyl, Cg aryl, polyalkylene glycol, said substituent optionally carrying 'one or more functional groups of formula -F, -OR', -OC(O)R', -CN, -NR' 2 , -O-Si(OR') 3 , -Si(R') 3 , - SO3R', -OP(O)(OR') 2 , -P(O)(OR) 2 , - C(O)OR', -C(O)R', -C(O)-S-R' , -C(O)-NR' 2 , -NR' 3 + in which R' is independently selected for each substituent of the functional group from the group consisting of H, C1.C5 alkyl, C 2 .C 5 alkenyl, C4- C5 cycloalkenyl, C3-C5 cycloalkyl, Cg aryl and polyalkylene glycol. More particularly, the substituent R is selected from the group of substituents consisting of C1.C5 alkyl, Cg aryl, polyalkylene glycol, said substituent optionally carrying one or more functional groups of formula -F, -OR', -OC( O)R', -CN, -NR'2, -O-Si(OR') 3 , -Sï(R') 3 , -SO3R', -OP(O)(OR') 2 , -P(O )(OR) 2 , -C(O)OR', -C(O)R', -C(O)-S-R', -C(O)-NR' 2 , - NR' 3 + in which R' is independently selected for each functional group substituent from the group consisting of H, C1-C5 alkyl, C 2 -C 5 alkenyl, C4 -C5 cycloalkenyl, C 3 -C 5 cycloalkyl, Cg aryl and polyalkylene glycol.
De manière privilégiée, le substituant R est sélectionné parmi le groupe de substituants consistant en C1.C5 alkyle, Cg aryle, polyalkylene glycol, ledit substituant étant optionnellement porteur d'un ou plusieurs groupements fonctionnels de formule -F, -OR', -O-C(O)R', -CN, -NR'2, -C(O)OR', -C(O)R', -C(O)-NR'2, -NR'3 + dans laquelle R' est indépendamment sélectionné pour chaque substituant du groupement fonctionnel parmi le groupe consistant en H, C1.C5 alkyle, C2. C5 alkényle, C4-C5 cycloalkényle, C3.C5 cycloalkyle, Cg aryle et polyalkylene glycol. Preferably, the substituent R is selected from the group of substituents consisting of C1.C5 alkyl, Cg aryl, polyalkylene glycol, said substituent optionally carrying one or more functional groups of formula -F, -OR', -OC (O)R', -CN, -NR' 2 , -C(O)OR', -C(O)R', -C(O)-NR' 2 , -NR' 3 + in which R' is independently selected for each functional group substituent from the group consisting of H, C1.C5 alkyl, C 2 . C 5 alkenyl, C4-C5 cycloalkenyl, C 3 .C 5 cycloalkyl, Cg aryl and polyalkylene glycol.
Dans la présente demande, le terme polyalkylene glycol se réfère notamment à des composés de formule -CH2CH2(OCH2CH2)n-OCH3 ou -CH2CH2O(CH2CH2O)n-CH3 ou -CH2CH2C(O)NH- CH2CH2O-(CH2CH2O)CH3 OU -(CH2CH2O)n-CH2CO2H ou -CH2CH2(OCH2CH2)n-OCH2CH2SH ou - (CH2CH2O)n-CH2CH2CO2H ou à des composés comprenant des motifs polyéthylène glycol - (CH2CH2O)n et/ou polypropylène glycol (OCH(CH3)CH2)n distribués de manière aléatoire ou en bloc ; ou l'une quelconque des formules ci-dessus dans laquelle un ou plusieurs atomes d'hydrogène sont substitués par un atome de fluor ; avec n un entier de 1 à 100, avantageusement de 1 à 75, de préférence de 1 à 50, plus préférentiellement de 1 à 25, en particulier de 1 à 10. Le polyalkylène glycol peut être fonctionnalisé par un groupement de formule -Y2-C(Y1)-C(R10)=C(R8)(R9), -Y2-CH2-C(R10)=C(R8)(R9), -Y2- C(R10)=C(R8)(R9) ou -Y2-C6H4- C(R10)=C(R8)(R9), dans laquelle R8, R9 et R10 sont indépendamment les uns des autres sélectionnés parmi le groupe consistant en H, F, Cl, Br, I, C1-C10 alkyle ; et Y1 et Y2 sont indépendamment l'un de l'autre sélectionné parmi O et S. De préférence, R8, R9 et R10 sont indépendamment les uns des autres sélectionnés parmi le groupe consistant en H, F, Cl, C1-C5 alkyle. En particulier, R8, R9 et R10 sont indépendamment les uns des autres sélectionnés parmi le groupe consistant en H, F et Ci-C3 alkyle. In the present application, the term polyalkylene glycol refers in particular to compounds of formula -CH 2 CH 2 (OCH 2 CH 2 ) n -OCH 3 or -CH 2 CH 2 O(CH 2 CH 2 O) n -CH 3 or -CH 2 CH 2 C(O)NH- CH 2 CH 2 O-(CH 2 CH 2 O)CH 3 OR -(CH 2 CH 2 O) n -CH 2 CO 2 H or -CH 2 CH 2 ( OCH 2 CH 2 ) n -OCH 2 CH 2 SH or - (CH 2 CH 2 O) n -CH 2 CH 2 CO 2 H or to compounds comprising polyethylene glycol units - (CH 2 CH 2 O) n and/ or polypropylene glycol (OCH(CH 3 )CH 2 ) n distributed randomly or in bulk; or any of the above formulas in which one or more hydrogen atoms are substituted by a fluorine atom; with n an integer from 1 to 100, advantageously from 1 to 75, preferably from 1 to 50, more preferably from 1 to 25, in particular from 1 to 10. The polyalkylene glycol can be functionalized by a group of formula -Y 2 -C(Y 1 )-C(R 10 )=C(R 8 )(R 9 ), -Y 2 -CH 2 -C(R 10 )=C(R 8 )(R 9 ), -Y 2 - C(R 10 )=C(R 8 )(R 9 ) or -Y 2 -C 6 H 4 - C(R 10 )=C(R 8 )(R 9 ), in which R 8 , R 9 and R 10 are independently of each other selected from the group consisting of H, F, Cl, Br, I, C1-C10 alkyl; and Y 1 and Y 2 are independently of each other selected from O and S. Preferably, R 8 , R 9 and R 10 are independently of each other selected from the group consisting of H, F, Cl, C1-C5 alkyl. In particular, R 8 , R 9 and R 10 are independently of each other selected from the group consisting of H, F and Ci-C 3 alkyl.
