WO2016095207A1 - Carbon/fluoropolymer composite and manufacturing methods thereof - Google Patents
Carbon/fluoropolymer composite and manufacturing methods thereof Download PDFInfo
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- WO2016095207A1 WO2016095207A1 PCT/CN2014/094372 CN2014094372W WO2016095207A1 WO 2016095207 A1 WO2016095207 A1 WO 2016095207A1 CN 2014094372 W CN2014094372 W CN 2014094372W WO 2016095207 A1 WO2016095207 A1 WO 2016095207A1
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- 239000002131 composite material Substances 0.000 title claims abstract description 62
- 229920002313 fluoropolymer Polymers 0.000 title claims abstract description 25
- 239000004811 fluoropolymer Substances 0.000 title claims abstract description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title description 27
- 229910052799 carbon Inorganic materials 0.000 title description 18
- 238000004519 manufacturing process Methods 0.000 title description 7
- 229920000642 polymer Polymers 0.000 claims abstract description 71
- 238000000034 method Methods 0.000 claims abstract description 41
- 239000000203 mixture Substances 0.000 claims abstract description 39
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 26
- 150000004676 glycans Chemical class 0.000 claims abstract description 25
- 229920001282 polysaccharide Polymers 0.000 claims abstract description 24
- 239000005017 polysaccharide Substances 0.000 claims abstract description 24
- 239000012736 aqueous medium Substances 0.000 claims abstract description 12
- 238000010335 hydrothermal treatment Methods 0.000 claims abstract description 12
- 238000002360 preparation method Methods 0.000 claims abstract description 7
- 239000000178 monomer Substances 0.000 claims description 45
- 229920002907 Guar gum Polymers 0.000 claims description 28
- 239000000665 guar gum Substances 0.000 claims description 28
- 235000010417 guar gum Nutrition 0.000 claims description 28
- 229960002154 guar gum Drugs 0.000 claims description 28
- 239000003054 catalyst Substances 0.000 claims description 27
- 125000005843 halogen group Chemical group 0.000 claims description 25
- 229910052731 fluorine Inorganic materials 0.000 claims description 23
- 150000001768 cations Chemical class 0.000 claims description 19
- 229910052794 bromium Inorganic materials 0.000 claims description 16
- 229910052801 chlorine Inorganic materials 0.000 claims description 16
- 229910052740 iodine Inorganic materials 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 16
- 229910052736 halogen Inorganic materials 0.000 claims description 15
- 150000002367 halogens Chemical class 0.000 claims description 15
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 14
- 238000005341 cation exchange Methods 0.000 claims description 13
- 125000001153 fluoro group Chemical group F* 0.000 claims description 13
- 239000001913 cellulose Substances 0.000 claims description 10
- 229920002678 cellulose Polymers 0.000 claims description 10
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 229910006080 SO2X Inorganic materials 0.000 claims description 7
- 229920001577 copolymer Polymers 0.000 claims description 7
- 229910006095 SO2F Inorganic materials 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 125000001033 ether group Chemical group 0.000 claims description 5
- HTTJABKRGRZYRN-UHFFFAOYSA-N Heparin Chemical compound OC1C(NC(=O)C)C(O)OC(COS(O)(=O)=O)C1OC1C(OS(O)(=O)=O)C(O)C(OC2C(C(OS(O)(=O)=O)C(OC3C(C(O)C(O)C(O3)C(O)=O)OS(O)(=O)=O)C(CO)O2)NS(O)(=O)=O)C(C(O)=O)O1 HTTJABKRGRZYRN-UHFFFAOYSA-N 0.000 claims description 4
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 4
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- KXCLCNHUUKTANI-RBIYJLQWSA-N keratan Chemical compound CC(=O)N[C@@H]1[C@@H](O)C[C@@H](COS(O)(=O)=O)O[C@H]1O[C@@H]1[C@@H](O)[C@H](O[C@@H]2[C@H](O[C@@H](O[C@H]3[C@H]([C@@H](COS(O)(=O)=O)O[C@@H](O)[C@@H]3O)O)[C@H](NC(C)=O)[C@H]2O)COS(O)(=O)=O)O[C@H](COS(O)(=O)=O)[C@@H]1O KXCLCNHUUKTANI-RBIYJLQWSA-N 0.000 claims description 4
- 229920002472 Starch Polymers 0.000 claims description 3
- 150000007942 carboxylates Chemical class 0.000 claims description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- KIUKXJAPPMFGSW-DNGZLQJQSA-N (2S,3S,4S,5R,6R)-6-[(2S,3R,4R,5S,6R)-3-Acetamido-2-[(2S,3S,4R,5R,6R)-6-[(2R,3R,4R,5S,6R)-3-acetamido-2,5-dihydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-2-carboxy-4,5-dihydroxyoxan-3-yl]oxy-5-hydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylic acid Chemical compound CC(=O)N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@H](O[C@H]2[C@@H]([C@@H](O[C@H]3[C@@H]([C@@H](O)[C@H](O)[C@H](O3)C(O)=O)O)[C@H](O)[C@@H](CO)O2)NC(C)=O)[C@@H](C(O)=O)O1 KIUKXJAPPMFGSW-DNGZLQJQSA-N 0.000 claims description 2
- OMDQUFIYNPYJFM-XKDAHURESA-N (2r,3r,4s,5r,6s)-2-(hydroxymethyl)-6-[[(2r,3s,4r,5s,6r)-4,5,6-trihydroxy-3-[(2s,3s,4s,5s,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl]oxyoxan-2-yl]methoxy]oxane-3,4,5-triol Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@@H]1OC[C@@H]1[C@@H](O[C@H]2[C@H]([C@@H](O)[C@H](O)[C@@H](CO)O2)O)[C@H](O)[C@H](O)[C@H](O)O1 OMDQUFIYNPYJFM-XKDAHURESA-N 0.000 claims description 2
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 2
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 claims description 2
- GJCOSYZMQJWQCA-UHFFFAOYSA-N 9H-xanthene Chemical compound C1=CC=C2CC3=CC=CC=C3OC2=C1 GJCOSYZMQJWQCA-UHFFFAOYSA-N 0.000 claims description 2
- 229920002101 Chitin Polymers 0.000 claims description 2
- 229920001661 Chitosan Polymers 0.000 claims description 2
- 229920001287 Chondroitin sulfate Polymers 0.000 claims description 2
- 229920002307 Dextran Polymers 0.000 claims description 2
- 229920000926 Galactomannan Polymers 0.000 claims description 2
- 229920000288 Keratan sulfate Polymers 0.000 claims description 2
- JYDNKGUBLIKNAM-UHFFFAOYSA-N Oxyallobutulin Natural products C1CC(=O)C(C)(C)C2CCC3(C)C4(C)CCC5(CO)CCC(C(=C)C)C5C4CCC3C21C JYDNKGUBLIKNAM-UHFFFAOYSA-N 0.000 claims description 2
- 229920001218 Pullulan Polymers 0.000 claims description 2
- 239000004373 Pullulan Substances 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 229940072056 alginate Drugs 0.000 claims description 2
- 235000010443 alginic acid Nutrition 0.000 claims description 2
- 229920000615 alginic acid Polymers 0.000 claims description 2
- FVWJYYTZTCVBKE-ROUWMTJPSA-N betulin Chemical compound C1C[C@H](O)C(C)(C)[C@@H]2CC[C@@]3(C)[C@]4(C)CC[C@@]5(CO)CC[C@@H](C(=C)C)[C@@H]5[C@H]4CC[C@@H]3[C@]21C FVWJYYTZTCVBKE-ROUWMTJPSA-N 0.000 claims description 2
- MVIRREHRVZLANQ-UHFFFAOYSA-N betulin Natural products CC(=O)OC1CCC2(C)C(CCC3(C)C2CC=C4C5C(CCC5(CO)CCC34C)C(=C)C)C1(C)C MVIRREHRVZLANQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000679 carrageenan Substances 0.000 claims description 2
- 229920001525 carrageenan Polymers 0.000 claims description 2
- 235000010418 carrageenan Nutrition 0.000 claims description 2
- 229940113118 carrageenan Drugs 0.000 claims description 2
- 125000001072 heteroaryl group Chemical group 0.000 claims description 2
- 229920002674 hyaluronan Polymers 0.000 claims description 2
- 229960003160 hyaluronic acid Drugs 0.000 claims description 2
- 229920005610 lignin Polymers 0.000 claims description 2
- 235000019423 pullulan Nutrition 0.000 claims description 2
- 229910021653 sulphate ion Inorganic materials 0.000 claims description 2
- 229920001864 tannin Polymers 0.000 claims description 2
- 239000001648 tannin Substances 0.000 claims description 2
- 235000018553 tannin Nutrition 0.000 claims description 2
- 229920001285 xanthan gum Polymers 0.000 claims description 2
- UHVMMEOXYDMDKI-JKYCWFKZSA-L zinc;1-(5-cyanopyridin-2-yl)-3-[(1s,2s)-2-(6-fluoro-2-hydroxy-3-propanoylphenyl)cyclopropyl]urea;diacetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O.CCC(=O)C1=CC=C(F)C([C@H]2[C@H](C2)NC(=O)NC=2N=CC(=CC=2)C#N)=C1O UHVMMEOXYDMDKI-JKYCWFKZSA-L 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 16
- HFJRKMMYBMWEAD-UHFFFAOYSA-N dodecanal Chemical compound CCCCCCCCCCCC=O HFJRKMMYBMWEAD-UHFFFAOYSA-N 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 12
- 150000001721 carbon Chemical class 0.000 description 12
