WO2008031199A1 - Ionic compounds having bronsted acidity and uses thereof - Google Patents

Ionic compounds having bronsted acidity and uses thereof Download PDF

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Publication number
WO2008031199A1
WO2008031199A1 PCT/CA2007/001586 CA2007001586W WO2008031199A1 WO 2008031199 A1 WO2008031199 A1 WO 2008031199A1 CA 2007001586 W CA2007001586 W CA 2007001586W WO 2008031199 A1 WO2008031199 A1 WO 2008031199A1
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compound
polymer
substituted
polymerizable
polymerizable moiety
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PCT/CA2007/001586
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French (fr)
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Amer Hammami
Benoît MARSAN
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Transfert Plus, S.E.C.
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Publication of WO2008031199A1 publication Critical patent/WO2008031199A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/54—Quaternary phosphonium compounds
    • C07F9/5442—Aromatic phosphonium compounds (P-C aromatic linkage)
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C279/00—Derivatives of guanidine, i.e. compounds containing the group, the singly-bound nitrogen atoms not being part of nitro or nitroso groups
    • C07C279/18—Derivatives of guanidine, i.e. compounds containing the group, the singly-bound nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of guanidine groups bound to carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
    • C07D213/16—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
    • C07D213/18—Salts thereof
    • 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
    • C08F26/00—Homopolymers and 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 single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F26/06—Homopolymers and 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 single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
    • 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
    • C08F30/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F30/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/20—Manufacture of shaped structures of ion-exchange resins
    • C08J5/22—Films, membranes or diaphragms
    • C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
    • C08J5/2218—Synthetic macromolecular compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/122—Ionic conductors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
    • H01M8/103—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having nitrogen, e.g. sulfonated polybenzimidazoles [S-PBI], polybenzimidazoles with phosphoric acid, sulfonated polyamides [S-PA] or sulfonated polyphosphazenes [S-PPh]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
    • H01M8/1034—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having phosphorus, e.g. sulfonated polyphosphazenes [S-PPh]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
    • H01M8/1072—Polymeric electrolyte materials characterised by the manufacturing processes by chemical reactions, e.g. insitu polymerisation or insitu crosslinking
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0082—Organic polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to improvements in the field of electrochemistry.
  • this invention relates to compounds that can be used for various purposes such as preparation of various polymers, proton exchange membranes for fuel cells, anti-static agents, static charge dissipators, or reversible switchable redox systems.
  • R 1 and R 2 are the same or different and are selected from the group consisting of a hydrogen atom, C 1 -C- 12 alkyl which is linear or branched, C 3 -Ci 2 cycloalkyl, C-1-C12 heterocyclyl, C 2 -Cs alkenyl, C 2 -C 8 alkynyl, C 6 -Ci2 aryl, C 6 -C 20 aralkyl, C 6 -C2 0 alkylaryl, CrCi 2 heteroaryl,
  • R 1 and R 2 are joined together to form a substituted 5 to 14 membered heterocyclyl in which R 3 is absent, a hydrogen atom, or a bond between N and R 1 or between N and R 2 ; or to form a substituted 5 to 14 membered heteroaryl in which R 3 is absent, a hydrogen atom, a bond between N and R 1 or between N and R 2 , the substituted 5 to 14 membered heterocyclyl, and the substituted 5 to 14 membered heteroaryl being substituted with at least one polymerizable moiety;
  • R 3 is a polymerizable moiety
  • R 4 and R 5 are the same or different and are selected from the group consisting of a hydrogen atom, C 1 -C- 12 alkyl which is linear or branched, C 3 -C-
  • R 4 and R 5 are joined together to form a 5 to 14 substituted membered heterocyclyl in which R 6 is absent, a hydrogen atom, or a bond between P and R 4 or between P and R 5 ; or to form a substituted 5 to 14 membered heteroaryl ring in which R 6 is absent, a hydrogen atom, a bond between P and R 4 or between P and R 5 , the substituted 5 to 14 membered heterocyclyl, and the substituted 5 to 14 membered heteroaryl being substituted with at least one polymerizable moiety;
  • R 6 is a polymerizable moiety
  • X " is (FSOz) 2 N-, (CF 3 SO 2 ) 2 N-, (C 2 F 5 SOz) 2 N-, (CF 3 SO 2 ) 3 C-, CF 3 SO 3 -, CF 3 COO-, AsF 6 -, CH 3 COO-, (CN) 2 N “ , NO 3 ' , CN “ , HSO 4 " , H 2 PO 3 “ , PO 4 3” , F ' , CI “ , Br “ , I “ , PF 6 “ , BF 4 “ , CIO 4 “ , saccharin(o-benzoic sulfimide), (C 8 H 16 SO 2 ) 2 N “ , or C 3 H 3 N 2 " .
  • n is an integer having a value from O to 48 and p is an integer having a value from O to 48.
  • X “ is (FSO 2 ) 2 N “ , (CF 3 SOz) 2 N-, (C 2 F 5 SO 2 ) 2 N “ , (CF 3 SO 2 ) 3 C “ , CF 3 SO 3 “ , CF 3 COO “ , AsF 6 “ , CH 3 COO “ , (CN) 2 N “ , NO 3 “ , CN “ , HSO 4 “ , H 2 PO 3 “ , PO 4 3” , F “ , Cl “ , Br “ , I “ , PF 6 “ , BF 4 “ , CIO 4 “ , saccharin(o-benzoic sulfimide), (C 8 H 16 SO 2 )2N “ , or C 3 H 3 N 2 “ .
  • n is an integer having a value from 0 to 48 and p is an integer having a value from 0 to 48.
  • R 11 and R 12 are same or different and are chosen from a hydrogen atom, C 1 -C 20 alkyl which is linear or branched, a C 3 -Ce cycloalkyl, a C 6 -Ci2 aryl and C1-C12 heteroaryl; and
  • X “ is (FSOZ) 2 N “ , (CF 3 SOZ) 2 N “ , (C 2 F 5 SOZ) 2 N “ , (CF 3 SO 2 ) 3 C “ , CF 3 SO 3 “ , CF 3 COO “ , AsF 6 “ , CH 3 COO “ , (CN) 2 N “ , NO 3 “ , CN “ , HSO 4 ' , H 2 PO 3 “ , PO 4 3” , F “ , Cl “ , Br “ , I “ , PF 6 “ , BF 4 “ , CIO 4 “ , saccharin (o-benzoic sulfimide), (C 8 Hi 6 SOz) 2 N “ , or C 3 H 3 N 2 “ .
  • n is an integer having
  • R 11 and R 12 are same or different and are chosen from a hydrogen atom, C 1 -C 20 alkyl which is linear or branched, a C3-C8 cycloalkyl, a C6-C 12 aryl and C 1 -C- 12 heteroaryl; and
  • X- is (FSOz) 2 N-, (CF 3 SOz) 2 N-, (C 2 F 5 SO 2 ) 2 N-, (CF 3 SO 2 ) 3 C-, CF 3 SO 3 -, CF 3 COO-, AsF 6 " , CH 3 COO “ , (CN) 2 N ' , NO 3 " , CN “ , HSO 4 “ , H 2 PO 3 “ , PO 4 3” , F “ , CI “ , Br “ , I “ , PF 6 “ , BF 4 “ , CIO 4 -, saccharin(o-benzoic sulfimide), (C 8 Hi 6 SO 2 ) 2 N-, or C 3 H 3 N 2 " ,
  • n having a value of 1 , 2, or 3;
  • polymers obtained by reacting together reactants comprising a compound of formula (I) and a compound of formula (VII) or a compound of formula (II) and a compound of formula (VIII):
  • R 1 and R 2 are the same or different and are selected from the group consisting of a hydrogen atom, C 1 -C12 alkyl which is linear or branched, C 3 -C12 cycloalkyl, C1-C12 heterocyclyl, C2-C 8 alkenyl, C 2 -Ce alkynyl, C 6 -Ci 2 aryl, C 6 -C 2 O aralkyl, C 6 -C 20 alkylaryl, Ci-d 2 heteroaryl,
  • R 1 and R 2 are joined together to form a substituted 5 to 14 membered heterocyclyl in which R 3 is absent, a hydrogen atom, or a bond between N and R 1 or between N and R 2 ; or to form a substituted 5 to 14 membered heteroaryl in which R 3 is absent, a hydrogen atom, a bond between N and R 1 or between N and R 2 , the substituted 5 to 14 membered heterocyclyl, and the substituted 5 to 14 membered heteroaryl being substituted with at least one polymerizable moiety;
  • R 3 is a polymerizable moiety
  • R 4 and R 5 are the same or different and are selected from the group consisting of a hydrogen atom, C-1-C 12 alkyl which is linear or branched, C3-C12 cycloalkyl, Ci-C 12 heterocyclyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, C 6 -Ci2 aryl, Ce-C 20 aralkyl, Ce-C 20 alkylaryl, Ci-Ci 2 heteroaryl, C n H 2n +-!, Ph 2 P-, Me 2 P, Ph 2 P(S), Me 2 P(S), CN;
  • R 4 and R 5 are joined together to form a 5 to 14 substituted membered heterocyclyl in which R 6 is absent, a hydrogen atom, or a bond between P and R 4 or between P and R 5 ; or to form a substituted 5 to 14 membered heteroaryl ring in which R 6 is absent, a hydrogen atom, a bond between P and R 4 or between P and R 5 , the substituted 5 to 14 membered heterocyclyl, and the substituted 5 to 14 membered heteroaryl being substituted with at least one polymerizable moiety;
  • R 6 is a polymerizable moiety
  • X- is (FSO 2 ) 2 N-, (CF 3 SO 2 )2N-, (C 2 F 5 SO 2 ) 2 N-, (CF 3 SO 2 ) 3 C-, CF 3 SO 3 -, CF 3 COO-, AsF 6 -, CHsCOO “ , (CN) 2 N “ , CN “ , NO 3 " , HSO 4 “ , H 2 PO 3 “ , PO 4 3” , F “ , Cl “ , Br “ , I “ , PF 6 “ , BF 4 “ , CIO 4 “ , saccharin(o-benzoic sulfimide), (C 8 H 16 SO 2 ) 2 N-, or C 3 H 3 N 2 -;
  • n is an integer having a value from O to 48 and p is an integer having a value from O to 48. It was found that by reacting the compounds of formula (I) and (II) with their respective unprotonated forms (compounds of formulas (VII) and (VIII)), very interesting polymers have been obtained. In particular, these polymers have been found to be very effective for proton exchange. The proton exchange is quite efficient since it occurs mainly between an acid (compounds of formula (I) or (II)) and its conjugated base (or unprotonated form) (compounds of formula (VII) or (VIII)).
