[0089] Any combination of the above mentioned block copolymers are possible. 

[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: 

[0092] Sulfonation: 

[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) 

[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) 

[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 

[0097] Phosphonation 

[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.). 

$^{15 }$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 

[0099] Carboxylation 

[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 

[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: 

[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. 

## Application Examples 