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 12
- -1 such as HF Substances 0.000 description 12
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- 239000003377 acid catalyst Substances 0.000 description 10
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- 238000005470 impregnation Methods 0.000 description 8
- 239000000377 silicon dioxide Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
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- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 5
- 125000002091 cationic group Chemical group 0.000 description 5
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 5
- 150000004706 metal oxides Chemical class 0.000 description 5
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 5
- 238000000634 powder X-ray diffraction Methods 0.000 description 5
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- 239000011347 resin Substances 0.000 description 5
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- 235000014692 zinc oxide Nutrition 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
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- 244000007835 Cyamopsis tetragonoloba Species 0.000 description 4
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- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical class [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 4
- 229910000323 aluminium silicate Inorganic materials 0.000 description 4
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- 235000013980 iron oxide Nutrition 0.000 description 4
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 4
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- 229910000476 molybdenum oxide Inorganic materials 0.000 description 4
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical class [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 4
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- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 3
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- 239000011737 fluorine Substances 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
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- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
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- NQNBVCBUOCNRFZ-UHFFFAOYSA-N nickel ferrite Chemical compound [Ni]=O.O=[Fe]O[Fe]=O NQNBVCBUOCNRFZ-UHFFFAOYSA-N 0.000 description 1
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- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
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- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
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- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
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Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/08—Ion-exchange resins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/08—Ion-exchange resins
- B01J31/10—Ion-exchange resins sulfonated
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08L27/18—Homopolymers or copolymers or tetrafluoroethene
Definitions
- US 2001037045 (E.I. DUPONT DE NEMOURS) 2001/11/1discloses a sol-gel process for manufacturing a porous microcompositecomprising an inorganic oxide and a perfluorinated ion-exchange polymer comprising pendant sulfonic and/or carboxylic acid groups.
- US 20020137626 (E.I. DUPONT DE NEMOURS) 2002/9/26 seems to describe a structurally similar catalyst made by sol-gel process, the catalyst comprising a stationary acid component chosen among, inter alia, a perfluorinated ion exchange polymer on an inert support and a mobile acid component.
- Yet another object of the present invention is the use of said composite (C) as catalyst, especially in heterogeneous catalysis.
- Polymer (I) comprises advantageously at most 75 %, preferably at most 50 %, more preferably at most 30 %, even more preferably at most 20 % by moles of recurring units derived from the functional monomer, based on the total moles of recurring units.
- w is an integer between 0 and 2
- RF1 and RF 2 are independently -F, -Cl or a C 1- 10 perfluoroalkyl group, optionally substituted with one or more ether oxygens
- y is an integer between 0 and 6
- X’ is chosen among H, halogens (Cl, F, Br, I) , -O - M + , wherein M + is a cation selected among H + , NH 4 + , K + , Li + , Na + , or mixtures thereof; preferably X’ is fluorine; preferred sulfonatedperfluoroalkoxyvinylether complies with formula (M3) here above, wherein w is 1, RF 1 is -CF 3 , y is 1 and RF 2 is -F and X’ is F [formula (M3-A) , also called “PSEPVE” (perfluoro-2- (2-
- w, y, RF 1 and RF 2 have the same meaning as above defined, and R H ⁇ is a C 1-10 alkyl or fluoroalkyl group; preferred perfluoroalkoxyvinylether carboxylate complies with formula (M4) here above, wherein w is 0, y is 2, R H ⁇ is methyl and RF 2 is -F [formula (M4-A) ] :
- Preferred polymer (I) is chosen among functional per (halo) fluoropolymers comprising (preferably consisting essentially of) recurring units derived from at least one functional per (halo) fluoromonomer and at least one per (halo) fluoromonomer chosen among:
- C 3 -C 8 perfluoroolefins preferably tetrafluoroethylene (TFE) and/or hexafluoropropylene (HFP) ;
- the Applicant thinks, without limiting the scope of its invention, that the proper combination of the above-described metallic or semi-metallic oxide compound in the composite (C) can substantially modify its surface properties, advantageously enabling improved accessibility of the polymer (I) active sites.
- Type 3 HP8FF guar gum obtained from Solvay Novecare, whch is a hydroxypropyl guar
- HZSM-5 a commercialized acidic zeolite catalyst purchased from the Dow Chemical Company.
- a carbon/PFSA composite was synthesized in this Example using cellulose as the carbon source.
- a 20wt% aqueous solution was prepared by adding 1 g powder of PW66-S to 20 mL of deionized water in a glass beaker, with subsequent stirring at a temperature of 50°C.
- 1 g of cellulose was slowly added into the solution under vigorous stirring, forming a white suspension.
- the suspension was covered and left to stand for 2 hours at 50°C, and the cellulose was neither dissolved nor gelled.
- the suspension was transferred to a sealed Teflon autoclave (50mL) and hydrothermal reaction was performed at 180°C for 24 hours.
- Acid density of so-obtained composites/carbon materials was determined using acid-base titration with a Metrohm 794 Basic Titrano instrument. Prior to titration with 0.01 M NaOH solution, the samples were subjected to ion-exchange with a 0.5M NaCl solution at room temperature, for 24 hours.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Provided is a process for the preparation of a composite (C) comprising at least one functional fluoropolymer [polymer (I)] and at least one carbon material, wherein the weight percentage of the polymer (I) in the composite (C) is from 0.1 to 85 percent, said process comprising the steps of: (a) preparing a mixture (A) comprising at least one polymer (I) and at least one polysaccharide in an aqueous medium; and (b) subjecting the mixture (A) to a hydrothermal treatment to yield the composite (C).
Description
The present invention pertains to a carbon/fluoropolymer composite， a process for its manufacture， and its uses as catalyst.
Background Art
In chemical industry， acid catalysed processes were traditionally carried out using homogeneous catalysts， i.e. catalysts soluble in the reaction medium， such as HF， sulphuric acid and nitric acid， which are effective in providing required acidity but are known as dangerous and polluting substances， and are generally difficult to separate from the reaction mixture.
Thus， over the past two decades， various heterogenised acid catalysts were developed as an alternative to these homogeneous acid catalysts. Among them， special attention has been paid to solid organic polymers able to exchange H+ ions (or “ionomers” ， hereinafter) ， which advantageously provide a wide range of acidity and fair chemical stability， and are relatively easy to recover.
