Malononitrile-derivative anion salts, and their uses as ionic conducting materials

Abstract

The invention is related to ionic compounds, derivatives of malononitrile, in which the anionic load has been displaced. An ionic compound disclosed by the invention includes an anionic portion combined with at least one cationic portion M +m in sufficient number to ensure overall electronic neutrality; the compound is further comprised of M as a hydroxonium, a nitrosonium NO + , an ammonium —NH 4 +, a metallic cation with the valence m, an organic cation with the valence m, or an organometallic cation with the valence m. The anionic portion corresponds to one of the formulas R D —Y—C(C≡N) 2 − or Z-C(C≡N) 2 − in which Z is an electroattractive group, R D is an organic radical, and Y is a carbonyl, a thiocarbonyl, a sulfonyl, a sulfinyl, or a phosphonyl. The compounds can be used notably for ionic conducting materials, electronic conducting materials, colorants, and the catalysis of various chemical reactions.

1 . Ionic compound derived from malononitrile comprising an anionic part associated to at least one cationic part M m+  in sufficient number to provide electronic neutrality of the assembly, characterized in that M is an hydroxonium, a nitrosonium NO + , an ammonium-NH 4   + , a metallic cation having a valency m, an organic cation having a valency m or an organometallic cation having a valency m, and that the anionic part corresponds to one of the formula R D —Y—C(C≡N) 2   −  or Z-C(C≡N) 2   −  in which: 
 Z represents an electroattractor radical having a Hammett parameter at least equal to that of a phenyl radical, selected from: 
 j) —CN, —NO 2 , —SCN, —N 3 , FSO 2 —, —CF 3 , R′ F CH 2 — (R° F  being a perfluorinated radical, preferably CF 3 —), fluoroalkyloxy, fluoroalkylthioxy, fluoroalkenyloxy, fluoroalkenylthioxy radicals;  
 jj) radicals comprising one or more aromatic nuclei possibly containing at least one nitrogen, oxygen, sulfur or phosphorus atom, said nuclei possibly being condensed nuclei and/or said nuclei possibly carrying at least one substituent selected from halogens, —CN, —NO 2 , —SCN, —N 3 , CF 2 ═CF—O—, radicals R F — and R F CH 2 — in which R F  is a perfluoroalkyl alkyl having 1 to 12 carbon atoms, fluoroalkyloxy groups, fluoroalkylthioxy groups, alkyl, alkenyl, oxa-alkyl, oxa-alkenyl, aza-alkyl, aza-alkenyl, thia-alkyl, thia-alkenyl radicals, polymer radicals, radicals having at least one cationic ionophorous group and/or at least one anionic ionophorous group;  
 with the proviso that one substituent Z may be a monovalent radical, a multivalent radical, or part of a multivalent radical (including a dendrimer) carrying at least one group —C(C≡N) 2 , or a segment of a polymer;  
 
 Y represents a carbonyl group, a thiocarbonyl group, a sulfonyl group, a sulfinyl group or a phosphonyl group and:  
 R D  is a radical selected from: 
 a) alkyl or alkenyl radicals, aryl, arylalkyl, alkylaryl or alkenylaryl radicals, alicyclic or heterocyclic radicals, including polycyclic radicals;  
 b) alkyl or alkenyl radicals comprising at least one functional ether, thioether, amine, imine, amide, carboxyl, carbonyl, isocyanate, isothiocyanate, hydroxy;  
 c) aryl, arylalkyl, arylalkenyl, alkylaryl or alkenylaryl radicals, in which the aromatic nuclei and/or at least one substituent of the nucleus comprises heteroatoms such as nitrogen, oxygen, sulfur;  
 d) radicals comprising condensed aromatic cycles which possibly comprise at least one heteroatom selected from nitrogen, oxygen, sulfur;  
 e) halogenated or perhalogenated alkyl, alkenyl, aryl, arylalkyl, alkylaryl radicals, said radicals possibly comprising functional ether, thioether, imine, amine, carboxyl, carbonyl or hydroxy groups;  
 f) radicals R C C(R′)(R″)—O— in which R C  is an alkyl perfluorinated radical and R′ et R″ are independently from one another an hydrogen atom or a radical such as defined in a), b), c) or d) above [for example CF 3 CH 2 O—, (CF 3 ) 3 CO—, (CF 3 ) 2 CHO—, CF 3 CH(C 6 H 5 )O—, —CH 2 (CF 2 ) 2 CH 2 —];  
 g) radicals (R B ) 2 N—, in which the radicals R B  which are identical or different are such as defined in a), b), c), d) and e) above, one of the R B  may be a halogen atom, or the two radicals R B  together form a divalent radical which constitutes a cycle with N;  
 h) polymer radicals;  
 i) radicals having one or more cationic ionophorous groups and/or one or more anionic ionophorous groups;  
 with the proviso that one substituent R D  may be a monovalent radical, part of a multivalent radical carrying a plurality of —Y—C − (C≡N) 2  groups or a segment of a polymer;  
 with the proviso that when Y is a carbonyl and R D  is a perfluoroalkyl radical having 1 to 3 carbon atoms, or when Z is —CN, M is different from an alkali metal.  
 