  • R 1 and R 2 are the same or different and are selected from the group consisting of a hydrogen atom, C-1-C1 2 alkyl which is linear or branched, C3-C12 cycloalkyl, C1-C-12 heterocyclyl, C2-C8 alkenyl, C 2 -Ce alkynyl, C 6 -Ci 2 aryl, C 6 -C 2 O aralkyl, C 6 -C 20 alkylaryl, C1-C-12 heteroaryl,
  • R 1 and R 2 are joined together to form a substituted 5 to 14 membered heterocyclyl in which R 3 is absent, a hydrogen atom, or a bond between N and R 1 or between N and R 2 ; or to form a substituted 5 to 14 membered heteroaryl in which R 3 is absent, a hydrogen atom, a bond between N and R 1 or between N and R 2 , the substituted 5 to 14 membered heterocyclyl, and the substituted 5 to 14 membered heteroaryl being substituted with at least one polymerizable moiety;
  • R 3 is a polymerizable moiety
  • R 4 and R 5 are the same or different and are selected from the group consisting of a hydrogen atom, C 1 -C 12 alkyl which is linear or branched, C 3 -C12 cycloalkyl, C1-C12 heterocyclyl, C 2 -Cs alkenyl, C 2 -Cs alkynyl, C 6 -Ci 2 aryl, C 6 -C 20 aralkyl, C 6 -C 20 alkylaryl, C1-C12 heteroaryl, C n H 2n+ I, Ph 2 P-, Me 2 P, Ph 2 P(S), Me 2 P(S), CN;
  • R 4 and R 5 are joined together to form a 5 to 14 substituted membered heterocyclyl in which R 6 is absent, a hydrogen atom, or a bond between P and R 4 or between P and R 5 ; or to form a substituted 5 to 14 membered heteroaryl ring in which R 6 is absent, a hydrogen atom, a bond between P and R 4 or between P and R 5 , the substituted 5 to 14 membered heterocyclyl, and the substituted 5 to 14 membered heteroaryl being substituted with at least one polymerizable moiety;
  • R 6 is a polymerizable moiety
  • X- is (FSO 2 ) 2 N-, (CF 3 SOz) 2 N-, (C 2 F 5 SO 2 ) 2 N-, (CF 3 SO 2 ) 3 C-, CF 3 SO 3 -, CF 3 COO-, AsF 6 -, CH 3 COO-, (CN) 2 N “ , CN ' , NO 3 " , HSO 4 ' , H 2 PO 3 “ , PO 4 3” , F “ , Cl “ , Br “ , I “ , PF 6 “ , BF 4 “ , CIO 4 “ , saccharin(o-benzoic sulfimide), (C 8 Hi 6 SO 2 ) 2 N-, or C 3 H 3 N 2 " ;
  • aryl refers to a cyclic or polycyclic aromatic ring.
  • the aryl group is phenyl or napthyl.
  • heteroaryl refers to an aromatic cyclic or fused polycyclic ring system having at least one heteroatom selected from the group consisting of N, O, and S.
  • Preferred heteroaryl groups are furyl, thienyl, pyridyl, quinolinyl, isoquinolinyl, indolyl, isoindolyl, triazolyl, pyrrolyl, tetrazolyl, imidazolyl, pyrazolyl, oxazolyl, thiazolyl, benzofuranyl, benzothiophenyl, carbazolyl, benzoxazolyl, pyrimidinyl, benzimidazolyl, quinoxalinyl, benzothiazolyl, naphthyridinyl, isoxazolyl, isothiazolyl, purinyl, quinazolinyl, and so on.
  • heterocyclyl includes non-aromatic rings or ring systems that contain at least one ring having at least one hetero atom (such as nitrogen, oxygen or sulfur). Preferably, this term includes all of the fully saturated and partially unsaturated derivatives of the above mentioned heteroaryl groups.
  • heterocyclic groups include pyrrolidinyl, tetrahydrofuranyl, morpholinyl, thiomorpholinyl, piperidinyl, piperazinyl, thiazolidinyl, isothiazolidinyl, and imidazolidinyl.
  • the compound of formula (I) can be a compound of formula (Ia):
  • R 7 is a polymerizable moiety and X is as previously defined.
  • the compound of formula (I) can be a compound of formula (Ib):
  • R 7 is a polymerizable moiety and X " is as previously defined.
  • the compound of formula (I) can be a compound of formula (Ic):
  • R 7 is a polymerizable moiety and X " is as previously defined.
  • the compound of formula (I) can be a compound of formula (Id):
  • the compound of formula (II) can be a compound of formula (Ha):
  • R 7 is a polymerizable moiety and X " is as previously defined.
  • the compound of formula (III) can be a compound of formula (Ilia):
  • the compound of formula (III) can be a compound of formula (1Mb):
  • the polymer can be obtained by reacting together a compound of formula (Ia) and a compound of formula (Vila):
  • R 7 is a polymerizable moiety and X is as previously defined.
  • the polymer can be obtained by reacting together a compound of formula (Ib) and a compound of formula (VIIb):
  • the polymer can be obtained by reacting together a compound of formula (Ic) and a compound of formula (VIIc):
  • R 7 is a polymerizable moiety and X ' is as previously defined.
  • the polymer can be obtained by reacting together a compound of formula (Id) and a compound of formula (VIId):
  • R 7 is a polymerizable moiety and X " is as previously defined.
  • the polymer can be obtained by reacting together a compound of formula (Ma) and a compound of formula (Villa):
  • R 7 is a polymerizable moiety and X " is as previously defined.
  • the compound of formula (II) can be a compound of formula (III) and the compound of formula (VIII) can be a compound of formula (IX):
  • R 8 , R 9 and R 10 are same or different and each represent a polymerizable moiety
  • X is as previously defined.
  • R 7 in the compounds and polymers of the present invention can be a C 2 -C 8 alkenyl such as vinyl or allyl.
  • Rs, R 9 and Ri 0 in the compounds and polymers of the present invention can be a C 2 -C 8 alkenyl such as vinyl or allyl.
  • the polymerizable moiety can comprise at least one polymerizable entity chosen from a double bond, a triple bond, a carbonyl, a free radical acceptor, and a polymerizable cyclic compound.
  • the polymerizable cyclic compound can be an epoxide, an aziridine, a cyclopropene, or a thiophene.
  • the polymerizable moiety can be chosen from a cyclopropenyl, a C 4 -C 2O alkylcyclopropenyl, a C 4 -C 2 O cyclopropenylalkyl, an epoxide, a C 3 -C 20 alkyloxirane, a C3-C 2 o oxiranealkyl, C2-C20 alkenyl, and C 2 -C 2 O alkynyl.
  • the reactants can comprise a polymerization initiator.
  • the reactants can also comprise at least one additive.
  • the at least one additive can be chosen from cross-linking agents, surfactants, spacers, and monomers.
  • the additive can be a monomer chosen from chosen from ethylene, propene, butene, isoprene, styrene, ethylene oxide, propylene oxide, vinyl fluoride, chloro ethylene, fluoro ethylene, isobutadiene, vinyl sulfonic acid or salts thereof and mixtures thereof.
  • the reactants can comprise an additive (monomer) chosen from ethylene, propene, butene, isoprene, styrene, ethylene oxide, propylene oxide, isobutadiene, said additive being unsubstitued or substituted with at least one substituant chosen from -F, -Cl, -CF 3 , -C2F 5 , -CN, -NO 3 ' , -Cr Cs alkyl, phenyl and -SO 3 H or salts thereof.
  • X " can be (FSO 2 ) 2 N-, (CF 3 SO 2 )2N-, (C 2 F 5 SOa) 2 N “ , or (CN) 2 N-.
  • X " can be (FSO 2 ) 2 N “ or (CF 3 SO 2 J 2 N-.
  • X can also be BF 4 " or PF 6 -.
  • R 11 and R 12 can both represent an unsubstituted phenyl. Alternatively, R 11 and R 12 represent a polymerizable moiety.
  • a polymer obtained by polymerizing a compound as defined in the present invention together with at least one other monomer obtained by polymerizing a compound as defined in the present invention together with at least one other monomer.
  • a compound of the present invention in the manufacture of a proton conducting membrane.
  • a compound of the present invention in the manufacture of a polymer or copolymer.
  • a method of using a compound as defined in the present invention comprising polymerizing the compound so as to obtain a polymer.
  • a method of using a compound as defined in the present invention comprising reacting the compound together with at least one other monomer so as to obtain a copolymer.
  • a composite material comprising at least one polymer as defined in the present invention and at least one other polymer.
  • the other polymer can be chosen from PVDF, HDPE, polybutadiene, polyisoprene, polyethylene, polypropylene, polyethylene oxide, and polyurethane.
  • a method of using a polymer as defined in the present invention comprises mixing the polymer with at least one other polymer in order to prepare a composite material.
  • the other polymer can be one as previously discussed.
  • the compounds of the present invention can be copolymerized with various types of monomers.
  • Such monomers can be chosen according to the desired properties of the polymer to be prepared.
  • Non-limiting examples of such monomers are ethylene, propene, butene, isoprene, styrene, ethylene oxide, propylene oxide, isobutadiene.
  • These monomers can be unsubstitued or substituted with at least one substituant chosen from -F, -Cl, -CF 3 , -C 2 F 5 , -CN, -NO 3 " , -CrCs alkyl, phenyl and -SO 3 H or salts thereof.
  • the compounds of the present invention can also be added as comonomers with monomers used for preparing polyurethanes, polyvinyl chlorides, polystyrenes, polyesters, polyvinylpyridines, polyvinylimidazoles, polyethylenes, polypropylenes, or polyethylenetherephtalates, PVC, or polyethyleneoxide.
  • the compounds of the present invention when used as anti-static agent, can be comprised within a matrix.