Notably， functional fluoropolymers， in particular fluoroionomers having sulfonic acid pendant groups， have shown substantial advantages over other heterogenised acid catalysts. This is largely attributed to their fluorocarbon portion in the molecule， which not only gives extraordinary chemical and thermal stability， but also provides an electron-withdrawing effect to render stronger acid groups.
Nevertheless， despite the higher cost， the high swelling of many fluoroionmers in polar media have limited their catalytic use and inconvenienced the subsequent recycling.
It has thus been suggested in the past to support the functional fluoropolymer on suitable inorganic carriers for acid catalyst use.
For instance， US 2001037045 (E.I. DUPONT DE NEMOURS) 2001/11/1discloses a sol-gel process for manufacturing a porous
microcompositecomprising an inorganic oxide and a perfluorinated ion-exchange polymer comprising pendant sulfonic and/or carboxylic acid groups. Said ″inorganic oxide″ is chosen among metallic， semimetallic or other inorganic oxide compounds， including， for example， alumina， silica， titania， germania， zirconia， alumino-silicates， zirconyl-silicates， chromic oxides， germanium oxides， copper oxides， molybdenum oxides， tantalum oxides， zinc oxides， yttrium oxides， vanadium oxides， and iron oxides. Among these alumina， silica， titania and zirconia are preferred， and silica is most preferred.
Also， US 20020137626 (E.I. DUPONT DE NEMOURS) 2002/9/26 seems to describe a structurally similar catalyst made by sol-gel process， the catalyst comprising a stationary acid component chosen among， inter alia， a perfluorinated ion exchange polymer on an inert support and a mobile acid component. For said “inert support” ， silica is preferred but a metal oxide (metallic or semimetallic oxide compounds， including， e.g.， alumina， silica， titania， germania， zirconia， alumino-silicates， zirconyl-silicates， chromic oxides， germanium oxides， copper oxides， molybdenum oxides， tantalum oxides， zinc oxides， yttrium oxides， vanadium oxides， and iron oxides) can be substituted to replace silica.
US 2003176729 (E.I. DUPONT DE NEMOURS) 2003/9/18 describes another type of supported ionomer catalyst prepared by sol-gel process， which takes the form of porous microcomposites and is prepared from perfluorinated ion-exchange polymer and metal oxides such as silica. Other suitable “metal oxides” mentioned therein include various metallic or semi-metallic oxide compounds， i.e. alumina， titania， germania， zirconia， alumino-silicates， zirconyl-silicates， chromic oxides， germanium oxides， copper oxides， molybdenum oxides， tantalum oxides， zinc oxides， yttrium oxides， vanadium oxides， and iron oxides.
US 2005245658 (ROCKWELL SCIENTIFIC LICENSING) 2005/11/3 discloses a different method for forming fluoropolymer-metal oxide nanocomposites， which is based on ion exchange and precipitation within a polymer matrix. Said nanocomposites comprising a wettable polymer having ion-exchangeable groups pendant therefrom and metal oxides
trapped within the polymer structure， wherein the metal oxides may be selected from a group consisting of Fe2O3， MnFe2O4， CoFe2O4， NiFe2O4， Ni-Fe alloys and ZnO.
EP 1911796 A (SOLVAY SOLEXIS S.P.A.) 2008/4/16 discloses yet another type of supported fluoropolymer catalyst， which comprises at least one functional fluoropolymer and a cerium compound. In the examples therein， said supported catalyst was synthesized using incipient wetness impregnation or adsorption-precipitation approach.
Different from the aforedescribed oxide-supported polymer catalysts， CN 103599815 (NANJING FORESTRY UNIV) 2014/2/26 discloses an active carbon-supported PFSA (perfluorosulfonic acid) polymer catalyst， also manufactured by an impregnation-based method. According to CN 103599815， this catalyst manufacturing process requires a specific， multi-step pre-treatment of active carbon material， before mixing it with a PFSA solution and subjecting the mixture to reflux-impregnation， evaporation， grinding， and activation of the ground powders at 100-120℃ after treating the powders by inorganic acid， reflux impregnation， suction filtration， water washing and suction filtration.
Nevertheless， supported polyacid catalysts of the above prior art， limited by their support material selection and/or complicated manufacturing processes， do not satisfy all the efficiency and environmental requirements for an ideal replacement of traditional homogeneous acid catalysts.
There is thus still a need for a solid acid catalyst that is sufficiently active， economically viable， and also conveniently produced by an environmental friendly method.
Brief description of drawings
Fig. 1 shows the PXRD (powder X-ray diffraction) patterns of the composites or carbon materials obtained from the working examples (curves I， II， III， IV， and V respectively correspond to Ex. 2， Ex. 1-C， Ex. 1-B，Ex. 1-A， and Comp. Ex. 1) ， as well as the
polymer as
purchased (curve VI) . The x-axis is 2θ angle in degrees and the y-axis is intensity in arbitrary units.
Fig. 2A shows the FTIR (Fourier Transform Infrared) spectra for a composite obtained from guar gum and
by hydrothermal treatment (Ex. 1-B， the middle curve ii) ， a composite obtained from active carbon and
using impregnation method (Comp. Ex. 3， the upper curve iii) ， and
polymer by itself (the lower curve i) . The x-axis is wavenumber in cm-1.
Fig. 2B shows the FTIR spectra for an active carbon material (the lower curve a) and a carbon material obtained from hydrothermal carbonization of guar gum (the upper curve b) . The x-axis is wavenumber in cm-1.
Summary of invention
It is therefore one object of the present invention to provide a process for the preparation of a composite (C) comprising at least one functional fluoropolymer [polymer (I) ] and at least one carbon material， wherein the weight percentage of the polymer (I) in the composite (C) is from 0.1 to 85 percent， said process comprising the steps of：
(a) preparing a mixture (A) comprising at least one polymer (I) and at least one polysaccharide in an aqueous medium； and
(b) subjecting the mixture (A) to a hydrothermal treatment to yield the composite (C) .
Advantageously， compared to the prior art， the above process not only simplifies the manufacture of various carbon/fluoropolymer composites for industrial uses， but also provides shaped composites with better handling characteristics and enhanced catalytic activity in many chemical reactions.
Another object of the present invention is a composite (C) produced by the above process.
Yet another object of the present invention is the use of said composite (C) as catalyst， especially in heterogeneous catalysis.
As mentioned above， the invented process is for the preparation of a composite (C) comprising at least one polymer (I) and at least one carbon
material， wherein the weight percentage of the polymer (I) in the composite (C) is from 0.1 to 85 percent. Preferably， the weight percentage of the polymer (I) is from 0.1 to 50 percent， more preferably from 0.1 to 25 percent.
In step (a) of the invented process， the ″at least one functional fluoropolymer [polymer (I) ] ″is intended to denote one or more than one polymer (I) . In the same way， the expression of “at least one polysaccharide” is intended to denote one or more than one type of polysaccharide. Mixtures of polymers (I) or polysaccharides can be advantageously used in the step (a) . For illustrative purposes， polymer (I) and polysaccharide are described in detail below.
In the rest of the text， the singular form of ″functional fluoropolymer″， ″polymer (I) ″or “polysaccharide” is intended to include both singular and plural unless the context clearly indicates otherwise.
Polymer (I)
For the purpose of the present invention， the term ″functional fluoropolymer″or ″polymer (I) ″is intended to denote any polymer comprising：
-recurring units derived from at least one ethylenically unsaturated monomer comprising at least one fluorine atom ( “fluorinated monomer” ， hereinafter) ； and
-a substantial amount of recurring units derived from at least one ethylenically unsaturated monomer comprising at least one cation exchange group ( “functional monomer” ， hereinafter) .
The term ″at least one ethylenically unsaturated monomer comprising at least one fluorine atom [fluorinated monomer] ″is understood to mean that the functional fluoropolymer can comprise recurring units derived from one or more than one fluorinated monomer. As used herein， the expression ″fluorinated monomer″is understood to include both singular and plural， unless the context clearly indicates otherwise.
