Ionomers with ionogenic groups in the sidechain

Abstract

The invention relates to ionomeric membranes, comprising a non- or partly-fluorinated, non-, partly- or fully-aromatic backbone and a non- or partly-fluorinated sidechain with ionogenic groups, or the non-ionic precursors thereof and a method for production of said ionomeric membranes.

1 . Polymeric ionomers and ionomer membranes, characterised in that they are composed of a non- or partly-fluorinated, partly or fully aromatic main chain and a non- or partly fluorinated side chain with ionic groups or their non-ionic precursor and if are necessary covalently cross-linked. 
   
   
       2 . Polymeric ionomers and ionomer membranes according to  claim 1 , characterised in that they contain the following structure: 
     
       
         
         
             
             
         
       
     
   
   
       3 . Polymeric ionomers and ionomer membranes according to  claim 1 , characterised in that as polymer main chain the following polymers are possible:
 Polyolefines like Polyethylen, Polypropylen, Polyisobutylen, Polynorbornen, Polymethylpenten, Poly(1,4-isopren), Poly(3,4-isopren), Poly(1,4-butadien), Poly(1,2-butadien) and Block-, alternating or statistical copolymers of polydiene, polybutadiene and polyisoprene with styrole   styrol(co)polymere like polystyrole, poly(methylstyrole), poly(α,β,β-trifluorstyrole), poly(pentafluorostyrole)   perfluorinated ionomeres like Nafion® or the SO 2 Hal-precursor of Nafion® (Hal=F, Cl, Br, I), Dow®-Membrane, GoreSelect®-Membrane.   partly-fluorinated polymeres like polyvinylidenfluoride, polyvinylfluoride and their copolymeres with polyolefines or with arylmain chain polymers of  FIG. 5  (see below) N-basic polymeres like polyvinylcarbazole, polyethylenimine, poly(2-vinylpyridine), poly(3-vinylpyridine), poly(4-vinylpyridine)   (Het)aryl main chain polymers containing the construction units of  FIG. 5 .   
   
   
       4 . Polymeric ionomeres and ionomer membranes according to  claim 1 , characterised in that as polymer main chain the following polymers are preferred:
 polyetherketones like polyetherketone PEK Victrex®, polyetheretherketone PEEK Victrex®, polyetheretherketoneketone PEEKK, polyetherketonetherketone-ketone PEKEKK Ultrapek®   polyethersulfone like polysulfone Udel®, polyphenylsulfone Radel R®, polyetherethersulfone Radel A®, polyethersulfone PES Victrex®   poly(benz)imidazole like PBI Celazol® and other oligomers and polymers containing the (Benz)imidazole unit, whereby the (Benz)imidazole group can be in main chain or in the polymer side chain polyphenylenether like Poly(2,6-dimethyloxyphenylen), Poly(2,6-diphenyloxyphenylen)   polyphenylensulfide and copolymeres   poly(1,4-phenylene) or poly(1,3-phenylene), which are modified in the side chain if necessary with benzoyl-, naphtoyl- or o-phenyloxy-1,4-benzoylgroups, m-phenyloxy-1,4-benzoylgroup or p-phenyloxy-1,4-benzoylgroups.
 poly(benzoxazole) and copolymers 
 poly(benzthiazole) and copolymers 
 poly(phtalazinone) and copolymers 
 polyanilin and copolymers 
 polythiazoles 
 polypyrroles 
   
   
   
       5 . Process to produce polymeric ionomeres and ionomer membranes according to  claim 1 , characterised in that as reagents for the Arylpolymer-Deprotonation the following reagents are used:
 n-Butyllithium, sec-Butyllithium, tert. Butyllithium, Methyllithium, Phenyllithium, Grignard reagents as phenylmagnesiumhalogenide and other Grignard reagents, lithiumdiisopropylamide, and other lithium amides, sodium naphtalide, potassium naphtalide, zinc organic compounds (“Rieke metals”).   
   
   
       6 . Process to produce polymeric ionomeres and ionomer membranes according to  claim 1 , characterised in that as solvents for the deprotonation reaction the following solvents are used:
 ether solvents like THF, diethylether, glyme, diglyme, triglyme, dioxane and other ether solvents as well as hydrocarbon solvents C n F 2n+2 , cyclohexane, benzene, toluene, xylole and other C—H— aromatic solvants and any other mixtures thereof and with ether solvents, wherein ether solvents are preferred and THF is especially preferred.   
   
   
       7 . Process to produce polymeric ionomeres and ionomer membranes according to  claim 1 , characterised in that as compounds with nucleophilically substitutable halogene atoms and ionic groups compounds with the following structure are used:
   Hal-C(R 1 ) x —Y,   
     wherein Y and R 1  are defined in  FIG. 2 . 
   
   
       8 . Process to produce polymeric ionomeres and ionomer membranes according to  claim 7 , characterised in that as compounds with nucleophilically substitutable halogene atoms and ionic groups compounds with the following structure are preferred: Hal-(CH 2 ) x —Y, wherein Y and R 1  are defined in  FIG. 2 . 
   
   
       9 . Process to produce polymeric ionomeres and ionomer membranes according to  claim 7 , characterised in that as halogen atoms iodine and bromine are preferred. 
   
   
       10 . Process to produce polymeric ionomeres and ionomer membranes according to  claim 2 , characterised in that the following dihalogene compounds are used in the reaction with the deprotonated polymers:
   Hal-(C(R 1 ) 2 ) x -Hal (Hal=F,Cl,Br,I; R 1 ═H,F,C n H 2n+1 , Aryl)     Br—(C(R 1 ) 2 ) x —I     Hal-(C(R 1 ) 2 ) x -Aryl-Hal     Hal-(C(R 1 ) 2 ) x —Z-Aryl-Hal, wherein Z is defined in FIG.  5 .   
   
   
       11 . Process to produce polymeric ionomeres and ionomer membranes according to  claim 2 , characterised in that the following nucleophilic compounds are used in the reaction with the side-chain halogenated polymers: 
     
       
         
         
             
             
         
       
     
   
   
       12 . Process to produce polymeric ionomeres and ionomer membranes according to  claims 2  and  11 , characterised in that for the reaction with side-chain halogenated polymers, compounds with a sulfinate group are preferred as nucleophilic compounds, which react by S-Alkylation with the halogenated polymers. 
   
   
       13 . Process to produce polymeric ionomeres and ionomer membranes according to  claims 2  and  11 , characterised in that as solvents for the reaction of the side-chain halogenated polymers with compounds containing a nucleophilic group and the ionic group or their non-ionic precursor are ether solvents as described above, hydrocarbon solvents (aliphatic or aromatic, as described above), dipolar-aprotic solvents such as NMP, DMAc, DMF, DMSO, Sulfolan, protic solvents such as alcoholes C n H 2n+1 , water or any other mixtures of these solvents with each other are used.