  • the matrix can be a polymer (such as polyurethanes, polyvinyl chlorides, polystyrenes, polyesters, polyethylenes, polypropylenes, or polyethylenetherephtalates), a solvent, a textile, clothes, an ink, a wax, a cleaning composition, a softening composition or agent, a petroleum-based composition, a composition comprising volatile or flammable ingredients, molded objects, shaped articles, articles comprising a polymer, electronic devices (such as a computer, TV, DVD, CD player, etc.), static charge dissipators, proton exchange membranes for fuel cells, etc.
  • the polymers of the present invention can also be used for similar purposes.
  • Fig. 1 is a graph showing the results obtained from a Differential Thermal Analysis (DTA) of an example of a polymer according to an embodiment
  • Fig. 2 is a graph showing the results obtained from a Thermal Gravimetric Analysis (TGA) of the polymer analyzed in Fig. 1 ;
  • Fig. 3 is a graph showing the results obtained from a Differential Thermal Analysis (DTA) of an example of a polymer according to another embodiment
  • Fig. 4 is a graph showing the results obtained from a Thermal Gravimetric Analysis (TGA) of the polymer analyzed in Fig. 3;
  • Fig. 5 is a plot showing the through-plan conductivity of examples of composite materials according to various embodiments.
  • Fig. 6 is another plot showing the through-plan conductivity of other examples of composite materials according to various embodiments; and Fig. 7 is a plot showing the in-plan conductivity of examples of composite materials according to various embodiments.
  • Another polymer was prepared by following the same general method as described in Example 4 but, with the exception that the ratio 1-vinylimidazole : 1-vinylimidazolium trifluoromethane sulfonimide was 1.5 : 1.
  • Films have been made using Polymers A and B as previously described.
  • films of composite materials have been made by preparing composite material by mixing Polymers A and B with other polymers such as poly(vinylidene fluoride) (PVDF) and high density polyethylene (HDPE).
  • PVDF poly(vinylidene fluoride)
  • HDPE high density polyethylene
  • Tables 2 to 5 list various composite materials that have been used for preparing the films.
  • the films have been prepared by hot pressing powder mixtures described in Tables 2 to 5. The tests have showed that such mixtures can be hot pressed at a temperature of about 220 0 C.
  • films made with HDPE generally have better mechanical properties than the films made with PVDF. Moreover, the films comprising HDPE showed a good flexibility.
  • Ionic conductivity of the films prepared from the composite materials 1 to 10 listed in Tables 2 to 5 has been measured in the plan of the film (in-plan measurement) and through the plan of the film (through-plan measurement).
  • the through-plan measurements have been carried out in deionized water (Milli-QTM : 18.2 M ⁇ .cm) at a temperature of 23 0 C.
  • Figs. 5 and 6 show the through-plan conductivity values obtained for various films. Figs. 5 and 6 thus permit to compare the results obtained for the conductivity of various films made of composite materials 1 to 10 as compared to the conductivity of films made solely of Polymer A or Polymer B.
  • Fig. 5 shows the results of composite materials 1, 2, 6 and 7 and Fig.
  • the conductivity as well as the mechanical and physicochemical properties of the compounds and polymers previously mentioned can be modified or controlled by adding at least one additive.
  • the at least one additive can be chosen from cross-linking agents, surfactants, spacers, and various other monomers.
  • Various nanocomposite materials can also be prepared by mixing together the previously mentioned compounds and polymers with at least one other polymer.

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Abstract

There are provided compounds of formulas (I) and (II): Various chemical entities can be used for R1 to R6. These compounds comprise at least one polymerizable entity. These compounds can be useful for preparing various polymers. The polymers prepared by using such compounds can be used for preparing proton exchange membranes. For example, compounds (I) and (II) can be polymerized with various monomers including monomers representing their respective unprotonated form.

Description

IONIC COMPOUNDS HAVING BR0NSTED ACIDITY AND
USES THEREOF
TECHNICAL FIELD
The present invention relates to improvements in the field of electrochemistry. In particular, this invention relates to compounds that can be used for various purposes such as preparation of various polymers, proton exchange membranes for fuel cells, anti-static agents, static charge dissipators, or reversible switchable redox systems.
BACKGROUND OF THE INVENTION
Several manufacturers have undertaken the development of proton membrane fuel cells to power electric vehicles. However, improved membrane materials have to be developed to obtain high performance fuel cells and to overcome the main weakness of the existing materials. Traditional proton-conducting membranes (such as Nafion®), suffer from the volatility of water over 1000C and need to be hydrated continuously to transport protons. Such membranes are also very costly. It would therefore be desirable to be provided with some alternatives.
SUMMARY OF THE INVENTION
According to one aspect of the invention, there are provided compounds of formulas (I) or (II):
R1 R3 R4 R6 y° _.Θ y® J3
R2 XH (I) R5 H (H)
wherein
R1 and R2 are the same or different and are selected from the group consisting of a hydrogen atom, C1-C-12 alkyl which is linear or branched, C3-Ci2 cycloalkyl, C-1-C12 heterocyclyl, C2-Cs alkenyl, C2-C8 alkynyl, C6-Ci2 aryl, C6-C20 aralkyl, C6-C20 alkylaryl, CrCi2 heteroaryl,
or
R1 and R2 are joined together to form a substituted 5 to 14 membered heterocyclyl in which R3 is absent, a hydrogen atom, or a bond between N and R1 or between N and R2 ; or to form a substituted 5 to 14 membered heteroaryl in which R3 is absent, a hydrogen atom, a bond between N and R1 or between N and R2, the substituted 5 to 14 membered heterocyclyl, and the substituted 5 to 14 membered heteroaryl being substituted with at least one polymerizable moiety;
R3 is a polymerizable moiety;
R4 and R5 are the same or different and are selected from the group consisting of a hydrogen atom, C1-C-12 alkyl which is linear or branched, C3-C-|2 cycloalkyl, C1-C12 heterocyclyl, C2-C8 alkenyl, C2-C8 alkynyl, C6-Ci2 aryl, C6-C2O aralkyl, C6-C20 alkylaryl, C1-C12 heteroaryl, CnH2n+I, Ph2P-, Me2P, Ph2P(S)1 Me2P(S), CN;
or
R4 and R5 are joined together to form a 5 to 14 substituted membered heterocyclyl in which R6 is absent, a hydrogen atom, or a bond between P and R4 or between P and R5 ; or to form a substituted 5 to 14 membered heteroaryl ring in which R6 is absent, a hydrogen atom, a bond between P and R4 or between P and R5, the substituted 5 to 14 membered heterocyclyl, and the substituted 5 to 14 membered heteroaryl being substituted with at least one polymerizable moiety;
R6 is a polymerizable moiety;
X" is (FSOz)2N-, (CF3SO2)2N-, (C2F5SOz)2N-, (CF3SO2)3C-, CF3SO3-, CF3COO-, AsF6-, CH3COO-, (CN)2N", NO3 ', CN", HSO4 ", H2PO3 ", PO4 3", F', CI", Br", I", PF6 ", BF4 ", CIO4 ", saccharin(o-benzoic sulfimide), (C8H16SO2)2N", or C3H3N2 ".
The alkyl, cycloalkyl, heterocyclyl, alkenyl, alkynyl, aryl, aralkyl, alkylaryl, and heteroaryl being unsubstituted or substituted with at least one substitutent chosen from F, Cl, Br, I1 a Ci-C6 alkoxy, a Ci-C6 hydroxy alkyl, NO2, CN, CF3, SO3 ", PO4 3", CnF2n+I, Ci-Ci2 alkyl which is linear or branched, C6-Ci2 aryl, CnH2n+I, Ph2P-, Me2P, Ph2P(S), Me2P(S), C6H5CpH2P-, CpH2p+1C6H4- CpH2P+IC6H4CnH2n-, CH2=CHCpH2p— , CH2=CHC6Hs-, CH2=CHC6H4CpH2P+I-, CH2=CHCpH2pC6H4-, and a polymerizable moiety; and
n is an integer having a value from O to 48 and p is an integer having a value from O to 48.
According to another aspect of the invention, there are provided compounds of formula (III):
Figure imgf000004_0001
wherein
R8, R9 and R10 are same or different and are chosen from H, F, Cl, Br, I, OH, a d-C6 alkoxy, a Ci-C6 hydroxy alkyl, NO2, CN, CF3, SO3 ", PO4 3", CnF2n+I, CrCi2 alkyl which is linear or branched, C6-Ci2 aryl, CnH2n+I, Ph2P-, Me2P, Ph2P(S), Me2P(S), C6H5CpH2p- CpH2p+iC6H4- CpH2p+iC6H4CnH2n— , CH2=CHCpH2p— , CH2=CHC6Hs-, CH2=CHC6H4CpH2p+i— , CH2=CHCpH2pC6H4-, and a polymerizable moiety; and
X" is (FSO2)2N", (CF3SOz)2N-, (C2F5SO2)2N", (CF3SO2)3C", CF3SO3 ", CF3COO", AsF6 ", CH3COO", (CN)2N", NO3 ", CN", HSO4 ", H2PO3 ", PO4 3", F", Cl", Br", I", PF6 ", BF4 ", CIO4 ", saccharin(o-benzoic sulfimide), (C8H16SO2)2N", or C3H3N2 ".
n is an integer having a value from 0 to 48 and p is an integer having a value from 0 to 48.
According to another aspect of the invention, there are provided compounds of formula (IV) or (V) or any tautomers thereof:
Figure imgf000005_0001
X X
("V) (V)
wherein
R11 and R12 are same or different and are chosen from a hydrogen atom, C1-C20 alkyl which is linear or branched, a C3-Ce cycloalkyl, a C6-Ci2 aryl and C1-C12 heteroaryl; and
X" is (FSOZ)2N", (CF3SOZ)2N", (C2F5SOZ)2N", (CF3SO2)3C", CF3SO3 ", CF3COO", AsF6 ", CH3COO", (CN)2N", NO3 ", CN", HSO4 ', H2PO3 ", PO4 3", F", Cl", Br", I", PF6 ", BF4 ", CIO4 ", saccharin (o-benzoic sulfimide), (C8Hi6SOz)2N", or C3H3N2 ".