With regard to the fluorinated monomer in polymer (I) ， it can further comprise one or more other halogen atoms (Cl， Br， I) . Shall the fluorinated monomer be free of hydrogen atom， it is designated as
per (halo) fluoromonomer. Shall the fluorinated monomer comprise at least one hydrogen atom， it is designated as hydrogen-containing fluorinated monomer.
Non limitative examples of fluorinated monomers are notably tetrafluoroethylene (TFE) ， vinylidene fluoride (VdF) ， chlorotrifluoroethylene (CTFE) ， and mixtures thereof.
The term ″substantial amount″in the above definition of polymer (I) is intended to denote an amount of recurring units derived from the functional monomer which is effective to modify the polymer (I) in its properties. Generally， a substantial amount is of at least 1％ by moles， based on the total moles of recurring units.
As used in the above text and throughout the specification， the term ″cation exchange group″has its general meaning as intended in organic chemistry and encompasses atoms or combination of atoms bonded to the carbon skeleton of the ethylenically unsaturated monomer， which confers to said ethylenically unsaturated monomer ability to trap and release (i.e. exchange) cations in a process called ion exchange. Generally， cation exchange groups comprise negatively charged moieties which can bind cations.
The choice of the cation bound to the negatively charged moiety is not critical. For example， cation exchange groups usually come with sodium (Na+) or hydrogen (H+) ions attached to said exchange sites. Both of these ions have generally low affinities to the sites. It is widely understood that when such exchange sites are exposed to appropriate conditions (e.g. in a reactive environment) ， cations can be replaced by protons so as to obtain an acid catalysts possessing labile H+.
The polymer (I) has preferably linked on its cation exchange groups， hydrogen (H+) ions.
Non limitative examples of cation exchange groups are notably those complying with formula：
-SO2X， wherein X is chosen among halogens (Cl， F， Br， I) ， -O-M+， wherein M+ is a cation selected among H+， NH4
+， K+， Li+， Na+， or mixtures thereof；
-COY， wherein Y is chosen among halogens (Cl， F， Br， I) ； -O-M+， wherein M+ is a cation selected among H+， NH4
+， K+， Li+， Na+； -ORHy wherein RHy is a C1-C6 hydrocarbon group； -ORHf wherein RHf is a C1-C6 fluorocarbon or per (halo) fluorocarbon group； -N (RHy＊) 2， wherein RHy＊， equal or different at each occurrence， is hydrogen or a C1-C6 hydrocarbon group， or mixtures thereof； or
-PO2Z， wherein Z is chosen among halogens (Cl， F， Br， I) ； -O-M+， wherein M+ is a cation selected among H+， NH4
+， K+， Li+， Na+； -ORHy wherein RHy is a C1-C6 hydrocarbon group， and -ORHf， wherein RHf is a C1-C6 fluorocarbon or per (halo) fluorocarbon group， or mixture thereof.
Should the functional monomer comprise at least one fluorine atom which is not comprised in the functional group， it is designated as fluorinated functional monomer. Should the functional monomer be free of fluorine atoms other than those optionally comprised in the functional group， it is designated as hydrogenated functional monomer.
The fluorinated monomer and the fluorinated functional monomer may be the same monomer or may be different monomers， that is to say that the polymer (I) can be a homopolymer of a fluorinated functional monomer， or can be a copolymer of at least one fluorinated monomer and at least one functional monomer， fluorinated or hydrogenated.
Polymer (I) comprises advantageously at least 1 ％， preferably at least 2 ％， more preferably at least 3 ％， even more preferably at least 5 ％， by mole of recurring units derived from the functional monomer， based on the total moles of recurring units.
Polymer (I) comprises advantageously at most 75 ％， preferably at most 50 ％， more preferably at most 30 ％， even more preferably at most 20 ％ by moles of recurring units derived from the functional monomer， based on the total moles of recurring units.
Optionally， the polymer (I) may further comprise recurring units derived from at least one other monomer [ “comonomer (CM) ” ， hereinafter] .
The comonomer (CM) can notably be either hydrogenated (i.e. free of fluorine atom) [comonomer (HCM) ， hereinafter] or fluorinated (i.e. containing at least one fluorine atom) [comonomer (FCM) ， hereinafter] .
Non limitative examples of suitable hydrogenated comonomers (HCM) are notably ethylene， propylene， vinyl monomers such as vinyl acetate， acrylic monomers， like methyl methacrylate， acrylic acid， methacrylic acid and hydroxyethyl acrylate， as well as styrene monomers， like styrene and p-methylstyrene.
Non limitative examples of suitable fluorinated comonomers (FCM) are notably：
-C3-C8fluoro-and/or perfluoroolefins， such as hexafluoropropene， pentafluoropropylene， and hexafluoroisobutylene；
-C2-C8 hydrogenated monofluoroolefins， such as vinyl fluoride；
-1， 2-difluoroethylene， vinylidene fluoride and trifluoroethylene；
-perfluoroalkylethylenes complying with formula CH2＝CH-Rf0， in which Rf0 is a C1-C6 perfluoroalkyl；
-chloro-and/or bromo-and/or iodo-C2-C6fluoroolefins， like chlorotrifluoroethylene；
-fluoroalkylvinylethers complying with formula CF2＝CFORf1 in which Rf1 is a C1-C6 fluoro-or perfluoroalkyl， e.g. -CF3， -C2F5， -C3F7；
-fluoro-oxyalkylvinylethers complying with formula CF2＝CFOX0， in which X0 is a C1-C12 oxyalkyl， or a C1-C12 (per) fluorooxyalkyl having one or more ether groups， like perfluoro-2-propoxy-propyl；
-fluoroalkyl-methoxy-vinylethers complying with formula CF2＝CFOCF2ORf2 in which Rf2 is a C1-C6 fluoro-or perfluoroalkyl， e.g. -CF3， -C2F5， -C3F7 or a C1-C6 (per) fluorooxyalkyl having one or more ether groups， like-C2F5-O-CF3；
-fluorodioxoles， of formula：
wherein each of Rf3， Rf4， Rf5， Rf6， equal or different each other， is independently a fluorine atom， a C1-C6 fluoro-or per (halo) fluoroalkyl，
optionally comprising one or more oxygen atom， e.g. -CF3， -C2F5， -C3F7， -OCF3， -OCF2CF2OCF3.
Preferably， the polymer (I) comprises recurring units derived from at least one functional monomer chosen among：
(M1) sulfonatedperfluoroolefin of formula (M1) ：
wherein n is an integer between 0 and 6 and X’ is chosen among halogens (Cl， F， Br， I) ， -O-M+， wherein M+ is a cation selected among H+， NH4
+， K+， Li+， Na+， or mixtures thereof； preferred sulfonatedperfluoroolefin are those complying with formulae (M1-A) and (M1-B) ：
wherein X’ has the same meaning as above defined；
(M2) sulfonatedperfluorovinylethers of formula (M2) ：
wherein m is an integer between 1 and 10 and X’ is chosen among halogens (Cl， F， Br， I) ， -O-M+， wherein M+ is a cation selected among H+， NH4
+， K+， Li+， Na+， or mixtures thereof； preferred are sulfonatedperfluorovinylethers of formulae (M2-A) ， (M2-B) and (M2-C) ：
wherein X’ has the same meaning as above defined； most preferably， the sulfonatedperfluorovinylether is
perfuoro-5-sulphonylfluoride-3-oxa-1-pentene (also known as “SFVE” ) of formula (M2-D) ：
which can be in its -SO2F form or in any of the -SO2X’ forms， as above detailed；
(M3) sulfonatedperfluoroalkoxyvinylethers of formula (M3) ：
wherein w is an integer between 0 and 2， RF1 and RF2， equal or different from each other and at each occurrence， are independently -F， -Cl or a C1-
10 perfluoroalkyl group， optionally substituted with one or more ether oxygens， y is an integer between 0 and 6 and X’ is chosen among H， halogens (Cl， F， Br， I) ， -O-M+， wherein M+ is a cation selected among H+， NH4
+， K+， Li+， Na+， or mixtures thereof； preferably X’ is fluorine； preferred sulfonatedperfluoroalkoxyvinylether complies with formula (M3) here above， wherein w is 1， RF1 is -CF3， y is 1 and RF2 is -F and X’ is F [formula (M3-A) ， also called “PSEPVE” (perfluoro-2- (2-fluorosulfonylethoxy) propylvinyl ether) ] ：
which can be in its -SO2F form or in any of the -SO2X’ forms， as above detailed；
(M4) perfluoroalkoxyvinylether carboxylates of formula (M4) ：
wherein w， y， RF1 and RF2 have the same meaning as above defined， and RH§ is a C1-10 alkyl or fluoroalkyl group； preferred perfluoroalkoxyvinylether carboxylate complies with formula (M4) here above， wherein w is 0， y is 2， RH§ is methyl and RF2 is -F [formula (M4-A) ] ：
(M5) sulfonated aromatic (per) fluoroolefins of formula (M5) ：
wherein Ar is a C3-15 aromatic or heteroaromatic moiety and X’ is chosen among halogens (Cl， F， Br， I) ， -O-M+， wherein M+ is a cation selected among H+， NH4
+， K+， Li+， Na+， or mixtures thereof； and
(M6) mixtures thereof.