 
     
     
         2 . Compound according to  claim 1 , characterized in that the organic cation is an onium cation selected from the group consisting of R 3 O +  (oxonium), NR 4   +  (ammonium), RC(NHR 2 ) 2   +  (amidinium), C(NHR 2 ) 3   +  (guanidinium), C 5 R 6 N +  (pyridinium), C 3 R 5 N 2   +  (imidazolium), C 3 R 7 N 2   +  (imidazolinium), C 2 R 4 N 3   +  (triazolium), SR 3   +  (sulfonium), PR 4   +  (phosphonium), IR 2   +  (iodonium), (C 6 R 5 ) 3 C +  (carbonium) cations, the radicals R independently representing from one another a H or a radical selected from the group consisting of: 
 alkyl, alkenyl, oxa-alkyl, oxa-alkenyl, aza-alkyl, aza-alkenyl, thia-alkyl, thia-alkenyl, aryl, arylalkyl, alkylaryl, alkenylaryl radicals, dialkylamino radicals and dialkylazo radicals;  
 cyclic or heterocyclic radicals possibly comprising at least one lateral chain comprising heteroatoms such as nitrogen, oxygen, sulfur;  
 cyclic or heterocyclic radicals possibly comprising heteroatoms in the aromatic nucleus;  
 groups comprising a plurality of aromatic or heterocyclic nuclei, condensed or non-condensed, possibly containing at least one nitrogen, oxygen, sulfur or phosphorus atom;  
 with the proviso that a plurality of radicals R may together form aliphatic or aromatic cycles, possibly enclosing the center carrying the cationic charge.  
 
     
     
         3 . Compound according to  claim 2 , characterized in that the onium cation is part of the radical Z or the radical R D .  
     
     
         4 . Compound according to  claim 2 , characterized in that the onium cation is part of a recurring unit of a polymer.  
     
     
         5 . Compound according to  claim 2 , characterized in the cation M +  is a cationic heterocycle with aromatic character, including at least one nitrogen atom which is alkylated in the cycle.  
     
     
         6 . Compound according to  claim 5 , characterized in that the cation is an imidazolium, a triazolium, a pyridinium, a 4-dimethyl-amino-pyridinium, said cations possibly carrying a substituent on the carbon atoms of the cycle.  
     
     
         7 . Compound according to  claim 2 , characterized in that the cation M is a group having a bond —N═N, —N═N + , a sulfonium group, an iodonium group, or an arene-ferrocenium cation, which is substituted or non-substituted, possibly incorporated in a polymeric network.  
     
     
         8 . Compound according to  claim 2 , characterized in that the cation is a diaryliodonium, a dialkylaryliodonium cation, a triarylsulfonium cation, a trialkylaryl sulfonium cation, or a substituted or non-substituted phenacyl-dialkyl sulfonium cation.  
     