The alkyl, cycloalkyl, aryl and heteroaryl being unsubstituted or substituted with at least one substitutent chosen from F, Cl, Br, I, OH, a Ci-C6 alkoxy, a CrC6 hydroxy alkyl, NO2, CN, CF3, SO3 ", CnF2n+I, C1-C12 alkyl which is linear or branched, C6-Ci2 aryl, CnH2n+I, C6H5CpH2p-, CpH2p+iC6H4-, CpH2P+IC6H4CnH2n-, CH2=CHCpH2P-, CH2=CHC6Hs-, CH2=CHC6H4CpH2p+i— , CH2=CHCpH2pC6H4-, and a polymerizable moiety. n is an integer having a value from 0 to 48 and p is an integer having a value from 0 to 48.
According to another aspect of the invention, there are provided compounds of formula (Vl) or any tautomers thereof:
Figure imgf000006_0001
(Vl)
wherein
R11 and R12 are same or different and are chosen from a hydrogen atom, C1-C20 alkyl which is linear or branched, a C3-C8 cycloalkyl, a C6-C12 aryl and C1-C-12 heteroaryl; and
X- is (FSOz)2N-, (CF3SOz)2N-, (C2F5SO2)2N-, (CF3SO2)3C-, CF3SO3-, CF3COO-, AsF6 ", CH3COO", (CN)2N', NO3 ", CN", HSO4 ", H2PO3 ", PO4 3", F", CI", Br", I", PF6 ", BF4 ", CIO4-, saccharin(o-benzoic sulfimide), (C8Hi6SO2)2N-, or C3H3N2 ",
m having a value of 1 , 2, or 3;
The aryl and heteroaryl being unsubstituted or substituted with at least one substitutent chosen from F, Cl, Br, I, OH, a Ci-C6 alkoxy, a Ci-C6 hydroxy alkyl, NO2, CN, CF3, SO3 ", CnF2n+i, C1-C12 alkyl which is linear or branched, C6-Ci2 aryl, CnH2n+i, C6H5CpH2p— , CpH2p+iC6H4— , CpH2p+iC6H4CnH2n— , CH2 =CHCpH2p— , C
Figure imgf000006_0002
H2=CHC6Hs-, CH2=CHCpH2PC6H4- , and a polymerizable moiety; n is an integer having a value from 0 to 48 and p is an integer having a value from 0 to 48.
According to another aspect of the invention, there are provided polymers obtained by reacting together reactants comprising a compound of formula (I) and a compound of formula (VII) or a compound of formula (II) and a compound of formula (VIII):
Ri R3 R4 R6
V© XΘ V© χΘ
L \ / \
R2 H (I) R5 H (II)
R1 R3 R4 R6
\ / \ /
N P
/ /
R2 cvin R5 (VIII)
wherein
R1 and R2 are the same or different and are selected from the group consisting of a hydrogen atom, C1-C12 alkyl which is linear or branched, C3-C12 cycloalkyl, C1-C12 heterocyclyl, C2-C8 alkenyl, C2-Ce alkynyl, C6-Ci2 aryl, C6-C2O aralkyl, C6-C20 alkylaryl, Ci-d2 heteroaryl,
or
R1 and R2 are joined together to form a substituted 5 to 14 membered heterocyclyl in which R3 is absent, a hydrogen atom, or a bond between N and R1 or between N and R2 ; or to form a substituted 5 to 14 membered heteroaryl in which R3 is absent, a hydrogen atom, a bond between N and R1 or between N and R2, the substituted 5 to 14 membered heterocyclyl, and the substituted 5 to 14 membered heteroaryl being substituted with at least one polymerizable moiety;
R3 is a polymerizable moiety; R4 and R5 are the same or different and are selected from the group consisting of a hydrogen atom, C-1-C12 alkyl which is linear or branched, C3-C12 cycloalkyl, Ci-C12 heterocyclyl, C2-C8 alkenyl, C2-C8 alkynyl, C6-Ci2 aryl, Ce-C20 aralkyl, Ce-C20 alkylaryl, Ci-Ci2 heteroaryl, CnH2n+-!, Ph2P-, Me2P, Ph2P(S), Me2P(S), CN;
or
R4 and R5 are joined together to form a 5 to 14 substituted membered heterocyclyl in which R6 is absent, a hydrogen atom, or a bond between P and R4 or between P and R5 ; or to form a substituted 5 to 14 membered heteroaryl ring in which R6 is absent, a hydrogen atom, a bond between P and R4 or between P and R5, the substituted 5 to 14 membered heterocyclyl, and the substituted 5 to 14 membered heteroaryl being substituted with at least one polymerizable moiety;
R6 is a polymerizable moiety;
X- is (FSO2)2N-, (CF3SO2)2N-, (C2F5SO2)2N-, (CF3SO2)3C-, CF3SO3-, CF3COO-, AsF6-, CHsCOO", (CN)2N", CN", NO3 ", HSO4 ", H2PO3 ", PO4 3", F", Cl", Br", I", PF6 ", BF4 ", CIO4 ", saccharin(o-benzoic sulfimide), (C8H16SO2)2N-, or C3H3N2-;
the alkyl, cycloalkyl, heterocyclyl, alkenyl, alkynyl, aryl, aralkyl, alkylaryl, and heteroaryl being unsubstituted or substituted with at least one substitutent chosen from F, Cl, Br, I, a Ci-C6 alkoxy, a Ci-C6 hydroxy alkyl, NO2, CN, CF3, SO3 ", PO4 3", CnF2n+I, C1-C12 alkyl which is linear or branched, C6-Ci2 aryl, CnH2n+I, Ph2P-, Me2P, Ph2P(S), Me2P(S), C6H5CpH2p-, CpH2p+1C6H4- CpH2P+IC6H4CnH2n-, CH2=CHCpH2p— , CH2=CHC6Hs-, CH2=CHC6H4CpH2p+i— , CH2=CHCpH2pC6H4-, and a polymerizable moiety,
where n is an integer having a value from O to 48 and p is an integer having a value from O to 48. It was found that by reacting the compounds of formula (I) and (II) with their respective unprotonated forms (compounds of formulas (VII) and (VIII)), very interesting polymers have been obtained. In particular, these polymers have been found to be very effective for proton exchange. The proton exchange is quite efficient since it occurs mainly between an acid (compounds of formula (I) or (II)) and its conjugated base (or unprotonated form) (compounds of formula (VII) or (VIII)).
According to another aspect of the invention, there are provided polymers obtained by polymerizing a compound of formula (I) or (II):
Ri R3 R4 R6
V© xΘ )P(® χΘ
R2 H (I) R5 H (H)
wherein
R1 and R2 are the same or different and are selected from the group consisting of a hydrogen atom, C-1-C12 alkyl which is linear or branched, C3-C12 cycloalkyl, C1-C-12 heterocyclyl, C2-C8 alkenyl, C2-Ce alkynyl, C6-Ci2 aryl, C6-C2O aralkyl, C6-C20 alkylaryl, C1-C-12 heteroaryl,
or
R1 and R2 are joined together to form a substituted 5 to 14 membered heterocyclyl in which R3 is absent, a hydrogen atom, or a bond between N and R1 or between N and R2 ; or to form a substituted 5 to 14 membered heteroaryl in which R3 is absent, a hydrogen atom, a bond between N and R1 or between N and R2, the substituted 5 to 14 membered heterocyclyl, and the substituted 5 to 14 membered heteroaryl being substituted with at least one polymerizable moiety;
R3 is a polymerizable moiety; R4 and R5 are the same or different and are selected from the group consisting of a hydrogen atom, C1-C12 alkyl which is linear or branched, C3-C12 cycloalkyl, C1-C12 heterocyclyl, C2-Cs alkenyl, C2-Cs alkynyl, C6-Ci2 aryl, C6-C20 aralkyl, C6-C20 alkylaryl, C1-C12 heteroaryl, CnH2n+I, Ph2P-, Me2P, Ph2P(S), Me2P(S), CN;
or
R4 and R5 are joined together to form a 5 to 14 substituted membered heterocyclyl in which R6 is absent, a hydrogen atom, or a bond between P and R4 or between P and R5 ; or to form a substituted 5 to 14 membered heteroaryl ring in which R6 is absent, a hydrogen atom, a bond between P and R4 or between P and R5, the substituted 5 to 14 membered heterocyclyl, and the substituted 5 to 14 membered heteroaryl being substituted with at least one polymerizable moiety;
R6 is a polymerizable moiety;
X- is (FSO2)2N-, (CF3SOz)2N-, (C2F5SO2)2N-, (CF3SO2)3C-, CF3SO3-, CF3COO-, AsF6-, CH3COO-, (CN)2N", CN', NO3 ", HSO4 ', H2PO3 ", PO4 3", F", Cl", Br", I", PF6 ", BF4 ", CIO4 ", saccharin(o-benzoic sulfimide), (C8Hi6SO2)2N-, or C3H3N2 ";
the alkyl, cycloalkyl, heterocyclyl, alkenyl, alkynyl, aryl, aralkyl, alkylaryl, and heteroaryl being unsubstituted or substituted with at least one substitutent chosen from F, Cl, Br, I, a Ci-C6 alkoxy, a C1-C6 hydroxy alkyl, NO2, CN, CF3, SO3 ", PO4 3", CnF2n+I, CrCi2 alkyl which is linear or branched, C6-Ci2 aryl, CnH2n+I, Ph2P-, Me2P, Ph2P(S), Me2P(S), C6H5CpH2p-, CpH2p+iC6H4-, CpH2P+ICeH4CnH2n-, CH2=CHCpH2p— , CH2=CHC6Hs-, CH2=CHC6H4CpH2p+i— , CH2=CHCpH2pC6H4-, and a polymerizable moiety,
where n is an integer having a value from O to 48 and p is an integer having a value from O to 48. The term "aryl" as used herein refers to a cyclic or polycyclic aromatic ring. Preferably, the aryl group is phenyl or napthyl.
The term "heteroaryl" as used herein refers to an aromatic cyclic or fused polycyclic ring system having at least one heteroatom selected from the group consisting of N, O, and S. Preferred heteroaryl groups are furyl, thienyl, pyridyl, quinolinyl, isoquinolinyl, indolyl, isoindolyl, triazolyl, pyrrolyl, tetrazolyl, imidazolyl, pyrazolyl, oxazolyl, thiazolyl, benzofuranyl, benzothiophenyl, carbazolyl, benzoxazolyl, pyrimidinyl, benzimidazolyl, quinoxalinyl, benzothiazolyl, naphthyridinyl, isoxazolyl, isothiazolyl, purinyl, quinazolinyl, and so on.