Optionally， the polymer (I) may comprise recurring units derived from bis-olefins of formula：
wherein j is an integer between 2 and 10， preferably between 4 and 8， and R1， R2， R3， R4， equal or different from each other， are H or C1-5 alkyl or fluoroalkyl groups.
Should the polymer (I) comprise recurring units derived from a bis-olefin as above defined， it advantageously comprises said recurring units in a low amount of from 0.01 to 5 ％ by mole， with respect to all recurring units of polymer (I) .
Preferably， the polymer (I) is free from recurring units derived from bis-olefins as above specified.
In one preferred embodiment， the polymer (I) is a functional per (halo) fluoropolymer. For the purpose of the invention， the term “functional per (halo) fluoropolymer” is intended to denote a functional fluoropolymer substantially free of hydrogen atoms.
The term “substantially free of hydrogen atom” is understood to mean that the functional per (halo) fluoropolymer consists essentially of：
-recurring units derived from one or more than one ethylenically unsaturated monomer comprising at least one fluorine atom and free from hydrogen atoms [ “per (halo) fluoromonomer” ， hereinafter] ； and
-recurring units derived from one or more than one ethylenically unsaturated monomer comprising at least one fluorine atom and at least one cation exchange group， and free from hydrogen atoms (except those optionally comprised in the cation exchange group) [ “functional per (halo) fluoromonomer” ， hereinafter] .
The per (halo) fluoromonomer and the functional per (halo) fluoromonomer may be same or different monomers， that is to say that the functional
per (halo) fluoropolymer can be a homopolymer of a functional per (halo) fluoromonomer， or can be a copolymer of at least one per (halo) fluoromonomer and at least one functional per (halo) fluoromonomer.
Preferred polymer (I) is chosen among functional per (halo) fluoropolymers comprising (preferably consisting essentially of) recurring units derived from at least one functional per (halo) fluoromonomer and at least one per (halo) fluoromonomer chosen among：
C3-C8 perfluoroolefins， preferably tetrafluoroethylene (TFE) and/or hexafluoropropylene (HFP) ；
chloro-and/or bromo-and/or iodo-C2-C6 per (halo) fluoroolefins， like chlorotrifluoroethylene (CTFE) and/or bromotrifluoroethylene；
perfluoroalkylvinylethers (PAVE) complying with formula CF2＝CFORf1 in which Rf1 is a C1-C6 perfluoroalkyl， e.g. -CF3， -C2F5， -C3F7； and
perfluoro-oxyalkylvinylethers complying with formula CF2＝CFOX0， in which X0 is a C1-C12 perfluorooxyalkyl having one or more ether groups， like perfluoro-2-propoxy-propyl.
More preferred polymer (I) is chosen among tetrafluoroethylene (TFE) copolymers comprising (preferably consisting essentially of) recurring units derived from at least one functional per (halo) fluoromonomer as above defined.
Preferred functional per (halo) fluoromonomer are notably sulfonatedperfluorovinylethers of formula (M2) as above detailed and sulfonatedperfluoroalkoxyvinylethers of formula (M3) as above detailed， and mixtures thereof.
Even more preferred polymer (I) is selected among TFE copolymers comprising (preferably consisting essentially at) recurring units derived from PSEPVE (formula M3-Ahere above) and/or SFVE (formula M2-D here above) ， in their-SO2F or-SO2X” form， wherein X” is chosen among halogens (Cl， Br， I) ， -O-M+， and wherein M+ is a cation selected among H+， NH4
+， K+， Li+， Na+， or mixtures thereof； preferably in their-SO3H form.
Still more preferred polymer (I) is selected among TFE copolymers comprising (preferably consisting essentially of) ：
-from 5 to 25 ％ by moles of recurring units derived from PSEPVE and/or SFVE， in their-SO2F or-SO2X” form， wherein X” is chosen among halogens (Cl， Br， I) ， -O-M+， wherein M+ is a cation selected among H+， NH4
+， K+， Li+， Na+， or mixtures thereof； preferably in their-SO3H form； and
-from 95 to 75 ％ by moles of recurring units derived from TFE.
According to a preferred embodiment of the invention， the polymer (I) is chosen among TFE copolymers as above described wherein the functional monomer is SFVE， in its -SO2F or -SO2X” form， wherein X” is chosen among halogens (Cl， Br， I) ， -O-M+， wherein M is a cation selected among H+，NH4
+， K+， Li+， Na+， or mixtures thereof； preferably in its -SO3H form.
It has been surprisingly found that， by using the polymer (I) of this preferred embodiment in step (a) ， a composite (C) with improved catalytic behaviour can be produced， especially when used as acid catalysts， e.g. in the acetalization of glycol with dodecanal.
Polysaccharide
For the purpose of the invention， the term “polysaccharide″is intended to mean any polymer consisting of several monosaccharides linked together by O-glycoside bonds and having the general formula of Cx (H2O) ywhere x is usually a large number between 200 and 2500.
The polysaccharide used in step (a) of the invented process is not particularly limited， and the examples thereof include： cellulose and its derivatives， guar gum， lignin， tannins， betulin， chondroitin sulphate， keratan， keratan sulphate， heparin， heparin sulphate， xanthan， carrageenan， hyaluronic acid， chitin， chitosan， alginate， starch， dextran， pullulan， and galactomannan.
Preferably， the polysaccharide used in step (a) is selected among guar gum， cellulose， and derivative thereof， and is more preferably selected from guar gum and its derivatives. Notably， the derivatives of guar gum include cationic guar gum and anionic guar gum.
As used herein and as understood in the art， “guar gum” refers to the mucilage found in the seed of the leguminous plant
Cyamopsistetragono/obus. The seeds are composed of a pair of tough non-brittle endosperm sections， hereinafter referred to as guar splits. Guar splits contain guar gum but are tough and extremely difficult to grind into a powder form for recovery of the gum. After processing， native guar gum is obtained in the form of a yellow powder and has a molecular weight of between about 2,000,000 Daltons and 5,000,000 Daltons.
Derivatives of guar gum are usually made by grafting thereto a desired functional group， such as a cationic， nonionic or anionic substituent group， or a precursor thereof. Suitable cationic substituent groups include primary， secondary， or tertiary amino groups or quaternary ammonium， sulfonium， or phosphinium groups. Suitable nonionic substituent groups include hydroxyalkyl groups， such as hydroxypropyl groups. Suitable anionic groups include carboxyalkyl groups， such as carboxymethyl groups. The cationic， nonionic and/or anionic substituent groups may be introduced to the guar polysaccharide chains via a series of reactions or by simultaneous reactions with the respective appropriate derivatizing agents.
Native guar gum or its derivatives may be obtained from Solvay Novecare.
These polysaccharides may be used singly or in combination.