     
         9 . Compound according to  claim 2 , characterized in that the aryliodonium cation, or the alkylaryliodonium cation, or the triarylsulfonium cation, or the alkylaryl sulfonium cation, or the phenacyl-dialkyl sulfonium cation are part of a polymer chain.  
     
     
         10 . Compound according to  claim 2 , characterized in that M is an organic cation incorporating a group 2,2′[azobis(2-2′-imidazolinio-2-yl)propane] 2+  or 2,2′-azobis(2-amidiniopropane) 2+ .  
     
     
         11 . Compound according to  claim 1 , characterized in that the cation M is a metallic cation selected from the group consisting of cations of alkali metals, cations of alkali-earth metals, cations of transition metals, cations of trivalent metals and cations of rare earths.  
     
     
         12 . Compound according to  claim 1 , characterized in that the cation is a metallocenium, selected from the group consisting of cations derived from ferrocene, titanocene and zirconocene, indenocenium cations, arene metallocenium cations, cations of transition metals complexed with ligands possibly having a chirality and organometallic cations having one or more alkyl or aryl groups covalently bound to an atom or a group of atoms, said cations possibly being part of a polymer chain.  
     
     
         13 . Compounds according to  claim 1 , characterized in that the substituent Z is selected from the group consisting of —OC n F 2n+1 , —OC 2 F 4 H, —SC n F2n+ 1  and —SC 2 F 4 H, —OCF═CF 2 , —SCF═CF 2 , n being a whole number from 1 to 8.  
     
     
         14 . Compound according to  claim 1 , characterized in that Z is a radical C n F 2n+1 CH 2 —, n being a whole number from 1 to 8.  
     
     
         15 . Compound according to  claim 1 , characterized in that R D  is a radical selected from alkyl, alkenyl, oxa-alkyl, oxa-alkenyl, aza-alkyl, aza-alkenyl, thia-alkyl or thia-alkenyl having 1 to 24 carbon atoms, or from aryl, arylalkyl, alkylaryl or alkenylaryl having 5 to 24 carbon atoms.  
     
     
         16 . Compound according to  claim 1 , characterized in that R D  is a radical selected from alkyl or alkenyl radicals having 1 to 12 carbon atoms and possibly comprising at least one heteroatom O, N or S in the main chain or in a lateral chain, and/or possibly carrying a hydroxy group, a carbonyl group, am amino group, or a carboxyl group.  
     
     
         17 . Compound according to  claim 1 , characterized in that R D  is a radical selected from aryl, arylalkyl, alkylaryl or alkenylaryl, in which the aromatic nuclei and/or their substituents comprise heteroatoms such as nitrogen, oxygen, sulfur.  
     
     
         18 . Compound according to  claim 1 , characterized in that R D  is part of a poly(oxyalkylene) radical or a polystyrene radical.  
     
     
         19 . Compound according to  claim 1 , characterized in that R D  is a radical having an iodonium, sulfonium, oxonium, ammonium, amidinium, guanidinium, pyridinium, imidazolium, triazolium, phosphonium or carbonium, said ionic group behaving totally or partially as cation M + .  
     
     
         20 . Compound according to  claim 1 , characterized in that R D  has one or more anionic ionophorous groups consisting of a carboxylic function (—CO 2   − ), a sulfonic function (—SO 3   − ), a sulfonimide function (—SO 2 NSO 2 —) or a sulfonamide function(—SO 2 N—).  
     
     
         21 . Compound according to  claim 1 , characterized in that R D  includes at least one ethylenic unsaturation and/or a condensable group and/or a group which is dissociable by thermal means, by photochemical means or by ionic dissociation.  
     
     
         22 . Compound according to  claim 1 , characterized in that R D  represents a mesomorphous group or a chromophore group or a self-doped electronically conductive polymer or a hydrolysable alkoxysilane.  
     
     
         23 . Compound according to  claim 1 , characterized in that R D  represents a recurring unit or a polymer chain.  
     
     
         24 . Compound according to  claim 1 , characterized in that R D  includes a group capable of trapping free radicals.  
     
     
         25 . Compound according to  claim 1 , characterized in that R D  includes a dissociating dipole.  
     