Mise en œuyre de l'étape b) Implementation of step b)
De préférence, l'étape b) du présent procédé est mise en oeuvre en présence d'un solvant. Ledit solvant peut être un solvant organique apte à solubiliser les composés B et C. Alternativement,
ledit solvant peut être de l'eau. Ainsi, de manière non limitative, ledit solvant peut être sélectionné parmi le groupe consistant en eau, acétone, diméthylsulfoxide, diméthylformamide, N,N-diméthylacétamide, l-methyl-2-pyrrolidone, isobutyle méthyle cétone et dihydrolévoglucosénone. De préférence, le solvant est l'eau. Ceci permet d'éviter des impuretés organiques qui nécessiteraient la mise en oeuvre d'étapes supplémentaires de purification.Preferably, step b) of the present process is carried out in the presence of a solvent. Said solvent may be an organic solvent capable of solubilizing compounds B and C. Alternatively, said solvent may be water. Thus, in a non-limiting manner, said solvent can be selected from the group consisting of water, acetone, dimethylsulfoxide, dimethylformamide, N,N-dimethylacetamide, l-methyl-2-pyrrolidone, isobutyl methyl ketone and dihydrolevoglucosenone. Preferably, the solvent is water. This makes it possible to avoid organic impurities which would require the implementation of additional purification steps.
Selon un mode de réalisation préféré, l'étape b) est mise en oeuvre à une température de 10°C à 80°C, de préférence de 10°C à 50°C. According to a preferred embodiment, step b) is carried out at a temperature of 10°C to 80°C, preferably 10°C to 50°C.
Selon un mode de réalisation particulier, l'étape b) est mise en oeuvre en présence d'un composé thiolate B tel que décrit ci-dessus en présence de peroxyde d'hydrogène H2O2 et d'eau. Le composé thiolate B et le peroxyde d'hydrogène étant soluble dans l'eau, ceci permet de combiner des avantages supplémentaires, même si le procédé peut être mis en oeuvre avec de bons rendements avec d'autres composés peroxydes C ou dans un autre solvant. L'utilisation particulièrement privilégiée de H2O2 et d'eau permet de mettre en oeuvre le procédé à une température de 10°C à 50°C avec de bons rendements sans l'utilisation de solvants organiques potentiellement inflammables ou toxiques, dans des conditions respectueuses de l'environnement et ne nécessitant pas une consommation d'énergie excessive. According to a particular embodiment, step b) is carried out in the presence of a thiolate compound B as described above in the presence of hydrogen peroxide H2O2 and water. The thiolate compound B and hydrogen peroxide being soluble in water, this makes it possible to combine additional advantages, even if the process can be carried out with good yields with other peroxide compounds C or in another solvent . The particularly preferred use of H2O2 and water makes it possible to carry out the process at a temperature of 10°C to 50°C with good yields without the use of potentially flammable or toxic organic solvents, in conditions respectful of the environment and not requiring excessive energy consumption.
L'utilisation à l'étape b) du composé thiolate B plutôt que son précurseur thiol (RSH) permet de faciliter la réaction de fonctionnalisation du polymère. En effet, il a été observée de manière surprenante que le composé thiolate B étant très facilement activé par le composé peroxyde C, notamment H2O2, par rapport au précurseur thiol. La fonctionnalisation du polymère halogéné Al se trouve ainsi facilité en mettant en oeuvre l'étape b) du présent procédé par rapport à une étape mettant en oeuvre un dérivé thiol. The use in step b) of the thiolate compound B rather than its thiol precursor (RSH) makes it possible to facilitate the functionalization reaction of the polymer. Indeed, it was surprisingly observed that the thiolate compound B was very easily activated by the peroxide compound C, in particular H2O2, compared to the thiol precursor. The functionalization of the halogenated polymer Al is thus facilitated by implementing step b) of the present process compared to a step using a thiol derivative.
Polymère A2 Polymer A2
Comme mentionné ci-dessus, la mise en oeuvre de l'étape b) permet le formation d'un polymère halogéné A2. Ledit polymère A2 comprend des unités monomériques M3 de formule -CHfR1)- C(R2)(SR)- et lesdites unités monomériques Ml comprenant au moins un atome d'halogène, de préférence de fluor ; R, R1 et R2 étant tels que définis ci-dessus. As mentioned above, the implementation of step b) allows the formation of a halogenated polymer A2. Said polymer A2 comprises monomeric units M3 of formula -CHfR 1 )- C(R 2 ) (SR)- and said monomeric units Ml comprising at least one halogen atom, preferably fluorine; R, R 1 and R 2 being as defined above.
Selon un mode de réalisation préféré, les unités monomériques Ml sont de formule -C(Y1)(Y2)- C(Y3)(Y4)- dans laquelle Y1, Y2, Y3 et Y4 sont indépendamment les uns des autres sélectionnés parmi le groupe consistant en H, C1-C5 alkyle, C1-C5 (per)halogénoalkyle, F, Br, I et Cl ; de préférence indépendamment les uns des autres sélectionnés parmi le groupe consistant en F,
CF3, Cl, Br, I et H ; à condition que les substituants Y1, Y2, Y3 et Y4 ne soient pas simultanément H ou Ci-C5 alkyle. According to a preferred embodiment, the monomeric units Ml are of formula -C(Y 1 )(Y 2 )- C(Y 3 )(Y 4 )- in which Y 1 , Y 2 , Y 3 and Y 4 are independently each other selected from the group consisting of H, C1-C5 alkyl, C1-C5 (per)haloalkyl, F, Br, I and Cl; preferably independently of each other selected from the group consisting of F, CF 3 , Cl, Br, I and H; provided that the Y 1 , Y 2 , Y 3 and Y 4 substituents are not simultaneously H or Ci-C 5 alkyl.