Generally， in the mixture (A) obtained at the end of step (a) ， the weight ratio of polysaccharide to polymer (I) is from 1∶3 to 3∶1， and preferably from 1∶1.5 to 1.5∶1， in the aqueous medium.
As used herein， the term ″aqueous medium″generally means a liquid medium that contains water. The water content is said aqueous medium is typically at least 25 wt％， more typically at least 50 wt％， and even more typically at least 75 wt％. Optionally， the aqueous medium may contain one or more water miscible organic liquids， such as an alcohol， in an amount of typically less than 75 wt％， more typically less than 50 wt％， and even more typically less than 25 wt％. An aqueous medium according to the present invention may also optionally contain one or more solutes dissolved therein. In one embodiment， the liquid portion of an aqueous medium consists essentially of water. In another embodiment， the liquid portion of an aqueous medium consists solely of water.
The weight percentage of polymer (I) or polysaccharide in the mixture (A) is not particularly limited， as long as both may be dispersed in the aqueous medium.
For instance， the mixture (A) may contain from 1％ to 25％ by weight of at least one polymer (I) as described above.
Moreover， the mixture (A) may contain from 2％ to 30％ by weight of at least one polysaccharide as described above.
The mixture (A) may take a gel form or ungelled form， at the end of step (a) .
In the subsequent step (b) of the invented process， the mixture (A) is subjected to a hydrothermal treatment.
The hydrothermal treatment in step (b) is carried out at an elevated temperature of preferably at least 80℃ and an elevated pressure of higher than 1 bar.
Generally， the hydrothermal treatment in step (b) may be carried out at a temperature in a range of 100℃ to 250℃ and preferably 140℃ to 220℃， and a pressure in a range of 1 to 15 bar and preferably 2 to 10 bar.
Generally， the hydrothermal treatment in step (b) may be carried out for a time period of at least 1 hour， preferably during 1 to 70 hours， and more preferably from 5 to 36 hours.
The hydrothermal treatment of mixture (A) in step (b) yields a reaction mixture， where the target composite (C) is easily separated from minor components， if present， such as by dissolution， centrifugation and filtration.
Accordingly， the invented process may further include a post-treatment step (c) ， which consists of washing and drying the reaction mixture obtained from step (b) .
Moreover， the invented process may further include a step (d) of grinding the reaction mixture obtained from step (b) ， whether post-treated or not， to provide particles having smaller sizes.
As mentioned， another embodiment of the invention is directed to a composite (C) produced by the above-described process， which comprises at least one polymer (I) and at least one carbon material， wherein the weight percentage of the polymer (I) in the composite (C) is from 0.1 to 85
percent， preferably from 0.1 to 50 percent， and more preferably from 0.1 to 25 percent.
The skilled in the art will select， as a matter of routine work， the precise weight percentage of polymer (I) as a function， notably， of the nature and concentration of cation exchange groups in the polymer (I) and of the reaction and conditions in which the composite (C) shall be employed as a catalyst.
The carbon material in the composite (C) comprises a carbon material obtained from the polysaccharide used in step (a) ， which is generally amorphous in nature and can take the form of active carbon and/or carbon black and/or graphitic carbon.
Preferably， the carbon material in the composite (C) comprises a porous carbon material obtained from the polysaccharide used in step (a) ， which is generally microporous or mesoporous structure with a large surface area and an average pore volume of ＜ 1ml/g.
Advantageously， the Applicant found that the hydrothermal treatment of step (b) could generate composite having porous carbon skeleton， which is characterized by large surface area and fair porosity to help immobilize the polymer (I) . Such porous carbon structure could also provide a good dispersion for the cation exchange group within the composite (C) and gives high catalytic activity by increasing reactant accessibility.
As a whole， the composite (C) can be provided under different forms. For instance， it can be provided under the form of powder， i.e. of discrete solid particles， under the form of shaped three-dimensional forms (e.g. extrudates， pellets) or can be shaped to yield self-standing membranes， with or without the use of suitable support polymeric materials.
Should the composite (C) be provided under the form of powder， it generally has an average particle size of 1 to 1000 μm， preferably from 5 to 100 μm. Selection of this range of particle size is particularly advantageous with the aim of maximizing surface area and still having a material easy to handle and which do not generate difficulties of separation in gas/solid reactions (e.g. in suspended bed reactions) .
The composite (C) can further comprise， in addition to polymer (I) and carbon material discussed above， additional components.
For instance， the composite (C) can comprise one or more of the usual additives and fillers used in combination with the polymer (I) or carbon. Mention can be notably made of processing aids， pigments， filling materials， electrically conductive particles， lubricating agents， heat stabilizer， anti-static agents， extenders， reinforcing agents， organic and/or inorganic pigments like TiO2， acid scavengers， such as MgO， flame-retardants， smoke-suppressing agents and the like.
By way of non-limiting examples of filling material， mention may be made of mica， alumina， talc， glass fibers， carbon fibers， graphite in the form of fibers or of powder， carbonates such as calcium carbonate， macromolecular compounds and the like.
As lubricating agents we can notably mention graphite， perfluorinated polymers， such as PTFE， silicone oil and the like.
According to a preferred embodiment of the invention， the composite (C) comprises at least one carrier/promoter chosen among metallic or semi-metallic oxide compounds； said carrier/promoter is preferably chosen among alumina， ceria， silica， titania， germania， zirconia， alumino-silicates， zirconyl-silicates， chromic oxides， germanium oxides， copper oxides， cobalt oxides， nickel oxides， molybdenum oxides， tantalum oxides， zinc oxides， yttrium oxides， vanadium oxides， iron oxides and mixtures thereof. Still preferably， the at least one carrier/promoter is chosen among ceria， zirconia， and mixture thereof.
The Applicant thinks， without limiting the scope of its invention， that the proper combination of the above-described metallic or semi-metallic oxide compound in the composite (C) can substantially modify its surface properties， advantageously enabling improved accessibility of the polymer (I) active sites.
The composite (C) of the invention can be used as catalyst， for various reactions using heterogeneous catalysis. Examples thereof include notably alkylation of aliphatic or aromatic hydrocarbons， such as the alkylation of naphthalene with propylene； for decomposing organic hydroperoxides，
such as cumenehydroperoxide； for sulfonating or nitrating organic compounds； for oxyalkylatinghydroxylic compounds， for the hydrocarbon isomerization and polymerization reactions， such as the isomerization of 1 -butene to 2-butenes； for carbonylation and carboxylation reactions； for hydrolysis and condensation/dehydration reactions； for esterifications and etherifications； for hydrations and oxidations； for oligomerizations； for aromatic acylation； for aromatic benzylation； and for isomerization and metathesis reactions.
Particularly， the composite (C) has found itself particularly advantageous when used as catalyst in various biphasic reactions， notably including the acetalization reaction of glycol with dodecanal， as described in the working examples.
When used as a catalyst， the composite (C) is contacted with the required reactants in a fixed-bed system， a moving-bed system， a fluidized-bed system， or in a batch-type operation. This contacting can be in the liquid phase， a mixed vapour-liquid phase， or a vapour phase. Inert diluents such as helium， nitrogen， argon， methane， ethane and the like can be notably present.
Reaction conditions using the present composite (C) as catalyst comprise reaction temperatures generally in the range of about 0℃ to about 300℃， preferably from about 24℃ to about 250℃. Pressure can range from ambient for gas phase or a pressure sufficient to keep reaction in the liquid phase. Reactor operating pressures usually will range from about one atmosphere to about 100 atmospheres， preferably from about one atmosphere to about 50 atmospheres. The skilled in the art will chose appropriate conditions as a matter of routinely work in view of the reaction to be carried out.
Should the composite (C) be used as catalyst in a process operated in continuous， the amount of catalyst in the reactor will provide an overall weight hourly space velocity (WHSV) of from about 0.1 to 100 hr-1， preferably from about 0.1 to 10 hr-1； most preferably 0.1 to 2 hr-1.