The term "heterocyclyl" includes non-aromatic rings or ring systems that contain at least one ring having at least one hetero atom (such as nitrogen, oxygen or sulfur). Preferably, this term includes all of the fully saturated and partially unsaturated derivatives of the above mentioned heteroaryl groups. Examples of heterocyclic groups include pyrrolidinyl, tetrahydrofuranyl, morpholinyl, thiomorpholinyl, piperidinyl, piperazinyl, thiazolidinyl, isothiazolidinyl, and imidazolidinyl.
For example, the compound of formula (I) can be a compound of formula (Ia):
Θ
Figure imgf000011_0001
(Ia)
wherein R7 is a polymerizable moiety and X is as previously defined.
For example, the compound of formula (I) can be a compound of formula (Ib):
Figure imgf000011_0002
(Ib)
wherein R7 is a polymerizable moiety and X" is as previously defined. For example, the compound of formula (I) can be a compound of formula (Ic):
Figure imgf000012_0001
(Ic)
wherein R7 is a polymerizable moiety and X" is as previously defined.
For example, the compound of formula (I) can be a compound of formula (Id):
Figure imgf000012_0002
(Id)
For example, the compound of formula (II) can be a compound of formula (Ha):
Figure imgf000012_0003
(Ha)
wherein R7 is a polymerizable moiety and X" is as previously defined.
For example, the compound of formula (III) can be a compound of formula (Ilia):
Figure imgf000013_0001
Θ
(Ilia) X
wherein X" is as previously defined.
For example, the compound of formula (III) can be a compound of formula (1Mb):
Figure imgf000013_0002
wherein X' is as previously defined.
For example, the polymer can be obtained by reacting together a compound of formula (Ia) and a compound of formula (Vila):
Figure imgf000013_0003
(Ia) (Vila)
wherein R7 is a polymerizable moiety and X is as previously defined.
For example, the polymer can be obtained by reacting together a compound of formula (Ib) and a compound of formula (VIIb):
θ
R7-N^NH X R7-N^N
(Ib) (VIIb) wherein R7 is a polymerizable moiety and X" is as previously defined.
For example, the polymer can be obtained by reacting together a compound of formula (Ic) and a compound of formula (VIIc):
Figure imgf000014_0001
(Ic) (VIIc)
wherein R7 is a polymerizable moiety and X' is as previously defined.
For example, the polymer can be obtained by reacting together a compound of formula (Id) and a compound of formula (VIId):
Figure imgf000014_0002
(Id) (VIId)
wherein R7 is a polymerizable moiety and X" is as previously defined.
For example, the polymer can be obtained by reacting together a compound of formula (Ma) and a compound of formula (Villa):
Figure imgf000014_0003
(Ha) (Vina)
wherein R7 is a polymerizable moiety and X" is as previously defined. For example, when preparing a polymer, the compound of formula (II) can be a compound of formula (III) and the compound of formula (VIII) can be a compound of formula (IX):
Figure imgf000015_0001
(III) (IX)
wherein
R8, R9 and R10 are same or different and each represent a polymerizable moiety; and
X" is as previously defined.
In one embodiment, R7, in the compounds and polymers of the present invention can be a C2-C8 alkenyl such as vinyl or allyl.
In another embodiment, Rs, R9 and Ri0, in the compounds and polymers of the present invention can be a C2-C8 alkenyl such as vinyl or allyl.
In the compounds and polymers of the present invention, the polymerizable moiety can comprise at least one polymerizable entity chosen from a double bond, a triple bond, a carbonyl, a free radical acceptor, and a polymerizable cyclic compound. For example, the polymerizable cyclic compound can be an epoxide, an aziridine, a cyclopropene, or a thiophene. For example, the polymerizable moiety can be chosen from a cyclopropenyl, a C4-C2O alkylcyclopropenyl, a C4-C2O cyclopropenylalkyl, an epoxide, a C3-C20 alkyloxirane, a C3-C2o oxiranealkyl, C2-C20 alkenyl, and C2-C2O alkynyl.
When preparing the polymers of the present invention, the reactants can comprise a polymerization initiator. The reactants can also comprise at least one additive. For example, the at least one additive can be chosen from cross-linking agents, surfactants, spacers, and monomers. The additive can be a monomer chosen from chosen from ethylene, propene, butene, isoprene, styrene, ethylene oxide, propylene oxide, vinyl fluoride, chloro ethylene, fluoro ethylene, isobutadiene, vinyl sulfonic acid or salts thereof and mixtures thereof. Alternatively, the reactants can comprise an additive (monomer) chosen from ethylene, propene, butene, isoprene, styrene, ethylene oxide, propylene oxide, isobutadiene, said additive being unsubstitued or substituted with at least one substituant chosen from -F, -Cl, -CF3, -C2F5, -CN, -NO3 ', -Cr Cs alkyl, phenyl and -SO3H or salts thereof.
For example, in the polymers and compounds of the present invention X" can be (FSO2)2N-, (CF3SO2)2N-, (C2F5SOa)2N", or (CN)2N-. Alternatively, X" can be (FSO2)2N" or (CF3SO2J2N-. X can also be BF4 " or PF6-.
R11 and R12 can both represent an unsubstituted phenyl. Alternatively, R11 and R12 represent a polymerizable moiety.
According to another aspect of the present invention there is provided a polymer obtained by polymerizing a compound as defined in the present invention.
According to another aspect of the present invention there is provided a polymer obtained by polymerizing a compound as defined in the present invention together with at least one other monomer.
According to another aspect of the present invention there is provided the use of a compound of the present invention as an antistatic agent.
According to another aspect of the present invention there is provided the use of a compound of the present invention in the manufacture of a proton conducting membrane. According to another aspect of the present invention there is provided the use of a compound of the present invention in the manufacture of a polymer or copolymer.
According to another aspect of the present invention there is provided a method of using a compound as defined in the present invention, comprising polymerizing the compound so as to obtain a polymer.
According to another aspect of the present invention there is provided a method of using a compound as defined in the present invention, comprising reacting the compound together with at least one other monomer so as to obtain a copolymer.
According to another aspect of the present invention there is provided a composite material comprising at least one polymer as defined in the present invention and at least one other polymer. For example, the other polymer can be chosen from PVDF, HDPE, polybutadiene, polyisoprene, polyethylene, polypropylene, polyethylene oxide, and polyurethane.
According to another aspect of the present invention there is provided a method of using a polymer as defined in the present invention. The method comprises mixing the polymer with at least one other polymer in order to prepare a composite material. The other polymer can be one as previously discussed.
The person skilled in the art will understand that the compounds of the present invention can be copolymerized with various types of monomers. Such monomers can be chosen according to the desired properties of the polymer to be prepared. Non-limiting examples of such monomers are ethylene, propene, butene, isoprene, styrene, ethylene oxide, propylene oxide, isobutadiene. These monomers can be unsubstitued or substituted with at least one substituant chosen from -F, -Cl, -CF3, -C2F5, -CN, -NO3 ", -CrCs alkyl, phenyl and -SO3H or salts thereof. The compounds of the present invention can also be added as comonomers with monomers used for preparing polyurethanes, polyvinyl chlorides, polystyrenes, polyesters, polyvinylpyridines, polyvinylimidazoles, polyethylenes, polypropylenes, or polyethylenetherephtalates, PVC, or polyethyleneoxide. The compounds of the present invention, when used as anti-static agent, can be comprised within a matrix. The matrix can be a polymer (such as polyurethanes, polyvinyl chlorides, polystyrenes, polyesters, polyethylenes, polypropylenes, or polyethylenetherephtalates), a solvent, a textile, clothes, an ink, a wax, a cleaning composition, a softening composition or agent, a petroleum-based composition, a composition comprising volatile or flammable ingredients, molded objects, shaped articles, articles comprising a polymer, electronic devices (such as a computer, TV, DVD, CD player, etc.), static charge dissipators, proton exchange membranes for fuel cells, etc. The polymers of the present invention can also be used for similar purposes.
BRIEF DESCRIPTION OF DRAWINGS
In the following drawings, which represent by way of example only, various embodiments of the invention :
Fig. 1 is a graph showing the results obtained from a Differential Thermal Analysis (DTA) of an example of a polymer according to an embodiment;
Fig. 2 is a graph showing the results obtained from a Thermal Gravimetric Analysis (TGA) of the polymer analyzed in Fig. 1 ;
Fig. 3 is a graph showing the results obtained from a Differential Thermal Analysis (DTA) of an example of a polymer according to another embodiment;
Fig. 4 is a graph showing the results obtained from a Thermal Gravimetric Analysis (TGA) of the polymer analyzed in Fig. 3;
Fig. 5 is a plot showing the through-plan conductivity of examples of composite materials according to various embodiments;
Fig. 6 is another plot showing the through-plan conductivity of other examples of composite materials according to various embodiments; and Fig. 7 is a plot showing the in-plan conductivity of examples of composite materials according to various embodiments.
DETAILLED DESCRIPTION OF THE INVENTION
Further features and advantages of the invention will become more readily apparent from the following description of non-limiting examples.
EXAMPLE 1
9.41 g (0.1 mol) of the 1-vinylimidazole 99+% was dissolved in 10OmL of distilled water and charged into a two-neck flask with magnetic stirrer. Hydrochloric acid (0.1 N) was slowly added into the flask until (pH = 0). Then, 30 mL of a solution of one equivalent of potassium bis(trifluoromethane sulfonimide) KTFSI in distilled water was added to the reaction mixture. A white precipitate was appearing (1-vinylimidazolium trifluoromethane sulfonimide). The ionic liquid was isolated by filtration, dissolved in 50 mL dichloromethane and extracted with 50 mL of distilled water. The organic layer was separated and dried with anhydrous MgSO4, the solvent was removed under vacuum and the desired product was oven dried at 4O0C under vacuum.
