US 2017/0170505 Al  5  Jun. 15,2017  [0089]  Any combination of the above mentioned block  copolymers are possible.  [0092]  Sulfonation:  [0097]  Phosphonation  [0103]  1. In 1 to 50% base (alkali base such as NaOH,  KOH, LiOH, etc., earth alkali such as Ba(OH) 2 ,Ca  (OH) 2 , aqueous ammonia or aqueous primary, second› ary or tertiary amines or quaternary ammonium salts) at  temperatures between Oto 100°  C. for 1 to 480 hours;  [0104]  2. in 0, 1 to 90% mineral acid (HCI, HBr, H 2 SO 4 ,  H 3 PO 4 ) at temperatures from Oto 100°  C. for 2 to 480  hours;  [0105]  3. in fully desalted water at temperatures from 0  to 100°  C. for 2 seconds to 480 hours;  [0106]  4. in 0,1 to 10 molar Zr0Cl 2 -solution at tem› peratures from O to 100°  C. for 2 to 480 hours;  [0107]  5. in fully desalted water at temperatures from 0  to 100°  C. for 2 seconds to 480 hours;  [0108]  6. in 0,1 to 90% H 3 PO 4  at temperatures from 0  to 100°  C. for 2 to 480 hours;  [0109]  7. in fully desalted water at temperatures from 0  to 100°  C. for 2 seconds to 480 hours.  [0099]  Carboxylation  Application Examples  $^{15 }$IT R. Allcock, M.A. Hofmann, C. M. Ambler, R. V. Morford,  Macromol› ecules  2002, 35, 3484-3489  16  B. Lafitte, P. Jannasch,  Journal of Polymer Science: Part A: Polymer  Chemistry  2005, 43, 273-286  $^{17 }$K. Jakoby,  K.  V. Peinemann, S. P. Nunes,  Macromol. Chem. Phys  204,  61-67, 2003  $^{18 }$Xu and I. Cabasso,  J. Polym. Mater. Sci.  1993, 120, 68  [0090]  Especially preferred polymer construction units  and polymers are presented in der  FIG.18,  FIG.  19,  FIG.  20,  FIG.  21,  FIG.  22,  FIG.  23,  FIG.  24,  FIG.  25,  FIG.  26,  FIG.  27,  FIG.  28,  FIG.  29,  FIG.  30,  FIG.  31,  FIG.  32  and FIG.  33.  [0091]  All common procedures for the phosphonation,  carboxylation and/or sulfonation of the polymers can be  applied. The most important procedures are presented in the  following:  [0093]  Process via metalation: first inetalation (e.g. with  n-butyl lithium), then reaction with a S-electrophil (SO 2 ,  SO 3 , SOCl 2 , SO 2 Cl 2 ), then if necessary reaction to the  sulfonic acid ( during the reaction of lithiated polymers with  SO 2  sulfinates are formed, which are processed with an  oxidation agent like H 2 O 2 , NaOCI, KMnO 4  etc. to the  corresponding sulfonates 47 , during the reaction of lithiated  polymers with SO 2 Cl 2  sulfochlorides are formed, which are  hydrolysed with water, acids or bases to the corresponding  sulfonic acids 48 ).  $^{47 }$J. Kerres, W. Cui, P. Reichle, J. Polym. Sci,: Part A: Polym. Chem, 34,  2421-2438 (1996)  $^{48 }$J. A. Kerres, A. J. van Zyl, J. Appl. Polym. Sci. 74, 428-438 (1999)  [0100]  The polymers can be carboxylated with all com› mon procedures. Picked is here the carboxylation of poly› mers via lithiated intermediates like the lithiation of poly› sulfon PSU Ude! or the lithiation of polyphenylene oxide  with subsequent reaction of the lithiated intermediate with  solid or gaseous CO/ 6 • 57 . From the polymeric carbonic acid  the corresponding acid halide can be made by reaction with  thionylchloride (for the following reaction with e.g. tris  (trimethylsilyl)phosphite to the corresponding l-hydroxym› ethylene-1, 1-bisphosphonic acid). Also the nucleophilic  substitution reaction of electron poor halogene aromates  with KCN and subsequent saponification of the CN group to  the COOH group are mentioned here. Moreover methyl  aromates can be reacted with potassium permanganate to the  corresponding aromatic carbonic acids, e.g. 2-, 3- or 4-meth› ylpyridines. Aliphatic carbonic acids are also obtainable by  oxidation of aliphatic alcohols or aldehydes.  $^{56 }$Guiver, M. D.  Ph. D. Dissertation,  Carletown university 1987, Ottawa› Ontario, Canada  $^{57 }$Beihoffer, T. W.; Glas, J.E.  Polymer  1986, 27, 1626-32  [0094]  Process via electrophilic sulfonation: reaction of  the polymer with concentrated sulfuric acid 49 ’ 50 , H 2 SO 4 _  SO/ 1 • 52 , chlorsulfonic acid, SO 3 -triethylphosphate, SO 3 - pyridine or other usual S-electrophiles.  [0095]  Also other not explicitly described sulfonation pro› cesses can be used for the introduction of the sulfonic acid  group.  $^{49 }$F.  Helmer-Metzmann,  F.  Osan, A. Schneller, H. Ritter.  K.  Ledjeff, R. Nolte,  R. Thorwirth, EP 0574 791 Bl, 22.12.1999  $^{50 }$S. Kaliuguine, S. D. Mikhailenko.  K.  P. Wang, P. Xing, G. P. Robertson, M.  D. Guiver,  Catalysis Today  2003, 82, 213-222  $^{51 }$H. H. Ulrich, G. Rafter,  Angew. Makromol. Chem.  1998, 263, 71-78  52  J, Kerres, C.-M. Tang, C. Graf,  Ind. Eng. Chem. Res.  2004, 43(16),  4571-4579 (available via URL: http://pubs.acs.org/cgibin/asap.cgi/iecred/  asap/pdf/ie0307 62d.pdf)  [0101]  1. Preparation of an ionically cross-linked blend  from a l-hydraxymethylene-1,1-bisphosphonic acid con› taining a pyridine group and a sulfonated arylene main-chain  polymer (universal procedure)  [0102]  3 g of the sulfonated arylene main-chain polymer  in the SO 3 Na form are dissolved in DMSO to a 10%  solution.  It is dissolved so much of the pyridine-containing  l-hydroxymethylene-1,1-bisphosphonic acid in the Na+  form in DMSO to a 10% solution, that there is 1 sulfonate  group per 1 pyridine group. Thereafter the solutions are  mixed together. The combined solution is cast onto a glass  plate to a thin film with a doctor knife. Then the DMSO is  removed via evaporation at temperatures between 50 and  150°  C. and, if necessary, low pressure of 800-10 mbar. Then  the polymer film is removed under water from the glass  plate. The polymer film is posttreated as follows:  [0096]  Also polymers can be used according to the inven› tion where sulfonated monomers are polymerised/polycon› densated, e.g. as described by McGrath et al. 53 • 54 55 .  $^{53 }$Y.  S. Kim,  F.  Wang, M. Rickner, T. A. Zawodzinski, J. E. McGrath.  J.  Membr. Sci.  2003, 212, 263  $^{54 }$W.  L.  Harrison.  F.  Wang, J.B. Mecham, V. A. Bhanu, M. Hill,  Y.  S. Kim,  J. E. McGrath.  J. Polym. Sci., Part A: Polym. Chem.  2003, 41,2264  $^{55 }$Y.  S.  Kim, M. A. Rickner,  L.  Dong, B. S. Pivovar. J. E. McGrath,  J. Membr. Sci.  2004, 243,317  [0098]  Apart from the processes according to the inven› tion of the reaction of carbonic acid groups or carbonic acid  derivatives like carbonic acid chloride or carbonic acid  anhydride with phosphorous acid derivatives like PCl 3 ,  phosphorous acid, phosphorous acid ester or tris(trimethyl› silyl)phosphite, the usual procedures (phosphonation of the  polymers 15 • 16 17 • 18  or phosphonation of monomers with sub› sequent polymerisation/polycondensation 14 ) can be applied.  The best known reactions for the phosphonation of polymers  are the Michaelis-Arbusov-reaction or the Michaelis› Becker-reaction. Also other here not explicitly described  phosphonation processes can be used for the introduction of  the phosphonic acid group. A possible process is the meta› lation of the polymer and the subsequent reaction of the  metallated polymer with a halogenated phosphor acid ester  or phosphonic acid ester (examples: Chlorphosphorsauredi› aryl16- or -alkylester, 2-bromethanphosphonic acid dialky› lester, 3-brompropan-phosphonic acid dialkylester etc.). 