In batch processes， short contact times ranging from about 0.01 hour to about 10 hours can give satisfactory results； preferably 0.1 hour to about 5
hours can be used with the composite (C) ， thanks to its high activity. Contact time may be reduced further at higher temperatures.
Description of embodiments
The present invention will now be described in more detailed with reference to the following examples， whose purpose is merely illustrative and not intended for limiting the scope of the present invention.
Examples
Raw Materials
Fluorinated polymers：
(1) 
PW98-S polymer， commercially available from Solvay Specialty Polymers Italy S.p.A， in powdered form and having an equivalent weight of ～ 980；
(2) 
PW66-S polymer， commercially available from Solvay Specialty Polymers Italy S.p.A， in powdered form and having an equivalent weight of ～ 650.
Guar gum：
(1) Type 1： 
C14S guar gum obtained from Solvay Novecare， which is a high molecular weight cationic guar polymer
(2) Type 2： Native guar gum obtained from Solvay Novecare
(3) Type 3： 
HP8FF guar gum obtained from Solvay Novecare， whch is a hydroxypropyl guar
Polysaccharides： cellulose powder ( Sigmacell Cellulose Type 50， 50 pm) and starch (puriss. p.a.， from potato， reag. ISO， reag. Ph. Eur.， soluble) ， both purchased from Sigma-Aldrich.
Disaccharides： D- (+) -Cellobiose (≥98％) and sucrose (BioXtra， ＞99.5％) ， both purchased from Sigma-Aldrich.
Monosaccharides： D- (+) -glucose (＞99％) ， D- (-) -fructose (＞ 99％) ， and D-(+) -xylose (＞ 99％) ， all purchased from Sigma-Aldrich.
Activated charcoal： purchased from Sigma-Aldrich， pre-washed by phosphoric acid and chloric acid in sequence， before use.
HZSM-5： a commercialized acidic zeolite catalyst purchased from the Dow Chemical Company.
H-Resin： an acidic resin catalyst purchased from the Dow Chemical Company.
Preparation of carbon/fluoropolymer composites
Example 1 Preparation of a carbon/PFSA composite from guar gum and 
resin
Three types of carbon/PFSA composites were synthesized， each using a different guar gum product (Type 1， 2， or 3) as the carbon source. Firstly， a 20wt％ aqueous
solution was prepared by adding 1 g of 
PW98-S to 20 mL of deionized water in a glass beaker， with subsequent stirring at a temperature of 50℃. Next， 1 g of guar gum (Type 1，2 or 3) was slowly added into the
solution under vigorous stirring， and a vicious， yellow-to-transparent gel was formed within seconds. Subsequently， the gel was covered and left to expand for 2 hours at 50℃， after which the gel was left to refrigerate for 24 hours at 5℃， remain covered. Afterwards， the gel was transferred to a sealed Teflon autoclave (50mL) and hydrothermal reaction was performed at 180℃ for 24 hours. The autoclave was quickly cooled to room temperature by ice， and the cooled suspension therein was filtrated to obtain a solid substance， which was repeatedly washed by deionized water until neutral pH. The solid was then dried under vacuum overnight， at a temperature of 100℃. The final dried material took the form of a black-to-brown fluffy powder， and gave a yield of approximately 0.4 g.
Example 2 Preparation of a carbon/PFSA composite from cellulose and 
resin
A carbon/PFSA composite was synthesized in this Example using cellulose as the carbon source. Firstly， a 20wt％ aqueous
solution was prepared by adding 1 g powder of
PW66-S to 20 mL of deionized water in a glass beaker， with subsequent stirring at a temperature of 50℃. Next， 1 g of cellulose was slowly added into the 
solution under vigorous stirring， forming a white suspension.
Subsequently， the suspension was covered and left to stand for 2 hours at 50℃， and the cellulose was neither dissolved nor gelled. Afterwards， the suspension was transferred to a sealed Teflon autoclave (50mL) and hydrothermal reaction was performed at 180℃ for 24 hours. The autoclave was quickly cooled to room temperature by ice， and the cooled suspension therein was filtrated to obtain a solid substance， which was repeatedly washed by deionized water until neutral pH. The solid was then dried under vacuum overnight， at a temperature of 100℃. The final dried material took the form of a black-to-brown fluffy powder， and gave a yield of approximately 0.4 g.
Comparative Example 1
Example 1 was essentially followed except no fluoropolymer was used， which gave three samples of carbonaceous material made from Type 1， 2 or 3 guar gum. The yield of each sample was about 0.2 g， also taking the form of a black-to-brown fluffy powder.
Comparative Example 2
Example 2 was essentially followed except no fluoropolymer was used， which gave one sample of carbonaceous material made from cellulose. The product yield was about 0.2 g， also taking the form of a black-to-brown fluffy powder.
Comparative Example 3
In this comparative example， a carbon/PFSA composite was prepared by impregnation method. Firstly， a 20wt％ aqueous
solution was prepared by adding 1 g powder of
PW98-Sto 20 mL of deionized water in a glass beaker， with continuous stirring at room temperature. Next， 1 g of activated charcoal was added into the
solution under stirring， and the resultant black suspension was stirred and refluxed at 80℃ for 2 hours， followed by vaporization treatment at 95℃. The so-obtained black solid was oven-dried at 100℃ overnight， which gave a final product in the form of a black fluffy powder.
Characterization of carbon/fluoropolymer composites
Phase and crystalline structure of so-obtained composites/carbon materials was determined by powder X-ray diffraction (PXRD) ， using a Rigaku D/Max 2200/PC Diffractometer provided with Cu Ka radiation (k ＝ 
) and a beam voltage of 45 kV. The patterns were registered in the 2θ domain (0-70°) with a measured step of 0.02°， and the time integration was fixed to 0.5 s. The results of PXRD analysis (Fig. 1) showed that the composites of Examples 1 and 2 have an amorphous structure and the combined features of
polymer and the polysaccharide-derived carbonaceous material.
Thermal stability of so-obtained composites/carbon materials was determined by thermo gravimetric analysis (TGA) using a TA SDT Q600 instrument. The samples were heated from 30 to 800℃ at a rate of 10℃ min-1 in the presence of air (100 mL (STP) min-1) . The heat flow data were dynamically normalized using the instantaneous weight of the sample at the respective temperature. It was found that
polymer by itself was thermally stable up to 300℃. Specifically， it started to decompose from 300℃ and was completely decomposed at about 550℃. The 
/carbon composites of Examples 1 and 2 showed a thermal stability similar to
which was notably higher than the carbon material obtained from guar gum in comparative Example 1 (which started to decompose at around 275℃) .
Surface area (S.A. ) and pore size of so-obtained composites/carbon materials (see Table 1) were determined by isothermal physisorption of nitrogen at 77K B.E.T. method according to ISO 9277 standard， using a Micromeritics ASAP 2010 instrument. For pre-condition， the test samples were de-gassed under vacuum at 150℃ for 3 hours before measurements.
Acid density of so-obtained composites/carbon materials (see Table 1) was determined using acid-base titration with a Metrohm 794 Basic Titrano instrument. Prior to titration with 0.01 M NaOH solution， the samples were subjected to ion-exchange with a 0.5M NaCl solution at room temperature， for 24 hours.
Table 1
＊The labels of “A” ， “B” and “C” in the samples are used to distinguish the product obtained from different guar gum carbon source ( “A” -Type 1， “B” -Type 2， ″C” -Type 3)
The 0.11-0.32 mmol H+/g acid density of the
/carbon composites of Examples 1 and 2， compared to the negligible acid density of its comparative examples shown in Table 1， was clearly attributed by the acidic PFSA loaded thereon.
Moreover， judging from the surface area and pore size data in Table 1， the 
/carbon composites of Examples 1 and 2 likely possess a microporous or mesoporous structure， resembling its comparative， polymer-free carbon samples.
Thus， with a good thermal stability， an active surface acidity， and convenient porous structure， it is clear that the so-obtained composites have combined the advantages of the PFSA and carbon material used， making themselves attractive for catalytic use and the like.