The structure was confirmed using 13C, 1H and IR
EXAMPLE 2
10.5 g (0.1 mol) of 4-vinylpyridine was dissolved in 100 mL of distilled water and charged into a two-neck flask with magnetic stirrer. Hydrochloric acid (0.1 N) was slowly added into the flask until (pH = 0). Then, 30 mL of a solution of one equivalent of KTFSI The ionic liquid obtained was isolated by filtration, dissolved in 50 mL dichloromethane and extracted with 50 mL of distilled water. The organic layer was separated and dried with anhydrous MgSO4, the solvent was removed under vacuum and the desired product was oven dried at 40°C under vacuum. The structure was confirmed using 13C, 1H and IR
EXAMPLE 3
2.11 g (0.01 mol) of 1 ,3-diphenylguanidine was dissolved in 100 ml_ of anhydrous THF and charged into a two-neck flask with magnetic stirrer under argon. A solution of 2.81 g (0.01 mol) trifluoromethanesulfonimide in 5OmL of anhydrous THF was slowly added into the flask under argon. After ten minutes of stirring at room temperature, the solvent was removed under vacuum and the crude product was dissolved in 50 mL of CH2CI2 and extracted with 3 times with 50 mL of distilled water. The organic layer was dried with a small amount of anhydrous MgSO4 and filtered off. The solvent was removed and the desired product obtained was dried under vacuum.
The structure was confirmed using 13C, 1H and IR
EXAMPLE 4 (Polymer A)
9.41 g (0.1 mol) of 1-vinylimidazole and 0.1 g AIBN, as initiator, were dissolved in 200 mL of toluene and mixed with one equivalent of 1- vinylimidazolium trifluoromethane sulfonimide (as prepared in Example 1) and the mixture was polymerized at 65°C under argon for 72h. The ratio 1- vinylimidazole : 1-vinylimidazolium trifluoromethane sulfonimide was thus 1 : 1. Then, the polymer (PVIM (polyvinylimidazole)) was precipitated in acetone and filtered out and oven-dried at 450C for 24h. Finally, the polymer was purified by dissolution in methanol and precipitation in acetone. This last step was repeated three times. EXAMPLE 5 (Polymer B)
Another polymer was prepared by following the same general method as described in Example 4 but, with the exception that the ratio 1-vinylimidazole : 1-vinylimidazolium trifluoromethane sulfonimide was 1.5 : 1.
EXAMPLE 6
Some test have been carried on Polymers A & B. Table 1 resumes the properties of the obtained polymers.
Table 1. Properties of Polymers of Polymers A & B.
Figure imgf000021_0001
Other tests have been made on these polymers at it can be seen in Figs. 1 to 4 in order to determine the thermal properties of these polymers. In particular a Differential Thermal Analysis (DTA) (see Fig. 1) and a Thermal Gravimetric Analysis (TGA) (see Fig. 2) have been carried on Polymer A. Analogously, a Differential Thermal Analysis (DTA) (see Fig. 3) and a Thermal Gravimetric Analysis (TGA) (see Fig. 4) have been carried on Polymer B. As it can be seen from Figs. 1 to 4, Polymers A and B have similar degradation curves. There is an onset around 340 0C and two main degradation peaks at 400 0C and 440 0C. It should be noted that these analyses (Figs. 1 to 4) have been carried out under an air atmosphere and at a rate of 10 0C / minute. EXAMPLE 7
Films have been made using Polymers A and B as previously described. In particular, films of composite materials have been made by preparing composite material by mixing Polymers A and B with other polymers such as poly(vinylidene fluoride) (PVDF) and high density polyethylene (HDPE). The Tables 2 to 5 list various composite materials that have been used for preparing the films. The films have been prepared by hot pressing powder mixtures described in Tables 2 to 5. The tests have showed that such mixtures can be hot pressed at a temperature of about 220 0C.
Table 2. Composite materials comprising Polymer A and PVDF.
Figure imgf000022_0001
Table 3. Composite materials comprising Polymer A and HDPE.
Figure imgf000022_0002
Table 4. Composite materials comprising Polymer B and PVDF.
Figure imgf000023_0001
Table 5. Composite materials comprising Polymer B and HDPE.
Figure imgf000023_0002
It was observed that films made with HDPE generally have better mechanical properties than the films made with PVDF. Moreover, the films comprising HDPE showed a good flexibility.
EXAMPLE 8
Ionic conductivity of the films prepared from the composite materials 1 to 10 listed in Tables 2 to 5 has been measured in the plan of the film (in-plan measurement) and through the plan of the film (through-plan measurement). The through-plan measurements have been carried out in deionized water (Milli-Q™ : 18.2 MΩ.cm) at a temperature of 23 0C. Figs. 5 and 6 show the through-plan conductivity values obtained for various films. Figs. 5 and 6 thus permit to compare the results obtained for the conductivity of various films made of composite materials 1 to 10 as compared to the conductivity of films made solely of Polymer A or Polymer B. Fig. 5 shows the results of composite materials 1, 2, 6 and 7 and Fig. 6 shows the results of composite materials 3, 4, 5, 8, 9, and 10. The through-plan conductivity of a film made of Polymer A was previously measured and was 1.8 x 10"5 S/cm. The conductivity of a film made of Polymer B was previously measured and was 5.0 x 10"5 S/cm. It can thus be seen that by mixing Polymers A or B with either PVDF or HDPE lowers the conductivity of one or two order of magnitude.
Some in-plan measurements have also been carried out on the films made with the composite materials 1 to 10 listed in Tables 2 to 5. The results are shown in Fig. 7 as well as in Table 6. In Fig. 7, the measurements have been carried out in deionized water (Milli-Q™ : 18.2 MΩ.cm) at a temperature of 23 0C. The dotted lines represent composite materials comprising HDPE and full lines represent composite material comprising PVDF.
Table 6. In-plan measurements of films made of various composite materials
Figure imgf000025_0001
In can thus be seen that all the in-plan conductivity values are in the order of magnitude of 1O-4 S/cm, which is quite encouraging for application in the field of membranes used in fuel cells. It can also be seen from Table 6 and Fig. 7 that conductivity increases with the concentration of Polymer A or B. It is easier to have a high content of Polymer A or B when using HDPE. Therefore, composite materials comprising HDPE have a higher conductivity. It was observed that varying the ratio 1-vinylimidazole : 1-vinylimidazolium trifluoromethane sulfonimide does not have a very important impact on the results when using PVDF (see the difference between the results of composite materials comprising Polymer A and composite materials comprising Polymer B (composite materials 1 and 2 as compared to composite materials 6 and 7)). However, in the composite materials comprising HDPE, it seems that a higher ratio of 1-vinylimidazole (Polymer B) permits to obtain a significant increase of the conductivity (see results of composite materials 3, 4, and 5 as compared to composite materials 8, 9, and 10). The composite material 8 had an interesting conductivity of 5.3 x 10"4 S/cm.
DTA, TGA, and conductivity measurements have been carried out at Industrial Materials Institute of the National Research Council of Canada at Boucherville, Quebec.
The person skilled in the art would clearly understand that the conductivity as well as the mechanical and physicochemical properties of the compounds and polymers previously mentioned can be modified or controlled by adding at least one additive. The at least one additive can be chosen from cross-linking agents, surfactants, spacers, and various other monomers. Various nanocomposite materials can also be prepared by mixing together the previously mentioned compounds and polymers with at least one other polymer.
While the invention has been described in connection with specific embodiments thereof, it will be understood that it is capable of further modifications and this application is intended to cover any variations, uses, or adaptations of the invention following, in general, the principles of the invention and including such departures from the present disclosure as come within known or customary practice within the art to which the invention pertains and as may be applied to the essential features hereinbefore set forth, and as follows in the scope of the appended claims.

Claims

WHAT IS CLAIMED IS:
1. A polymer obtained by reacting together reactants comprising a compound of formula (I) and a compound of formula (VII) or a compound of formula (II) and a compound of formula (VIII):
Ri R3 R4 R6
V© xΘ V© xΘ
R2 H (I) R5 H (II)
R1 R3 R4 R6
\ / \ /
N P
/
R2 (VII) R5 (VIII)
wherein
R1 and R2 are the same or different and are selected from the group consisting of a hydrogen atom, C1-C12 alkyl which is linear or branched, C3-C12 cycloalkyl, C1-C12 heterocyclyl, C2-C8 alkenyl, C2-Cs alkynyl, C6-Ci2 aryl, C6-C2O aralkyl, C6-C20 alkylaryl, Ci-Ci2 heteroaryl,
or
R1 and R2 are joined together to form a substituted 5 to 14 membered heterocyclyl in which R3 is absent, a hydrogen atom, or a bond between N and R1 or between N and R2 ; or to form a substituted 5 to 14 membered heteroaryl in which R3 is absent, a hydrogen atom, a bond between N and R1 or between N and R2, said substituted 5 to 14 membered heterocyclyl, and said substituted 5 to 14 membered heteroaryl being substituted with at least one polymerizable moiety;
R3 is a polymerizable moiety;
R4 and R5 are the same or different and are selected from the group consisting of a hydrogen atom, Ci-Ci2 alkyl which is linear or branched, C3-C12 cycloalkyl, CrC12 heterocyclyl, C2-C8 alkenyl, C2-C8 alkynyl, C6-Ci2 aryl, C6-C2O aralkyl, C6-C2O alkylaryl, Ci-Ci2 heteroaryl, CnH2n+I, Ph2P-, Me2P, Ph2P(S), Me2P(S), CN;
or
R4 and R5 are joined together to form a 5 to 14 substituted membered heterocyclyl in which R6 is absent, a hydrogen atom, or a bond between P and R4 or between P and R5 ; or to form a substituted 5 to 14 membered heteroaryl ring in which R6 is absent, a hydrogen atom, a bond between P and R4 or between P and R5, said substituted 5 to 14 membered heterocyclyl, and said substituted 5 to 14 membered heteroaryl being substituted with at least one polymerizable moiety;
R6 is a polymerizable moiety; and
X" is (FSO2)2N-, (CF3SOz)2N-, (C2F5SO2)2N-, (CF3SO2)3C-, CF3SO3-, CF3COO-, AsF6-, CH3COO-, (CN)2N", CN", NO3 ", HSO4 ', H2PO3-, PO4 3", F", Cl", Br", I", PF6 ", BF4 ", CIO4 ', saccharin(o-benzoic sulfimide), (C8H16SO2)2N-, or C3H3N2 ";
said alkyl, cycloalkyl, heterocyclyl, alkenyl, alkynyl, aryl, aralkyl, alkylaryl, and heteroaryl being unsubstituted or substituted with at least one substitutent chosen from F, Cl, Br, I, a CrC6 alkoxy, a CrC6 hydroxy alkyl, NO2, CN, CF3, SO3 ", PO4 3", CnF2n+1, CrCi2 alkyl which is linear or branched, C6-Ci2 aryl, CnH2n+I, Ph2P-, Me2P, Ph2P(S), Me2P(S), C6HsCpH2P-, CpH2p+iC6H4— , CpH2p+i C6H4CnH2n-, CH2=CHCpH2P-, CH2=CHC6Hs-, CH2=CHC6H4CpH2p+i— ,
CH2=CHCpH2pC6H4-, and a polymerizable moiety.
where n is an integer having a value from O to 48 and p is an integer having a value from O to 48.