Avantageusement, les unités monomériques Ml sont issues d'un monomère sélectionné parmi le groupe consistant en bromure de vinyle, iodure de vinyle, chlorure de vinyle, chlorure de vinylidène, tétrachloroéthylène, hexachloropropène, tétrachloropropène, trichloropropène, dichloropropène, difluoropropène, fluoropropène, fluorure de vinylidène, fluorure de vinyle, hexafluoropropène, tétrafluoroéthylène, chlorotrifluoroéthylène, trifluoroéthylène, 2, 3,3,3- tétrafluoropropène, E/Z-l,3,3,3-tétrafluoropropène, 3,3,3-trifluoropropène, (E/Z)-l-chloro- 2,3,3,3-tétrafluoropropène, 1,2,3,3,3-pentafluoropropène, (E/Z)-l-chloro-3,3,3- trifluoropropène, 2-chloro-3,3,3-trifluoropropène, et les mélanges de ceux-ci. Advantageously, the monomeric units Ml come from a monomer selected from the group consisting of vinyl bromide, vinyl iodide, vinyl chloride, vinylidene chloride, tetrachloroethylene, hexachloropropene, tetrachloropropene, trichloropropene, dichloropropene, difluoropropene, fluoropropene, fluoride vinylidene, vinyl fluoride, hexafluoropropene, tetrafluoroethylene, chlorotrifluoroethylene, trifluoroethylene, 2, 3,3,3- tetrafluoropropene, E/Z-l,3,3,3-tetrafluoropropene, 3,3,3-trifluoropropene, (E/Z)- l-chloro-2,3,3,3-tetrafluoropropene, 1,2,3,3,3-pentafluoropropene, (E/Z)-l-chloro-3,3,3-trifluoropropene, 2-chloro-3, 3,3-trifluoropropene, and mixtures thereof.
De préférence, les unités monomériques Ml sont issues d'un monomère sélectionné parmi le groupe consistant en fluorure de vinylidène, fluorure de vinyle, tétrafluoroéthylène, chlorotrifluoroéthylène, trifluoroéthylène et les mélanges de ceux-ci. De préférence, les unités monomériques Ml sont issues d'un monomère sélectionné parmi le groupe consistant en fluorure de vinylidène, tétrafluoroéthylène, hexafluoropropène, chlorotrifluoroéthylène et les mélanges de ceux-ci. En particulier, les unités monomériques Ml sont issues du fluorure de vinylidène. Preferably, the monomeric units Ml come from a monomer selected from the group consisting of vinylidene fluoride, vinyl fluoride, tetrafluoroethylene, chlorotrifluoroethylene, trifluoroethylene and mixtures thereof. Preferably, the monomeric units Ml come from a monomer selected from the group consisting of vinylidene fluoride, tetrafluoroethylene, hexafluoropropene, chlorotrifluoroethylene and mixtures thereof. In particular, the monomeric units Ml come from vinylidene fluoride.
Dans un mode de réalisation préféré, le polymère halogéné A2 comprend des unités monomériques Ml issues du fluorure de vinylidène et des unités monomériques M3 de formule -CH(R1)-C(R2)(SR)- avec R, R1 et R2 tels que définis ci-dessus dans la présente demande. Dans ce mode de réalisation, le polymère halogéné A2 peut également comprendre des unités monomériques Ml' issues d'un comonomère compatible avec le fluorure de vinylidène. Les comonomères compatibles avec le fluorure de vinylidène peuvent être halogénés (fluorés, chlorés, bromés ou iodés) ou non-halogénés. Des exemples de comonomères appropriés sont par exemple chlorure de vinyle, iodure de vinyle, bromure de vinyle, fluorure de vinyle, tétrafluoroéthylène, trifluoroéthylène, hexafluoropropène, les trifluoropropènes et notamment le 3,3,3-trifluoropropène, les tétrafluoropropènes et notamment le 2,3,3,3-tétrafluoropropène ou le 1,3,3,3-tétrafluoropropène, l'hexafluoroisobutylène, le perfluorobutyléthylène, les pentafluoropropènes et notamment le 1,1,3,3,3-pentafluoropropène ou le 1,2,3,3,3- pentafluoropropène, les perfluoroalkylvinyléthers et notamment ceux de formule générale Rf- 0-CF=CF2, Rf étant un groupement alkyle, de préférence en Cl à C4 (des exemples préférés étant le perfluoropropylvinyléther et le perfluorométhylvinyléther), les alkylvinyléthers et notamment ceux de formule générale Rf-O-CH=CH2, Rf étant un groupement alkyle, de
préférence en Cl à C4 (des exemples préférés étant le propylvinyléther et le méthylvinyléther), les alkanolates de vinyle et notamment ceux de formule générale Rf-C(O)-O-CH=CH2, Rf étant un groupement alkyle, de préférence en Cl à C4, en particulier l'acétate de vinyle. Le comonomère compatible avec le fluorure de vinylidène peut comporter un atome de chlore, de brome ou d'iode. Il peut en particulier être choisi parmi le bromotrifluoroéthylène, le chlorofluoroethylène, le chlorotrifluoroéthylène et le chlorotrifluoropropène. Le chlorofluoroéthylène peut désigner soit le 1-chloro-l-fluoroéthylène, soit le l-chloro-2- fluoroéthylène. L'isomère 1-chloro-l-fluoroéthylène est préféré. Le chlorotrifluoropropène est de préférence le l-chloro-3,3,3-trifluoropropène ou le 2-chloro-3,3,3-trifluoropropène. In a preferred embodiment, the halogenated polymer A2 comprises monomeric units Ml derived from vinylidene fluoride and monomeric units M3 of formula -CH(R 1 )-C(R 2 ) (SR)- with R, R 1 and R 2 as defined above in this application. In this embodiment, the halogenated polymer A2 can also comprise monomeric units Ml' derived from a comonomer compatible with vinylidene fluoride. Comonomers compatible with vinylidene fluoride can be halogenated (fluorinated, chlorinated, brominated or iodized) or non-halogenated. Examples of suitable comonomers are for example vinyl chloride, vinyl iodide, vinyl bromide, vinyl fluoride, tetrafluoroethylene, trifluoroethylene, hexafluoropropene, trifluoropropenes and in particular 3,3,3-trifluoropropene, tetrafluoropropenes and in particular 2, 3,3,3-tetrafluoropropene or 1,3,3,3-tetrafluoropropene, hexafluoroisobutylene, perfluorobutylethylene, pentafluoropropenes and in particular 1,1,3,3,3-pentafluoropropene or 1,2,3, 3,3-pentafluoropropene, perfluoroalkyl vinyl ethers and in particular those of general formula Rf- 0-CF=CF2, Rf being an alkyl group, preferably C to C4 (preferred examples being perfluoropropyl vinyl ether and perfluoromethyl vinyl ether), alkyl vinyl ethers and in particular those of general formula Rf-O-CH=CH2, Rf being an alkyl group, of preferably in Cl to C4 (preferred examples being propyl vinyl ether and methyl vinyl ether), vinyl alkanolates and in particular those of general formula Rf-C(O)-O-CH=CH2, Rf being an alkyl group, preferably in Cl to C4, in particular vinyl acetate. The comonomer compatible with vinylidene fluoride may contain a chlorine, bromine or iodine atom. It may in particular be chosen from bromotrifluoroethylene, chlorofluoroethylene, chlorotrifluoroethylene and chlorotrifluoropropene. Chlorofluoroethylene can refer to either 1-chloro-l-fluoroethylene or l-chloro-2-fluoroethylene. The 1-chloro-1-fluoroethylene isomer is preferred. The chlorotrifluoropropene is preferably 1-chloro-3,3,3-trifluoropropene or 2-chloro-3,3,3-trifluoropropene.