     
         26 . Compound according to  claim 1 , characterized in that R D  includes a redox couple.  
     
     
         27 . Compound according to  claim 1 , characterized in that R D  includes a complexing ligand.  
     
     
         28 . Compound according to  claim 1 , characterized in that R D —Y— is optically active.  
     
     
         29 . Compound according to  claim 1 , characterized in that R D —Y— represents an amino acid, or an optically or biologically active polypeptide.  
     
     
         30 . Compound according to  claim 1 , characterized in that R D  represents a radical having a valency v higher than 2, including at both free ends a group —C(C≡N) 2   − .  
     
     
         31 . Ionically conductive material comprising an ionic compound in solution in a solvent, characterized in that the ionic compound is a compound according to  claim 1 .  
     
     
         32 . Ionically conductive material according to  claim 31 , characterized in that the cation of the ionic compound is ammonium, or a cation derived from a metal, or an organic cation selected from a substituted ammonium, a imidazolium, a triazolium, a pyridinium, a 4-dimethylamino-pyridinium, said cation possibly carrying a substituent on the carbon atoms of the cycle.  
     
     
         33 . Ionically conductive material according to  claim 31 , characterized in that the substituent R D  of the ionic compound comprises an alkyl group, an aryl group, an alkylaryl group or an arylalkyl group; a mesomorphous group or a group comprising at least one ethylenic unsaturation and/or a condensable group and/or a group which is dissociable by thermal means, by photochemical means or by ionic dissociation; a self-doped electronically conductive polymer; a hydrolyzable alkoxysilane; a free radical trap; a dissociating dipole; a redox couple; a complexing ligand.  
     
     
         34 . Ionically conductive material according to  claim 31 , characterized in that the substituent R D  of the ionic compound is an alkyl or alkenyl which contains at least one heteroatom selected from O, N or S; an alkyl or an alkenyl carrying a hydroxy group, a carbonyl group, an amino group, a carboxyl group, an aryl, an arylalkyl, an alkylaryl or an alkenylaryl in which the lateral chains and/or the aromatic nuclei comprise heteroatoms.  
     
     
         35 . Material according to  claim 31 , characterized in that the substituent R D  is a recurring unit of a polymer.  
     
     
         36 . Ionically conductive material according to  claim 31 , characterized in that the substituent Z of the ionic compound is selected from the group consisting Of —OC n F 2n+1 , —OC 2 F 4 H, —SC n F 2n+1  and —SC 2 F 4 H, —OCF═CF 2 , —SCF═CF 2.    
     
     
         37 . Ionically conductive material according to  claim 31 , characterized in that the solvent is either an aprotic liquid solvent, selected from linear ethers and cyclic ethers, esters, nitriles, nitro derivatives, amides, sulfones, sulfolanes, sulfamides and partially halogenated hydrocarbons, or a polar polymer, or a mixture thereof.  
     
     
         38 . Ionically conductive material according to  claim 37 , characterized in that the solvent is a solvating polymer, cross-linked or non-cross-linked, which may carry grafted ionic groups.  
     
     
         39 . Ionically conductive material according to  claim 38 , characterized in that the solvating polymer is selected from polyethers of linear structure, comb or blocks, which may form a network, based on poly(ethylene oxide), copolymers containing the ethylene oxide or propylene oxide or allylglycidylether unit, polyphosphazene, cross-linked networks based on polyethylene glycol cross-linked with isocyanates, networks obtained by polycondensation and carrying groups enabling the incorporation of cross-linkable groups and block copolymers in which some blocks carry functions which have redox properties.  
     
     
         40 . Ionically conductive material according to  claim 31 , characterized in that the solvent consists essentially of an aprotic liquid solvent and a polar polymer solvent comprising units containing at least one heteroatom selected from sulfur, oxygen, nitrogen and fluorine.  
     
     
         41 . Ionically conductive material according to  claim 40 , characterized in that the polar polymer mainly contains units derived from acrylonitrile, vinylidene fluoride, N-vinylpyrrolidone or methyl methacrylate.  
     
     
         42 . Ionically conductive material according to  claim 31 , characterized in that it additionally contains at least one second salt.  
     