2. The polymer of claim 1 , wherein said polymer is obtained by reacting together a compound of formula (Ia) and a compound of formula (Vila): R7 R7
(Ia) (Vila)
wherein R7 is a polymerizable moiety and X is as previously defined.
3. The polymer of claim 1 , wherein said polymer is obtained by reacting together a compound of formula (Ib) and a compound of formula (VIIb):
Figure imgf000029_0001
(Ib) (VIIb)
wherein R7 is a polymerizable moiety and X" is as previously defined.
4. The polymer of claim 1 , wherein said polymer is obtained by reacting together a compound of formula (Ic) and a compound of formula (VIIc):
Figure imgf000029_0002
(Ic) (VIIc)
wherein R7 is a polymerizable moiety and X' is as previously defined.
5. The polymer of claim 1 , wherein said polymer is obtained by reacting together a compound of formula (Id) and a compound of formula (VIId):
R7
H
Figure imgf000029_0003
(Id) (VIId) wherein R >7 : is a polymerizable moiety and X" is as previously defined.
6. The polymer of claim 1 , wherein said polymer is obtained by reacting together a compound of formula (Na) and a compound of formula (Villa):
Figure imgf000030_0001
(Ha) (Villa)
wherein R7 is a polymerizable moiety and X" is as previously defined.
7. The polymer of claim 1 , wherein said compound of formula (II) is a compound of formula (III) and said compound of formula (VIII) is a compound of formula (IX):
Figure imgf000030_0002
(III) (IX)
wherein
R8, R9 and R10 are same or different and each represent a polymerizable moiety; and
X" is as previously defined.
8. The polymer of any one of claims 1 to 7, wherein said polymerizable moiety comprises at least one polymerizable entity chosen from a double bond, a triple bond, a carbonyl, a free radical acceptor, and a polymerizable cyclic compound.
9. The polymer of any one of claims 1 to 7, wherein said polymerizable moiety comprises at least one polymerizable entity chosen from a double bond, a triple bond, and a polymerizable cyclic compound.
10. The polymer of claim 8 or 9, wherein said polymerizable cyclic compound is an epoxide, an aziridine, a cyclopropene, or a thiophene.
11. The polymer of any one of claims 1 to 7, wherein said polymerizable moiety is chosen from a cyclopropenyl, a C4-C20 alkylcyclopropenyl, a C4-C20 cyclopropenylalkyl, an epoxide, a C3-C20 alkyloxirane, a C3-C20 oxiranealkyl, C2-C20 alkenyl, and C2-C20 alkynyl.
12. The polymer of any one of claims 1 to 7, wherein said polymerizable moiety is chosen from a cyclopropenyl, an epoxide, C2-C20 alkenyl, and C2-C20 alkynyl.
13. The polymer of any one of claims 2 to 6, wherein R7 is vinyl.
14. The polymer of claim 7, wherein Rs, R9 and R-m, are a vinyl.
15. The polymer of any one of claims 1 to 14, wherein said reactants comprise a polymerization initiator.
16. The polymer of any one of claims 1 to 14, wherein said reactants comprise at least one other monomer.
17. The polymer of any one of claims 1 to 14, wherein said reactants comprise an additive chosen from ethylene, propene, butene, isoprene, styrene, ethylene oxide, propylene oxide, vinyl fluoride, chloro ethylene, fluoro ethylene, isobutadiene, vinyl sulfonic acid or salts thereof and mixtures thereof.
18. The polymer of any one of claims 1 to 14, wherein said reactants comprise an additive chosen from ethylene, propene, butene, isoprene, styrene, ethylene oxide, propylene oxide, isobutadiene, said additive being unsubstitued or substituted with at least one substituant chosen from -F, -Cl, -CF3, -C2F5, -CN, -NO3 ", -CrC8 alkyl, phenyl and -SO3H or salts thereof.
19. A polymer obtained by polymerizing a compound of formula (I) or (II):
Ri R3 R4 R6
V© xΘ )/© xΘ
R2 H (I) R5 H (U)
wherein
R1 and R2 are the same or different and are selected from the group consisting of a hydrogen atom, C1-C12 alkyl which is linear or branched, C3-Ci2 cycloalkyl, CrCi2 heterocyclyl, C2-C8 alkenyl, C2-C8 alkynyl, C6-Ci2 aryl, C6-C2o aralkyl, C6-C20 alkylaryl, Ci-Ci2 heteroaryl,
or
R1 and R2 are joined together to form a substituted 5 to 14 membered heterocyclyl in which R3 is absent, a hydrogen atom, or a bond between N and R1 or between N and R2 ; or to form a substituted 5 to 14 membered heteroaryl in which R3 is absent, a hydrogen atom, a bond between N and R1 or between N and R2, said substituted 5 to 14 membered heterocyclyl, and said substituted 5 to 14 membered heteroaryl being substituted with at least one polymerizable moiety;
R3 is a polymerizable moiety;
R4 and R5 are the same or different and are selected from the group consisting of a hydrogen atom, C1-C12 alkyl which is linear or branched, C3-Ci2 cycloalkyl, Ci-Ci2 heterocyclyl, C2-C8 alkenyl, C2-C8 alkynyl, C6-C12 aryl, C6-C20 aralkyl, C6-C20 alkylaryl, C1-C12 heteroaryl, CnH2n+I, Ph2P-, Me2P, Ph2P(S), Me2P(S), CN;
or
R4 and R5 are joined together to form a 5 to 14 substituted membered heterocyclyl in which R6 is absent, a hydrogen atom, or a bond between P and R4 or between P and R5 ; or to form a substituted 5 to 14 membered heteroaryl ring in which R6 is absent, a hydrogen atom, a bond between P and R4 or between P and R5, said substituted 5 to 14 membered heterocyclyl, and said substituted 5 to 14 membered heteroaryl being substituted with at least one polymerizable moiety;
R6 is a polymerizable moiety;
X- is (FSO2)2N-, (CF3SO2)2N-, (C2F5SO2)2N-, (CF3SO2)3C-, CF3SO3 ", CF3COO-, AsF6 ", CH3COO-, (CN)2N-, CN", NO3 ", HSO4 ", H2PO3 ", PO4 3", F", Cl", Br", I", PF6 ", BF4 ", CIO4 ", saccharin(o-benzoic sulfimide), (C8H16SO2)2N-, or C3H3N2 ";
said alkyl, cycloalkyl, heterocyclyl, alkenyl, alkynyl, aryl, aralkyl, alkylaryl, and heteroaryl being unsubstituted or substituted with at least one substitutent chosen from F, Cl, Br, I, a CrC6 alkoxy, a CrC6 hydroxy alkyl, NO2, CN, CF3, SO3 ", PO4 3", CnF2n+1, Ci-Ci2 alkyl which is linear or branched, C6-Ci2 aryl, CnH2n+I, Ph2P-, Me2P, Ph2P(S), Me2P(S), CeHsCpH2P-, CpH2p+iC6H4— , CpH2P+iC6H4CnH2n— , CH2=CHCpH2p— , CH2=CHCeHs-, CH2=CHCeH4CpH2P+-I-,
CH2=CHCpH2PC6H4-, and a polymerizable moiety.
where n is an integer having a value from O to 48 and p is an integer having a value from O to 48.
20. The polymer of claim 19, wherein said polymerizable moiety comprises at least one polymerizable entity chosen from a double bond, a triple bond, a carbonyl, a free radical acceptor, and a polymerizable cyclic compound.
21. The polymer of claim 19, wherein said polymerizable moiety comprises at least one polymerizable entity chosen from a double bond, a triple bond, and a polymerizable cyclic compound.
22. The polymer of claim 20 or 21 , wherein said polymerizable cyclic compound is an epoxide, an aziridine, a cyclopropene, or a thiophene.
23. The polymer of claim 19, wherein said polymerizable moiety is chosen from a cyclopropenyl, a C4-C2O alkylcyclopropenyl, a C4-C2O cyclopropenylalkyl, an epoxide, a C3-C2o alkyloxirane, a C3-C2o oxiranealkyl, C2-C2O alkenyl, and C2-C2O alkynyl.
24. The polymer of claim 19, wherein said polymerizable moiety is chosen from a cyclopropenyl, an epoxide, C2-C2O alkenyl, and C2-C2O alkynyl.
25. The polymer of any one of claims 19 to 24, wherein said reactants comprise a polymerization initiator.
26. The polymer of any one of claims 19 to 24, wherein said reactants comprise at least one other monomer.
27. The polymer of any one of claims 19 to 24, wherein said reactants comprise an additive chosen from ethylene, propene, butene, isoprene, styrene, ethylene oxide, propylene oxide, vinyl fluoride, chloro ethylene, fluoro ethylene, isobutadiene, vinyl sulfonic acid or salts thereof and mixtures thereof.
28. The polymer of any one of claims 19 to 24, wherein said reactants comprise an additive chosen from ethylene, propene, butene, isoprene, styrene, ethylene oxide, propylene oxide, isobutadiene, said additive being unsubstitued or substituted with at least one substituant chosen from -F, -Cl, -CF3, -C2F5, -CN, -NO3 ", -CrC8 alkyl, phenyl and -SO3H or salts thereof.