Le polymère halogéné A2 peut également comprendre des unités monomériques portant au moins l'une des fonctions suivantes: acide carboxylique, anhydride d'acide carboxylique, esters d'acide carboxylique, groupes époxy (tel que le glycidyle), amide, hydroxyle, carbonyle, mercapto, sulfure, oxazoline, phénoliques, ester, éther, siloxane, sulfonique, sulfurique, phosphorique, phosphonique. La fonction est introduite par une réaction chimique qui peut être du greffage, ou une copolymérisation du monomère fluorure de vinylidène (VDF) avec un monomère portant au moins un desdits groupes fonctionnels et une fonction vinylique capable de copolymériser avec le monomère VDF, selon des techniques bien connues par l'homme du métier. Selon un mode de réalisation, les unités portant la fonction acide carboxylique comprennent en outre un hétéroatome choisi parmi l'oxygène, le soufre, l'azote et le phosphore. La teneur en groupes fonctionnels dudit polymère halogéné A2 peut être de préférence d'au moins 0,01% molaire, de préférence d'au moins 0,1 % molaire, et au plus de 15% molaire, de préférence au plus 10% molaire. The halogenated polymer A2 may also comprise monomeric units carrying at least one of the following functions: carboxylic acid, carboxylic acid anhydride, carboxylic acid esters, epoxy groups (such as glycidyl), amide, hydroxyl, carbonyl, mercapto, sulfide, oxazoline, phenolics, ester, ether, siloxane, sulfonic, sulfuric, phosphoric, phosphonic. The function is introduced by a chemical reaction which may be grafting, or a copolymerization of the vinylidene fluoride (VDF) monomer with a monomer bearing at least one of said functional groups and a vinyl function capable of copolymerizing with the VDF monomer, according to techniques well known to those skilled in the art. According to one embodiment, the units carrying the carboxylic acid function further comprise a heteroatom chosen from oxygen, sulfur, nitrogen and phosphorus. The content of functional groups in said halogenated polymer A2 may preferably be at least 0.01 mol%, preferably at least 0.1 mol%, and at most 15 mol%, preferably at most 10 mol%. .
En particulier, le polymère halogéné A2 peut également comprendre des unités monomériques Ml" issues de l'acide (méth)acrylique sélectionné parmi le groupe consistant en l'acide acrylique, l'acide méthacrylique, hydroxyéthyl(méth)acrylate, hydroxypropyl(méth)acrylate, hydroxyéthylhexyl(méth)acrylate, styrène, carbonate de vinylène, carbamate de vinyle, N-vinyle acétamide, méthacrylate de vinyle, l-vinyl-2-pyrrolidone et le méthacrylate de méthyle, les esters en Ci-Cis de l'acide acrylique ou l'acide méthacrylique ; ou un mélange de ceux-ci. In particular, the halogenated polymer A2 may also comprise monomeric units Ml" derived from (meth)acrylic acid selected from the group consisting of acrylic acid, methacrylic acid, hydroxyethyl(meth)acrylate, hydroxypropyl(meth) acrylate, hydroxyethylhexyl(meth)acrylate, styrene, vinylene carbonate, vinyl carbamate, N-vinyl acetamide, vinyl methacrylate, l-vinyl-2-pyrrolidone and methyl methacrylate, Ci-Cis esters of the acid acrylic or methacrylic acid; or a mixture thereof.
Ainsi, dans un mode de réalisation particulier, le polymère halogéné A2 comprend des unités monomériques Ml issues du fluorure de vinylidène, des unités monomériques M3 de formule -CH(R1)-C(R2)(SR)- avec R, R1 et R2 tels que définis ci-dessus et optionnellement des unités monomériques Ml' telles que définies ci-dessus, des unités monomériques Ml" telles que définies ci-dessus ; ou un mélange des deux.
Plus particulièrement, le polymère halogéné A2 comprend des unités monomériques Ml issues du fluorure de vinylidène, des unités monomériques M3 de formule -CH(R1)-C(R2)(SR)- avec R, R1 et R2 tels que définis ci-dessus et optionnellement des unités monomériques Ml' issues d'un monomère sélectionné parmi le groupe consistant en tétrafluoroéthylène, trifluoroéthylène, acétate de vinyle, méthylvinyléther, chlorotrifluoroéthylène et hexafluoropropène ou un mélange de ceux-ci, et des unités monomériques Ml" issues d'un monomère sélectionné parmi le groupe consistant en l'acide acrylique, l'acide méthacrylique, hydroxyéthyl(méth)acrylate, hydroxypropyl(méth)acrylate, hydroxyéthylhexyl(méth)acrylate, styrène, carbonate de vinylène, carbamate de vinyle, N-vinyle acétamide, méthacrylate de vinyle, l-vinyl-2- pyrrolidone et le méthacrylate de méthyle, les esters en Ci-Cis de l'acide acrylique ou l'acide méthacrylique ; ou un mélange de ceux-ci ; ou un mélange des unités monomériques Ml' et Ml". Thus, in a particular embodiment, the halogenated polymer A2 comprises monomeric units Ml derived from vinylidene fluoride, monomeric units M3 of formula -CH(R 1 )-C(R 2 )(SR)- with R, R 1 and R 2 as defined above and optionally monomeric units Ml' as defined above, monomeric units Ml" as defined above; or a mixture of the two. More particularly, the halogenated polymer A2 comprises monomeric units Ml derived from vinylidene fluoride, monomeric units M3 of formula -CH(R 1 )-C(R 2 ) (SR)- with R, R 1 and R 2 such that defined above and optionally monomeric units Ml' derived from a monomer selected from the group consisting of tetrafluoroethylene, trifluoroethylene, vinyl acetate, methyl vinyl ether, chlorotrifluoroethylene and hexafluoropropene or a mixture thereof, and monomeric units Ml" derived of a monomer selected from the group consisting of acrylic acid, methacrylic acid, hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate, hydroxyethylhexyl(meth)acrylate, styrene, vinylene carbonate, vinyl carbamate, N- vinyl acetamide, vinyl methacrylate, l-vinyl-2-pyrrolidone and methyl methacrylate, Ci-Cis esters of acrylic acid or methacrylic acid; or a mixture thereof; or a mixture of the units monomeric Ml' and Ml".