     
         43 . Ionically conductive material according to  claim 31 , characterized in that it additionally contains a mineral or organic charge in the form of powder or fibres.  
     
     
         44 . Electrochemical generator comprising a negative electrode and a positive electrode separated by an electrolyte, characterized in that the electrolyte is a material according to one of  claims 31  to  43 .  
     
     
         45 . Generator according to  claim 44 , characterized in that the negative elecrode consists of metallic lithium, or an alloy thereof, possibly in the form of a nanometric dispersion in lithium oxide, or a double nitride of lithium and a transition metal, or an oxide with low potential having the general formula Li 1+y+x/3 Ti 2−x/3 O 4  (0≦x≦1,0≦y≦1), or carbon and carbonated products derived from pyrolysis of organic materials.  
     
     
         46 . Generator according to  claim 44 , characterized in that the positive electrode is selected from vanadium oxides VO x  (2≦x≦2,5), LiV 3 O 8 , Li y Ni 1−x Co x O 2 , (0≦x≦1; 0≦y≦1), spinels of manganese Li y Mn 1−x M x O 2  (M═Cr, Al, V, Ni, 0≦x≦0,5; 0≦y≦2), organic polydisulfides, FeS, FeS 2 , iron sulfate Fe 2 (SO 4 ) 3 , phosphates and phosphosilicates of iron and lithium of olivine structure, or products thereof in which the iron is substituted by manganese, used alone or in mixtures.  
     
     
         47 . Generator according to  claim 44 , characterized in that the cathode collector is made of aluminum.  
     
     
         48 . Supercapacitance utilizing at least one carbon electrode of high specific surface, or an electrode containing a redox polymer in which the electrolyte is a material according to one of  claims 31  to  43 .  
     
     
         49 . Utilization of a material according to one of  claims 31  to  43  for doping p or n in an electronically conductive polymer.  
     
     
         50 . Electrochrome device in which the electrolyte is a material according to one of  claims 31  to  43 .  
     
     
         51 . Process of polymerization or cross-linking of monomers or prepolymers capable of cationic reaction, characterized in that a compound according to  claim 1  is used is used as photoinitiator constituting a source of acid catalyzing the reaction.  
     
     
         52 . Process according to  claim 41 , characterized in that the ionic compound is selected from those in which the cation has a bond —N═N + , —N═N—, a sulfonium group, an iodonium group or a substituted or non-substituted arene-ferrocenium, possibly incorporated in a polymeric network.  
     
     
         53 . Process according to  claim 51 , characterized in that the substituent R D  of the ionic compound is a non-substituted alkyl radical, a radical comprising an oxa group or a sulfone, a radical comprising a sulfoxide, sulfone, phosphine oxide or phosphonate group.  
     
     
         54 . Process according to  claim 51 , characterized in that the monomers are selected from the group consisting of compounds which include a cyclic ether function, a cyclic thioether function or a cyclic amine function, vinyl compounds, vinyl ethers, oxazolines, lactones and lactames.  
     
     
         55 . Process according to  claim 51 , characterized in that the prepolymer is selected from the group consisting of compounds in which epoxy groups are carried by an aliphatic chain, an aromatic chain, or an heterocyclic chain.  
     
     
         56 . Process according to  claim 51 , characterized in that it comprises mixing the photoinitiator with at least one monomer or prepolymer capable of cationic polymerization, and subjecting the mixture obtained to actinic radiation, including β radiation.  
     
     
         57 . Process according to  claim 56 , characterized in that the reaction mixture is subject to radiation after having been formed into a thin layer.  
     
     
         58 . Process according to  claim 51 , characterized in that the photoinitiator is used in the form of a solution in a solvent which is inert towards the polymerization reaction.  
     
     
         59 . Process according to  claim 58 , characterized in that the inert solvent is selected from the group consisting of acetone, methyl-ethyl ketone, acetonitrile, propylene carbonate, y butyrolactone, ether-esters of mono-, di-, tri-ethylene or propylene glycols, ether-alcohols of mono-, di-, tri-ethylene or propylene glycols, esters of phthalic or citric acid.  
     