29. The polymer of any one of claims 1 to 28, wherein X" is (FSO2)2N", (CF3SO2)2N-, (C2F5Sθ2)2N-, or (CN)2N-.
30. The polymer of any one of claims 1 to 28, wherein X' is (CF3SO2)2N\
31. The polymer of any one of claims 1 to 28, wherein X- is (FSO2)2N\
32. A compound of formula (I) or (II):
R1 R3 R4 R6
V© XΘ )/© χΘ
R2 H (I) R5 H (II)
wherein
R1 and R2 are the same or different and are selected from the group consisting of a hydrogen atom, CrC-I2 alkyl which is linear or branched, C3-C12 cycloalkyl, C1-C12 heterocyclyl, C2-C8 alkenyl, C2-Cg alkynyl, C6-C12 aryl, C6-C20 aralkyl, C6-C20 alkylaryl, C1-C12 heteroaryl,
or
R1 and R2 are joined together to form a substituted 5 to 14 membered heterocyclyl in which R3 is absent, a hydrogen atom, or a bond between N and R1 or between N and R2 ; or to form a substituted 5 to 14 membered heteroaryl in which R3 is absent, a hydrogen atom, a bond between N and R1 or between N and R2, said substituted 5 to 14 membered heterocyclyl, and said substituted 5 to 14 membered heteroaryl being substituted with at least one polymerizable moiety;
R3 is a polymerizable moiety;
R4 and R5 are the same or different and are selected from the group consisting of a hydrogen atom, C1-C12 alkyl which is linear or branched, C3-C12 cycloalkyl, C1-C-12 heterocyclyl, C2-C8 alkenyl, C2-C8 alkynyl, Cβ-Ci2 aryl, C6-C20 aralkyl, C6-C20 alkylaryl, Ci-Ci2 heteroaryl, CnH2n+1, Ph2P-, Me2P, Ph2P(S), Me2P(S), CN; or
R4 and R5 are joined together to form a 5 to 14 substituted membered heterocyclyl in which R6 is absent, a hydrogen atom, or a bond between P and R4 or between P and R5 ; or to form a substituted 5 to 14 membered heteroaryl ring in which R6 is absent, a hydrogen atom, a bond between P and R4 or between P and R5, said substituted 5 to 14 membered heterocyclyl, and said substituted 5 to 14 membered heteroaryl being substituted with at least one polymerizable moiety;
R6 is a polymerizable moiety; and
X- is (FSO2J2N", (CF3SOz)2N-, (C2F5SO2)2N-, or (CN)2N";
said alkyl, cycloalkyl, heterocyclyl, alkenyl, alkynyl, aryl, aralkyl, alkylaryl, and heteroaryl being unsubstituted or substituted with at least one substitutent chosen from F, Cl, Br, I, a CrCβ alkoxy, a C-i-Cε hydroxy alkyl, NO2, CN, CF3, SO3 , PO4 3 , CnF2n+I, CrCi2 alkyl which is linear or branched, C6-Ci2 aryl, CnH2n+I, Ph2P-, Me2P, Ph2P(S), Me2P(S), CeHsCpH2P-, CpH2p+iC6H4— , CpH2P+ICeH4CnH2n-, CH2 =CHCpH2p— , CH2=CHCeHs-, CH2 =CHCeH4CpH2p+i— ,
CH2=CHCpH2pC6H4-, and a polymerizable moiety.
where n is an integer having a value from O to 48 and p is an integer having a value from O to 48.
33. The compound of claim 32, wherein said compound is of formula (Ia):
(Ia)
wherein R7 is a polymerizable moiety and X is as previously defined.
34. The compound of claim 32, wherein said compound is of formula (Ib):
Figure imgf000037_0001
(Ib) wherein R7 is a polymerizable moiety and X' is as previously defined.
35. The compound of claim 32, wherein said compound is of formula (Ic):
Figure imgf000037_0002
(Ic) wherein R7 is a polymerizable moiety and X' is as previously defined.
36. The compound of claim 32, wherein said compound is of formula (Id):
Figure imgf000037_0003
(Id)
37. The compound of claim 32, wherein said compound is of formula (Na):
Figure imgf000037_0004
X
(Iia) wherein R7 is a polymerizable moiety and X" is as previously defined.
38. The compound of any one of claims 32 to 37, wherein said polymerizable moiety comprises at least one polymerizable entity chosen from a double bond, a triple bond, a carbonyl, a free radical acceptor, and a polymerizable cyclic compound.
39. The compound of any one of claims 32 to 37, wherein said polymerizable moiety comprises at least one polymerizable entity chosen from a double bond, a triple bond, and a polymerizable cyclic compound.
40. The compound of claim 38 or 39, wherein said polymerizable cyclic compound is an epoxide, an aziridine, a cyclopropene, or a thiophene.
41. The compound of any one of claims 32 to 37, wherein said polymerizable moiety is chosen from a cyclopropenyl, a C4-C20 alkylcyclopropenyl, a C4-C20 cyclopropenylalkyl, an epoxide, a C3-C20 alkyloxirane, a C3-C20 oxiranealkyl, C2-C20 alkenyl, and C2-C20 alkynyl.
42. The compound of any one of claims 32 to 37, wherein said polymerizable moiety is chosen from a cyclopropenyl, an epoxide, C2- C2O alkenyl, and C2-C2O alkynyl.
43. The compound of any one of claims 33 to 37, wherein R7 is vinyl.
44. The compound of claim 32, wherein said compound is of formula (MIb):
Figure imgf000038_0001
(IHb) X
wherein X" is as previously defined.
45. The compound of any one of claims 32 to 44, wherein X" is (CF3SO2)2N".
46. The compound of any one of claims 32 to 44, wherein X" is (FSO2)2N".
47. A compound of formula (IV) or (V) or any tautomers thereof:
Figure imgf000039_0001
wherein
R11 and R12 are same or different and are chosen from a hydrogen atom, C1-C20 alkyl which is linear or branched, a C3-Cs cycloalkyl, a C6-Ci2 aryl, C1-C12 heteroaryl, and a polymerizable moiety; and
X" is (FSOa)2N", (CF3SO2)2N", (C2F5SO2)2N-, (CF3SO2)3C", CF3SO3 ", CF3COO", AsF6-, CH3COO-, (CN)2N", CN', NO3 ", HSO4 ", H2PO3 ", PO4 3", F", Cl", Br", I", PF6 ", BF4 ", CIO4 ", saccharin (o-benzoic sulfimide), (C8Hi6SO2)2N", or C3H3N2 ";
said alkyl, cycloalkyl, aryl and heteroaryl being unsubstituted or substituted with at least one substitutent chosen from F, Cl, Br, I, OH, a d-C6 alkoxy, a CrC6 hydroxy alkyl, NO2, CN, CF3, SO3 ", CnF2n+I, C-ι-C-12 alkyl which is linear or branched, C6-Ci2 aryl, CnH2n+I, C6HsCpH2P-, CpH2p+iC6H4-, CpH2p+i C6H4CnH2n-, CH2=CHCpH2p— , CH2=CHC6Hs-, CH2=CHC6H4CpH2p+i— ,
CH2=CHCpH2pC6H4-, and a polymerizable moiety;
n is an integer having a value from O to 48 and p is an integer having a value from O to 48.
48. A compound of formula (Vl) or any tautomers thereof:
Figure imgf000040_0001
(Vl)
wherein
R11 and R12 are same or different and are chosen from a hydrogen atom, d-C2o alkyl which is linear or branched, a C3-C8 cycloalkyl, a C6-C12 aryl, C1-C-12 heteroaryl, and a polymerizable moiety; and
X- is (FSOs)2N-, (CF3SO2)2N-, (C2F5SO2)2N-, (CF3SO2)SC-, CF3SO3-, CF3COO-, AsF6-, CH3COO", (CN)2N", CN", NO3 ", HSO4 ", H2PO3 ", PO4 3", F', Cl", Br", r, PF6 ", BF4 ", CIO4 ", saccharin(o-benzoic sulfimide), (C8Hi6SO2)2N-, or C3H3N2 ",
m having a value of 1 , 2, or 3; and
said aryl and heteroaryl being unsubstituted or substituted with at least one substitutent chosen from F, Cl, Br, I, OH, a CrC6 alkoxy, a Ci-C6 hydroxy alkyl, NO2, CN, CF3, SO3 ", CnF2n+I, C1-C12 alkyl which is linear or branched, C6-Ci2 aryl, CnH2n+I, C6H5CpH2p-, CpH2P+IC6H4-, CpH2P+IC6H4CnH2n-, CH2=CHCpH2P-, CH2=CHC6Hs-,
CH2=CHC6H4CpH2P+I-, CH2=CHCpH2pC6H4- and a polymerizable moiety,
n is an integer having a value from O to 48 and p is an integer having a value from O to 48.
49. The compound of claim 47 or 48, wherein R11 and R12 both represent an unsubstituted phenyl.
50. The compound of claim 47 or 48, wherein at least one of R11 and R12 represent a polymerizable moiety.
51. The compound of claim 50, wherein said polymerizable moiety comprises at least one polymerizable entity chosen from a double bond, a triple bond, a carbonyl, a free radical acceptor, and a polymerizable cyclic compound.
52. The compound of claim 50, wherein said polymerizable moiety comprises at least one polymerizable entity chosen from a double bond, a triple bond, and a polymerizable cyclic compound.
53. The compound of claim 51 or 52, wherein said polymerizable cyclic compound is an epoxide, an aziridine, a cyclopropene, or a thiophene.
54. The compound of claim 50, wherein said polymerizable moiety is chosen from a cyclopropenyl, a C4-C20 alkylcyclopropenyl, a C4-C2O cyclopropenylalkyl, an epoxide, a C3-C20 alkyloxirane, a C3-C20 oxiranealkyl, C2-C20 alkenyl, and C2-C20 alkynyl.
55. The compound of claim 50, wherein said polymerizable moiety is chosen from a cyclopropenyl, an epoxide, C2-C2O alkenyl, and C2-C20 alkynyl.
56. A polymer obtained by polymerizing a compound as defined in any one of claims 32 to 46 and 50 to 55.
57. A polymer obtained by polymerizing a compound as defined in any one of claims 32 to 46 and 50 to 55 together with at least one other monomer.
58. Use of a compound as defined in any one of claims 32 to 46 as an antistatic agent.
59. Use of a compound as defined in any of claims 32 to 46 in the manufacture of a proton conducting membrane.
60. A method of using a compound as defined in any one of claims 32 to 46 and 50 to 55, comprising polymerizing said compound so as to obtain a polymer.
61. A method of using a compound as defined in any one of claims 32 to 46 and 50 to 55, comprising reacting said compound together with at least one other monomer so as to obtain a copolymer.
62. Use of a polymer as defined in any of claims 1 to 31 in the manufacture of a proton conducting membrane.
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