De préférence, la teneur molaire des unités monomériques M3 dans ledit polymère A2 est comprise entre 0,01 et 5%, de préférence entre 0,05 et 2%, en particulier entre 0,1 et 1%. Une teneur molaire des unités monomériques M3 dans ledit polymère A2 entre 0,01 et 1%, en particulier entre 0,1 et 1% est particulièrement privilégiée lorsque le polymère A2 est utilisé comme liant dans une batterie. Dans cette gamme de teneur molaire, les unités monomériques M3 ont un impact sur la performance de batteries utilisant comme liant ledit polymère A2. Preferably, the molar content of the monomeric units M3 in said polymer A2 is between 0.01 and 5%, preferably between 0.05 and 2%, in particular between 0.1 and 1%. A molar content of the monomeric units M3 in said polymer A2 between 0.01 and 1%, in particular between 0.1 and 1% is particularly preferred when the polymer A2 is used as a binder in a battery. In this molar content range, the M3 monomeric units have an impact on the performance of batteries using said A2 polymer as a binder.
Utilisation Use
Le polymère A2 tel que décrit dans la présente demande peut être utilisé dans de nombreuses applications. Ainsi, ledit polymère A2 peut être utilisé comme liant pour électrode (cathode ou anode). Selon un autre aspect de la présente invention, une électrode comprenant ledit polymère A2 est fourni. Selon un autre aspect, une batterie comprenant ladite électrode est également fournie. Polymer A2 as described in the present application can be used in numerous applications. Thus, said polymer A2 can be used as a binder for an electrode (cathode or anode). According to another aspect of the present invention, an electrode comprising said polymer A2 is provided. According to another aspect, a battery comprising said electrode is also provided.
Selon un autre aspect, ledit polymère A2 peut être utilisé dans la préparation d'un polymère conducteur, d'un électrolyte solide pour piles à combustibles, d'un revêtement hydrophile, d'un revêtement hydrophobe ou d'un revêtement absorbant l'UV.
According to another aspect, said polymer A2 can be used in the preparation of a conductive polymer, a solid electrolyte for fuel cells, a hydrophilic coating, a hydrophobic coating or a UV absorbing coating .
Exemple 1
5g de PVDF Kynar® 741 en poudre sont agités dans 55 ml d'une solution d'éthanol à 10% dans l'eau. A ce mélange, 2,5 ml d'une solution de NaOH (50 %pds dans l'eau) sont ajoutés et le milieu réactionnel est agité pendant 24h à température ambiante. Une décoloration de la poudre est observée indiquant que la réaction de déshydrofluoration a eu lieu (du blanc vers le marron ou noir). Le PVDF déshydrofluoré est isolé par filtration et lavé avec de l'eau jusqu'à l'obtention d'un filtrat incolore. Le PVDF déshydrofluoré est ensuite séché à 50°C pendant 24 h. Example 1 5g of Kynar® 741 PVDF powder are stirred in 55 ml of a 10% ethanol solution in water. To this mixture, 2.5 ml of a NaOH solution (50% by weight in water) are added and the reaction medium is stirred for 24 hours at room temperature. A discoloration of the powder is observed indicating that the dehydrofluorination reaction has taken place (from white to brown or black). The dehydrofluorinated PVDF is isolated by filtration and washed with water until a colorless filtrate is obtained. The dehydrofluorinated PVDF is then dried at 50°C for 24 h.
Exemple 2 Example 2
L'exemple 1 est reproduit en utilisant 18 ml d'une solution de NaOH à 50% dans l'eau. Example 1 is reproduced using 18 ml of a 50% NaOH solution in water.
Exemple 3 Example 3
L'exemple 2 est reproduit avec l'ajout de 0,05g de dodécyle sulfate de sodium en sus des 18 ml d'une solution de NaOH à 50% dans l'eau. Example 2 is reproduced with the addition of 0.05 g of sodium dodecyl sulfate in addition to 18 ml of a 50% NaOH solution in water.
Dans chacun des exemples 1 à 3, un PVDF déshydrofluoré est obtenu. Le PVDF ainsi obtenu comprend des unités monomériques Ml de formule -CH2CF2- et des unités monomériques M2 de formule -CH=CF- In each of Examples 1 to 3, a dehydrofluorinated PVDF is obtained. The PVDF thus obtained comprises Ml monomeric units of formula -CH2CF2- and M2 monomeric units of formula -CH=CF-
Fonctionnalisation du PVDF déshydrofluoré Functionalization of dehydrofluorinated PVDF
Exemple 4 (comparatif - pas de composé C) Example 4 (comparative - no compound C)
4,5 ml de triméthylamine sont ajoutés à une solution de 2,85 ml de méthyl-2- mercaptopropionate (composé thiolate B) dans 20 ml d'eau et mélangés jusqu'à complète dissolution. A ce mélange, 2g de PVDF déshydrofluoré, 40 ml d'eau, 10ml de tertbutanol et 0,03g de dodécyle sulfate de sodium sont ajoutés sous agitation. Une dispersion homogène est obtenue. Aucune décoloration n'est observée après 30h de réaction indiquant une absence de de fonctionnalisation du PVDF. 4.5 ml of trimethylamine are added to a solution of 2.85 ml of methyl-2-mercaptopropionate (thiolate compound B) in 20 ml of water and mixed until completely dissolved. To this mixture, 2 g of dehydrofluorinated PVDF, 40 ml of water, 10 ml of tertbutanol and 0.03 g of sodium dodecyl sulfate are added with stirring. A homogeneous dispersion is obtained. No discoloration is observed after 30 hours of reaction, indicating an absence of functionalization of the PVDF.