Furthermore， to investigate the structural distinctions between the composites of the present invention and those produced from prior art
impregnation methods， spectral analysis was performed for Ex. 1-B and Comp. Ex. 3 by FTIR (Fourier Transform Infrared) method， together with 
polymer by itself as a comparative standard. As observed from the FTIR spectra in Fig. 2A， while both composite samples have the characteristic bands for
(400-1300 cm-1) ， their spectrum bands clear differ in the wavenumber region of 1600-1800 cm-1. Thus， evidently， the composite of Ex. 1-B possesses more functional groups which are absent from the structure of the composite made from Comp. Ex. 3.
To have a further understanding of this observed structural difference， FTIR analysis was performed for the H3PO4-H2SO4 pre-treated active charcoal， as well as the carbon material obtained from hydrothermal carbonization of guar gum Type 2 (Comp Ex. 1-B) . From the thus-obtained FTIR spectra in Fig. 2B， it is clear that the guar gum-derived carbon has more variation bands in the wavenumber region of 1600-1800 cm-1， compared to the active charcoal spectrum， implying that the structural differences between the carbon/polymer composites tested above may mostly reside in the carbon material from different sources.
Thus， clearly， the hydrothermal treatment of the present invention has produced a carbon/polymer composite that is structurally distinguished from the prior art composite which uses impregnation method to load fluorinated polymer onto active carbon.
Catalyst Testing
Testing Example 1
Two
/carbon composites obtained from Examples 1 and 2 were tested for their catalytic performances in the acetalization reaction of glycerol with dodecanal， which was performed by the procedure below. Firstly， glycol (20 mmol) ， dodecannal (10mmol) and one composite as catalyst were well sealed in a 50mL glass reactor and vigorously stirred (900 rmp) at 60℃ for 1 hour. The mixture was diluted with tetrahydrofuran and 1， 2-dichlorobenzene was added as the internal standard. The catalyst was recovered by high-speed centrifugation. The conversion of dodecanal and the acetal product yields were analysed by GC and shown in Table 2.
Table 2
Comparative Testing Example 1
The procedure of Testing Example 1 was essentially followed， except that the acid catalyst has been replaced by HZSM-5 and H-Resin， both were commercially used as acid catalyst for industrial applications. The conversion of dodecanal and acetal product yields were analysed by GC and shown in Table 3.
Table 3
Comparative Testing Example 2
The procedure of Testing Example 1 was essentially followed， except that the
/carbon composites were replaced by
polymer powder by itself. The conversion of dodecanal was 90％ and product yield was 66％. However，
polymer produced a high swelling in the reaction mixture， making it difficult for the subsequent separation and recycling.
Comparative Testing Example 3
The procedure of Testing Example 1 was essentially followed， except that the
/carbon composites were replaced by the carbon material obtained from Comp. Ex. 1-B. The conversion of dodecanal was 5％ and
no product yield was detected.
The catalyst testing data as shown above clearly demonstrate the superiority of the invented carbon/polymer composites over the prior art acid catalysts， by obtaining an improved yield and efficiency in a reaction using heterogeneous catalysis， and further facilitating an easy recycle after use.
Claims (14)
- A process for the preparation of a composite (C) comprising at least one functional fluoropolymer [polymer (I) ] and at least one carbon material， wherein the weight percentage of the polymer (I) in the composite (C) is from 0.1 to 85 percent， said process comprising the steps of：(a) preparing a mixture (A) comprising at least one polymer (I) and at least one polysaccharide in an aqueous medium； and(b) subjecting the mixture (A) to a hydrothermal treatment to yield the composite (C) ，wherein the polymer (I) comprises：recurring units derived from at least one ethylenically unsaturated monomer comprising at least one fluorine atom (fluorinated monomer) ； anda substantial amount of recurring units derived from at least one ethylenically unsaturated monomer comprising at least one cation exchange group (functional monomer) .
- The process according to Claim 1， wherein the weight percentage of the polymer (I) is from 0.1 to 50 percent， more preferably from 0.1 to 25 percent.
- The process according to Claim 1 or 2， wherein the functional monomer is chosen among：(M1) sulfonatedperfluoroolefin of formula (M1) ：
wherein n is an integer between 0 and 6 and X’ is chosen among halogens (Cl， F，Br， I) ， -O-M+， wherein M+is a cation selected among H+， NH4 +， K+， Li+， Na+， or mixtures thereof：(M2) sulfonatedperfluorovinylethers of formula (M2) ：
wherein m is an integer between 1 and 10 and X’ is chosen among halogens (Cl， F， Br， I) ， -O-M+， wherein M+is a cation selected among H+， NH4 +， K+， Li+， Na+， or mixtures thereof；(M3) sulfonatedperfluoroalkoxyvinylethers of formula (M3) ：
wherein w is an integer between 0 and 2， RF1 and RF2， equal or different from each other and at each occurrence， are independently -F， -Cl or a C1- 10perfluoroalkyl group， optionally substituted with one or more ether oxygens， y is an integer between 0 and 6 and X’ is chosen among H， halogens (Cl， F， Br， I)，-O-M+， wherein M+ is a cation selected among H+， NH4 +， K+， Li+， Na+， or mixtures thereof；(M4) perfluoroalkoxyvinylether carboxylates of formula (M4) ：
wherein w， y， RF1 and RF2 have the same meaning as above defined， and RH§is a C1-10 alkyl or fluoroalkyl group；(M5) sulfonated aromatic (per) fluoroolefins of formula (M5) ：
wherein Ar is a C3-15 aromatic or heteroaromatic moiety and X’ is chosen among halogens (Cl， F， Br， I) ， -O-M+， wherein M+ is a cation selected among H+，NH4 +， K+， Li+， Na+， or mixtures thereof； and(M6) mixtures thereof. - The process according to claim 3， wherien the polymer (I) is a functional per(halo) fluoropolymer consisting essentially of：-recurring units derived from one or more than one ethylenically unsaturated monomer comprising at least one fluorine atom and free from hydrogen atoms [per (halo) fluoromonomer] ； and-recurring units derived from one or more than one ethylenically unsaturated monomer comprising at least one fluorine atom and at least one cation exchange group， and free from hydrogen atoms (except those optionally comprised in the cation exchange group) [functional per (halo) fluoromonomer] .
- The process according to claim 4， wherein the polymer (I) is selected among tetrafluoroethylene (TFE) copolymers comprising：from 5 to 25％by moles of recurring units derived from PSEPVE and/or SFVE， in their -SO2F or -SO2X” form， wherein X” is chosen among halogens (Cl， Br， I) ， -O-M+， wherein M+ is a cation selected among H+， NH4 +， K+， Li+， Na+， or mixtures thereof； andfrom 95 to 75％by moles of recurring units derived from TFE.
- The process according to any one of the preceding claims， wherein the polysaccharide is selected among cellulose and its derivatives， guar gum， lignin， tannins， betulin， chondroitin sulphate， keratan， keratan sulphate， heparin， heparin sulphate， xanthan， carrageenan， hyaluronic acid， chitin， chitosan， alginate， starch， dextran， pullulan， and galactomannan..
- The process according to claim 6， wherein the polysaccharide is selected among guar gum， cellulose， and derivative thereof.
- The process according to claim 7， wherein the polysaccharide is selected among guar gum and derivative thereof
- The process according to any one of the preceding claims， wherein in the mixture (A) ， the weight ratio of polysaccharide to polymer (I) is from 1： 3 to 3： 1 in the aqueous medium.
- The process according to any one of the preceding claims， wherein the hydrothermal treatment is carried out for a time period of 5 to 36 hours.
- A composite (C) obtained from any one of the preceding claims.
- The composite (C) of claim 11， provided under the form of powder and having an average particle size of 1 to 1000μm.
- The composite (C) of claim 11 or 12， further comprising at least one carrier/promoter chosen amongceria， zirconia， and mixture thereof.
- Use of any one of the composite (C) of claims 11-13 as catalyst.
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