     
         60 . Process according to  claim 51 , characterized in that the reaction is carried out in the presence of a solvent or a diluent consisting of a compound which is reactive towards polymerization.  
     
     
         61 . Process according to  claim 60 , characterized in that the reactive compound is selected from the group consisting of mono- and di-vinyl ethers of mono-, di-, tri-, tetra-ethylene or propylene glycols, trivinyl ether trimethylolpropane and divinylether of dimethanolcyclohexane, N-vinylpyrolidone, 2-propenylether of propylene carbonate.  
     
     
         62 . Process according to  claim 51 , characterized in that a photosensitizer is added to the reaction mixture.  
     
     
         63 . Process according to  claim 62 , characterized in that the photosensitizer is selected from the group consisting of anthracene, diphenyl-9,10-anthracene, perylene, phenothiazine, tetracene, xanthone, thioxanthone, isopropylthioxanthone, acetophenone, benzophenone, 1,3,5-triaryl-2-pyrazolines and their derivatives, in particular derivatives which are substituted on aromatic nuclei by alkyl, oxa- or aza-alkyl radicals.  
     
     
         64 . Process according to  claim 51 , characterized in that the reaction mixture additionally contains at least one monomer or prepolymer capable of free radical polymerization and a compound capable of releasing an initiator of free radical polymerization under the effect of actinic radiation or β radiation or the action of heat.  
     
     
         65 . Process for modifying solubility properties of a polymer having groups which are sensitive towards acids, characterized in that it consist in subjecting said polymer to actinic radiation or β radiation, in the presence of a compound according to  claim 1 .  
     
     
         66 . Process according to  claim 65 , characterized in that the polymer contains ester units or arylether units derived from tertiary alcohol.  
     
     
         67 . Process according to  claim 66 , characterized in that the polymer is selected from the group consisting of tertiobutyl polyacrylates, tertiobutyl or tertioamyl polyitaconates, poly(tertiobutoxycarbonyloxystyrene), poly(tertiobutoxy styrene).  
     
     
         68 . Process according to  claim 65 , characterized in that it is used for chemical amplification of photoresists.  
     
     
         69 . Process for the polymerization of vinyl monomers, characterized in that there is used as free radical initiator a compound according to  claim 10 .  
     
     
         70 . Composition of a cationic coloring material, characterized in that it contains a compound according to  claim 1 .  
     
     
         71 . Composition of a cationic coloring material according to  claim 70 , characterized in that the negative charge(s) of the anionic group R D —Y—C(C≡N) 2   −  or Z-C(C≡N) 2   −  are either fixed to the molecule of coloring material, or they constitute a counter-ion of positive charges of the coloring material.  
     
     
         72 . Utilization of an ionic compound according to  claim 1  as catalyst in Friedel-Crafts reactions, Diels-Alder reactions, aldolization reactions, additions of Michael, reactions of allylation, reactions of pinacolic coupling, reactions of glycosilation, reactions of opening of cycles of exetanes, reactions of metathesis of alcenes, polymerizations of Ziegler-Natta type, polymerizations of metathesis type by cycle opening and polymerizations of metathesis type of acyclic dienes.  
     
     
         73 . Utilization according to  claim 72 , characterized in that the cation of the ionic compound is selected from lithium, magnesium, copper, zinc, tin, trivalent metals, including rare earths, platinoids, and their organometallic couples.  
     
     
         74 . Utilization of a compound according to  claim 6 , as a solvent for carrying out chemical photochemical, electrochemical, photoelectrochemical reactions, said compound being used above its melting point.  
     
     
         75 . Electronically conductive material, characterized in that it comprises an ionic compound according to  claim 1 .  
     
     
         76 . Electronically conductive material according to  claim 75 , characterized in that the cationic part of the ionic compound is a polycation consisting of a doped “p” conjugated polymer.  
     
     
         77 . Electronically conductive material according to  claim 75 , characterized in that the substituent Z of the ionic compound comprises an alkyl chain having 6 to 20 carbon atoms.