Exemple 5 (comparatif - pas de composé B) Example 5 (comparative - no compound B)
1,4 ml de triéthylamine sont ajoutés à 20 ml d'eau. A ce mélange, 2g de PVDF déshydrofluoré, 40 ml d'eau, 10 ml d'éthanol sont ajoutés sous agitation. Une dispersion homogène est obtenue. Après 10 min d'agitation, 0,2 ml d'une solution d'H2O2 (35%pds dans l'eau) sont ajoutés au mélange réactionnel. Aucune décoloration n'est observée après 30h de réaction indiquant une absence de fonctionnalisation du PVDF.
Exemple 6 (invention) 1.4 ml of triethylamine are added to 20 ml of water. To this mixture, 2 g of dehydrofluorinated PVDF, 40 ml of water, 10 ml of ethanol are added with stirring. A homogeneous dispersion is obtained. After 10 min of stirring, 0.2 ml of a solution of H 2 O 2 (35% by weight in water) are added to the reaction mixture. No discoloration is observed after 30 hours of reaction, indicating an absence of functionalization of the PVDF. Example 6 (invention)
1,4 ml de triéthylamine sont ajoutés à une solution de 1,4 ml méthyl-2-mercaptopropionate (CH3OC(O)CH(CH3)SH pour former le composé thiolate B CH3OC(O)CH(CH3)S_ dans 20 ml d'eau et mélangés jusqu'à complète dissolution. A ce mélange, 2g de PVDF déshydrofluoré, 40 ml d'eau, 10 ml d'éthanol sont ajoutés sous agitation. Une dispersion homogène est obtenue. Après 10 min d'agitation, 0,2 ml d'une solution d'H2O2 (35%pds dans l'eau) sont ajoutés au mélange réactionnel. Une décoloration rapide est obtenue pour former une poudre blanche. Après 24h, la dispersion est filtrée, lavée à l'eau jusqu'à l'obtention d'un filtrat incolore. Le polymère PVDF ainsi obtenu comprend des unités monomériques Ml de formule -CH2CF2- et des unités monomériques M3 de formule - CHa(F)-C( H)(SR)- avec R = -CH(CH3)(C(O)OCH3). 1.4 ml of triethylamine are added to a solution of 1.4 ml methyl-2-mercaptopropionate (CH3OC(O)CH(CH3)SH to form the thiolate compound B CH3OC(O)CH(CH3)S _ in 20 ml of water and mixed until completely dissolved. To this mixture, 2 g of dehydrofluorinated PVDF, 40 ml of water, 10 ml of ethanol are added with stirring. A homogeneous dispersion is obtained. After 10 min of stirring, 0 .2 ml of a solution of H2O2 (35% by weight in water) are added to the reaction mixture. Rapid decolorization is obtained to form a white powder. After 24 hours, the dispersion is filtered, washed with water until 'to obtain a colorless filtrate. The PVDF polymer thus obtained comprises monomeric units Ml of formula -CH2CF2- and monomeric units M3 of formula - CH a (F)-C(H)(SR)- with R = -CH(CH3)(C(O)OCH 3 ).
La poudre est caractérisée par 1H RMN (Bruker Avance III 400 avec une sonde BBFO+ 5mm). L'échantillon est dissous dans le (CDshCO ou le (CDshSO. Un doublet de quadruplet est observée à 4,56 ppm caractéristique de l'hydrogène Ha de l'unité monomérique M3 suivante — CHa(F)- C(H)(SR)- avec R = -CH(CH3)(C(O)OCH3).
The powder is characterized by 1 H NMR (Bruker Avance III 400 with a BBFO+ 5mm probe). The sample is dissolved in (CDshCO or (CDshSO. A quadruplet doublet is observed at 4.56 ppm characteristic of hydrogen H a of the following monomeric unit M3 — CH a (F)- C(H) (SR)- with R = -CH(CH3)(C(O)OCH 3 ).
Claims
1. Procédé de préparation d'un polymère halogéné fonctionnalisé comprenant les étapes de : a) Fourniture d'un polymère halogéné Al comprenant des unités monomériques Ml comprenant au moins un atome d'halogène, de préférence de fluor, et des unités monomériques M2 comprenant au moins une double liaison carbone-carbone - C(R1)=C(R2)- ; b) Mise en contact dudit polymère halogéné Al avec un composé thiolate B de formule R-S- en présence d'un composé peroxyde C pour former un polymère A2 comprenant des unités monomériques M3 de formule -CH(R1)-C(R2)(SR)- et lesdites unités monomériques Ml comprenant au moins un atome d'halogène, de préférence de fluor ; R1 et R2 étant indépendamment l'un de l'autre sélectionné parmi le groupe consistant en H, C1-C5 alkyle, C1-C5 (per)halogénoalkyle, F, Br, I et Cl ; R étant un substituant hydrocarbure optionnellement fonctionnalisé. 1. Process for preparing a functionalized halogenated polymer comprising the steps of: a) Supply of a halogenated polymer Al comprising monomeric units Ml comprising at least one halogen atom, preferably fluorine, and monomeric units M2 comprising at least one carbon-carbon double bond - C(R 1 )=C(R 2 )-; b) Bringing said halogenated polymer Al into contact with a thiolate compound B of formula RS- in the presence of a peroxide compound C to form a polymer A2 comprising monomeric units M3 of formula -CH(R 1 )-C(R 2 ) (SR)- and said monomeric units Ml comprising at least one halogen atom, preferably fluorine; R 1 and R 2 being independently selected from the group consisting of H, C1-C5 alkyl, C1-C5 (per)haloalkyl, F, Br, I and Cl; R being an optionally functionalized hydrocarbon substituent.
2. Procédé selon la revendication précédente caractérisé en ce que le polymère halogéné Al est obtenu par une réaction de déshydrohalogénation d'un polymère halogéné A comprenant des monomériques Ml comprenant au moins un atome d'halogène, de préférence de fluor, et des unités monomériques M4 de formule -CH(R1)-C(R2)(X)- dans laquelle X est un halogène et R1 et R2 sont tels que définis à la revendication 1. 2. Method according to the preceding claim characterized in that the halogenated polymer Al is obtained by a dehydrohalogenation reaction of a halogenated polymer A comprising monomers Ml comprising at least one halogen atom, preferably fluorine, and monomeric units M4 of formula -CH(R 1 )-C(R 2 )(X)- in which X is a halogen and R 1 and R 2 are as defined in claim 1.
3. Procédé selon l'une quelconque des revendications précédentes caractérisé en que le composé thiolate B de formule R-S- est obtenu par réaction entre un composé de formule R-S-H et une base. 3. Method according to any one of the preceding claims, characterized in that the thiolate compound B of formula R-S- is obtained by reaction between a compound of formula R-S-H and a base.
4. Procédé selon la revendication précédente caractérisé en ce que la base est sélectionnée parmi le groupe consistant en LiOH, NaOH, KOH, CsOH, RbOH, Mg(OH)2, Ca(OH)2, N(CnH2n+i)3 avec n étant un entier de 1 à 10, N,N-Diisopropylethylamine, morpholine, pyridine, pyrrolidine, Piperidine, piperazine, 4-Methylmorpholine, N,N- Diisopropylethylamine, l,8-Diazabicyclo(5.4.0)undec-7-ene, 6-(Dibutylamino)-l,8- diazabicyclo[5.4.0]undec-7-ene, l,8-Diazabicyclo[5.4.0]undec-7-ene lié à du polystyrène, l,5,7-Triazabicyclo[4.4.0]dec-5-ene, 7-Methyl-l,5,7-
triazabicyclo[4.4.0]dec-5-ene, 1,1,3,3-Tetramethylguanidine, 2-tert-Butyl-l, 1,3,3- tetramethylguanidine, l,5,7-Triazabicyclo[4.4.0]dec-5-ene lié à du polystyrène, 1,4-4. Method according to the preceding claim characterized in that the base is selected from the group consisting of LiOH, NaOH, KOH, CsOH, RbOH, Mg(OH)2, Ca(OH)2, N(C n H2n+i) 3 with n being an integer from 1 to 10, N,N-Diisopropylethylamine, morpholine, pyridine, pyrrolidine, Piperidine, piperazine, 4-Methylmorpholine, N,N- Diisopropylethylamine, l,8-Diazabicyclo(5.4.0)undec-7 -ene, 6-(Dibutylamino)-1,8- diazabicyclo[5.4.0]undec-7-ene, l,8-Diazabicyclo[5.4.0]undec-7-ene linked to polystyrene, l,5,7 -Triazabicyclo[4.4.0]dec-5-ene, 7-Methyl-l,5,7- triazabicyclo[4.4.0]dec-5-ene, 1,1,3,3-Tetramethylguanidine, 2-tert-Butyl-l, 1,3,3-tetramethylguanidine, l,5,7-Triazabicyclo[4.4.0] dec-5-ene bonded to polystyrene, 1,4-
Diazabicyclo[2.2.2]octane, Quinuclidine, l,5-Diazabicyclo(4.3.0)non-5-ene, 2,6-Di-tert- butylpyridine, 2,8,9-Trimethyl-2,5,8,9-tetraza-l-phosphabicyclo[3.3.3]undecane,Diazabicyclo[2.2.2]octane, Quinuclidine, l,5-Diazabicyclo(4.3.0)non-5-ene, 2,6-Di-tert-butylpyridine, 2,8,9-Trimethyl-2,5,8, 9-tetraza-l-phosphabicyclo[3.3.3]undecane,
Cyclodiphosphazane, Lithium diisopropylamide, sodium diisopropylamide, potassium diisopropylamide, magnesium diisopropylamide, calcium diisopropylamide, rubidium diisopropylamide, lithium bis(trimethylsilyl)amide, sodium bis(trimethylsilyl)amide, potassium bis(trimethylsilyl)amide, magnesium bis(trimethylsilyl)amide, calcium bis(trimethylsilyl)amide, rubidium bis(trimethylsilyl)amide, lithium tetramethylpiperidide, sodium tetramethylpiperidide, potassium tetramethylpiperidide, magnesium tetramethylpiperidide, calcium tetramethylpiperidide, rubidium tetramethylpiperidide, [18-crown-6]-KHF2, KHF2,Cyclodiphosphazane, Lithium diisopropylamide, sodium diisopropylamide, potassium diisopropylamide, magnesium diisopropylamide, calcium diisopropylamide, rubidium diisopropylamide, lithium bis(trimethylsilyl)amide, sodium bis(trimethylsilyl)amide, potassium bis(trimethylsilyl)amide, magnesium bis(trimethylsilyl)amide, calcium bis (trimethylsilyl)amide, rubidium bis(trimethylsilyl)amide, lithium tetramethylpiperidide, sodium tetramethylpiperidide, potassium tetramethylpiperidide, magnesium tetramethylpiperidide, calcium tetramethylpiperidide, rubidium tetramethylpiperidide, [18-crown-6]-KHF2, KHF2,
N,N'-diisopropylimidazonium, bifluorure, tetrabutylammonium, N(CnH2n+i)4 OH- avec n étant un entier de 1 à 10. N,N'-diisopropylimidazonium, bifluoride, tetrabutylammonium, N(C n H2n+i)4 OH- with n being an integer from 1 to 10.
5. Procédé selon l'une quelconque des revendications précédentes caractérisé en ce que le composé peroxyde C est sélectionné parmi les peroxydes organiques, percarbonates, perborates et hydroperoxydes. 5. Method according to any one of the preceding claims, characterized in that the peroxide compound C is selected from organic peroxides, percarbonates, perborates and hydroperoxides.
6. Procédé selon l'une quelconque des revendications précédentes caractérisé en ce que le composé thiolate B est de formule R-S dans laquelle R est sélectionné parmi le groupe de substituants consistant en Ci-Cis alkyle, C2-C18 alkényle, C4-C18 cycloalkényle, C3-C18 cycloalkyle, Cg-Cis aryle, polyalkylene glycol, ledit substituant étant optionnellement porteur d'un ou plusieurs groupements fonctionnels de formule -F, -OR', -O-C(O)R', - CN, -NR'2, -O-Si(OR')3, -Sï(R')3, -SO3R', -O-P(O)(OR')2, -P(O)(OR)2, -C(O)OR', -C(O)R', -C(O)- S-R', -C(O)-NR'2, -NR'3 + dans laquelle R' est indépendamment sélectionné pour chaque substituant du groupement fonctionnel parmi le groupe consistant en H, Ci.Cis alkyle, C2-C18 alkényle, C4-C18 cycloalkényle, C3-C18 cycloalkyle, Cg-Cis aryle, polyalkylene glycol. 6. Process according to any one of the preceding claims, characterized in that the thiolate compound B is of formula RS in which R is selected from the group of substituents consisting of Ci-Cis alkyl, C2-C18 alkenyl, C4-C18 cycloalkenyl, C3-C18 cycloalkyl, Cg-Cis aryl, polyalkylene glycol, said substituent optionally carrying one or more functional groups of formula -F, -OR', -OC(O)R', - CN, -NR' 2 , -O-Si(OR') 3 , -Sï(R') 3 , -SO3R', -OP(O)(OR') 2 , -P(O)(OR) 2 , -C(O)OR' , -C(O)R', -C(O)- S-R', -C(O)-NR' 2 , -NR' 3 + in which R' is independently selected for each substituent of the functional group among the group consisting of H, Ci.Cis alkyl, C2-C18 alkenyl, C4-C18 cycloalkenyl, C3-C18 cycloalkyl, Cg-Cis aryl, polyalkylene glycol.
7. Procédé selon l'une quelconque des revendications précédentes caractérisé en ce que lesdites unités monomériques Ml sont issues d'un monomère sélectionné parmi le groupe consistant en bromure de vinyle, iodure de vinyle, chlorure de vinyle, chlorure de vinylidène, tétrachloroéthylène, hexachloropropène, tétrachloropropène, trichloropropène, dichloropropène, difluoropropène, fluoropropène, fluorure de
vinylidène, fluorure de vinyle, hexafluoropropène, tétrafluoroéthylène, chlorotrifluoroéthylène, trifluoroéthylène, 2,3,3,3-tétrafluoropropène, E/Z-l, 3,3,3- tétrafluoropropène, 3,3,3-trifluoropropène, (E/Z)-l-chloro-2,3,3,3-tétrafluoropropène, 1,2,3,3,3-pentafluoropropène, (E/Z)-l-chloro-3,3,3-trifluoropropène, 2-chloro-3,3,3- trifluoropropène, et les mélanges de ceux-ci. 7. Method according to any one of the preceding claims characterized in that said monomeric units Ml come from a monomer selected from the group consisting of vinyl bromide, vinyl iodide, vinyl chloride, vinylidene chloride, tetrachloroethylene, hexachloropropene , tetrachloropropene, trichloropropene, dichloropropene, difluoropropene, fluoropropene, fluoride vinylidene, vinyl fluoride, hexafluoropropene, tetrafluoroethylene, chlorotrifluoroethylene, trifluoroethylene, 2,3,3,3-tetrafluoropropene, E/Zl, 3,3,3- tetrafluoropropene, 3,3,3-trifluoropropene, (E/Z)- l-chloro-2,3,3,3-tetrafluoropropene, 1,2,3,3,3-pentafluoropropene, (E/Z)-l-chloro-3,3,3-trifluoropropene, 2-chloro-3, 3,3-trifluoropropene, and mixtures thereof.
8. Procédé selon l'une quelconque des revendications précédentes caractérisé en ce que l'étape b) est mise en oeuvre en présence d'un solvant sélectionné parmi le groupe consistant en eau, acétone, diméthylsulfoxide, diméthylformamide, N,N- diméthylacétamide, l-methyl-2-pyrrolidone, isobutyle méthyle cétone et dihydrolévoglucosénone. 8. Method according to any one of the preceding claims characterized in that step b) is carried out in the presence of a solvent selected from the group consisting of water, acetone, dimethylsulfoxide, dimethylformamide, N,N-dimethylacetamide, l-methyl-2-pyrrolidone, isobutyl methyl ketone and dihydrolevoglucosenone.
9. Polymère halogéné fonctionnalisé A2 comprenant des unités monomériques M3 de formule -CH(R1)-C(R2)(SR)- et des unités monomériques Ml comprenant au moins un atome d'halogène, de préférence de fluor, avec R, R1 et R2 tel que défini dans l'une quelconque des revendications précédentes 1 ou 6. 9. Functionalized halogenated polymer A2 comprising monomeric units M3 of formula -CH(R 1 )-C(R 2 )(SR)- and monomeric units Ml comprising at least one halogen atom, preferably fluorine, with R , R 1 and R 2 as defined in any one of preceding claims 1 or 6.
10. Polymère selon la revendication précédente caractérisé en ce que la teneur molaire des unités monomériques M3 est comprise entre 0,01 et 5%, de préférence entre 0,05 et 2%, en particulier entre 0,1 et 1% dans ledit polymère. 10. Polymer according to the preceding claim characterized in that the molar content of the monomeric units M3 is between 0.01 and 5%, preferably between 0.05 and 2%, in particular between 0.1 and 1% in said polymer .
11. Liant pour électrode comprenant ledit polymère selon l'une quelconque des revendications 9 ou 10. 11. Binder for electrode comprising said polymer according to any one of claims 9 or 10.
12. Electrode comprenant ledit polymère selon l'une quelconque des revendications 9 ou 10. 12. Electrode comprising said polymer according to any one of claims 9 or 10.
13. Batterie comprenant ladite électrode selon la revendication précédente. 13. Battery comprising said electrode according to the preceding claim.
14. Utilisation dudit polymère fonctionnalisé selon l'une quelconque des revendications 9 et 10 dans la préparation d'un polymère conducteur, d'un électrolyte solide pour piles à combustibles, d'un revêtement hydrophile, d'un revêtement hydrophobe ou d'un revêtement absorbant l'UV.
14. Use of said functionalized polymer according to any one of claims 9 and 10 in the preparation of a conductive polymer, a solid electrolyte for fuel cells, a hydrophilic coating, a hydrophobic coating or a UV absorbing coating.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FRFR2209434 | 2022-09-19 | ||
| FR2209434A FR3139823A1 (en) | 2022-09-19 | 2022-09-19 | Functionalized halogenated polymer and preparation method thereof |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1138698A1 (en) * | 2000-03-31 | 2001-10-04 | Atofina | Structure comprising a fluorinated primer and electrode composed of said structure |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1138698A1 (en) * | 2000-03-31 | 2001-10-04 | Atofina | Structure comprising a fluorinated primer and electrode composed of said structure |
Non-Patent Citations (1)
| Title |
|---|
| TAN SHAOBO ET AL: "Base Catalyzed Thiol-Ene Click Chemistry toward Inner ?CH?CF? Bonds for Controlled Functionalization of Poly(vinylidene fluoride)", MACROMOLECULAR CHEMISTRY AND PHYSICS, vol. 219, no. 11, 1 June 2018 (2018-06-01), DE, pages 1700632, XP093023109, ISSN: 1022-1352, DOI: 10.1002/macp.201700632 * |
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