[0056] 2. Production of Polymeric l-hydroxymethylene- 1,1-bisphosphonic Acids from Carboxylated Polymers 

[0057] As already mentioned in part 1, it is known, that l-hydroxymethylene-1,1-bisphosphonic acids can be made from acid chlorides R-COCI or acid anhydrides with tris (trimethylsilyl)phosphite and following hydrolysis of the silyl compound or by reaction of carbonic acids with phos› phorous trichloride in phosphorous acid. Surprisingly it has been found that this reaction is successful also with poly› meric carbonic acids/polymeric carbonic acid halides. Poly› mers modified with the l-hydroxymethylene-1,1-bisphos› phonic acid groups are also part ofthis invention. In FIG. 12 is shown the production of polysulfone Ude!fi modified with l-hydroxymethylene-1, 1-bisphosphonic acid groups from PSU-carbonic acid chloride. In principal with this synthetic method all carboxylated polymers can be reacted to polymers containing the l-hydroxymethylene-1,1-bispho› sphonic acid group. 

[0058] Semi empirical calculation with the SoftwareACD Laboratories (pKA module) have shown surprisingly, that the acidity of l-hydroxymethylene-1, 1-bisphosphonic acids of the type R-C(PO$_{3}$H$_{2}$)x(OH)y (here x=2 and y=l) as in FIG. 13 and FIG. 14 have a high acidity for phosphonic acids of pKA=O up to even pKA=-1. Semi empirical calculation with the Software ACD Laboratories (pKA module) on polymeric model compounds containing the l-hydroxymethylene-1,1- bisphosphonic acid groups have shown surprisingly that also the phosphonic acid groups of the corresponding polymers show a high acidity for phosphonic acids of about pKA=O (FIG. 15). 

[0059] 3. Production of Polymeric l-hydroxymethylene- 1,1-bisphosphonic Acids from Polymers Containing Carbo› nyl Groups (Aldehyde or Ceio Groups) 

[0060] In the literature there is one publication describing the production of l-hydroxymethylene-1,1-bisphosphonic acids from aldehyds 44 . It has been found surprisingly, that this reaction can be carried out with polymers carrying aldehyd groups. The reaction is shown exemplarily in FIG. 16 for an aldehyd-modified polythioethersulfone made from lithiated polythioethersulfone by reaction of N,N-dimethyl› formamide (DMF) 45 . Also surprisingly was that polymers carrying ceto groups (made for example as in 46 ) can be modified with this method with l-hydroxymethylene-1,1- bisphosphonic acid groups. An example of such a reaction is shown in FIG. 17. 

$^{44 }$Y. L. Xie. Q. Zhu. X. R. Qin, Y. Y. Xie, Chinese Chemical Letters 2003, 14(1), 25-28 

$^{45 }$M. D. Guiver. H. Zhang, G. P. Robertson, Y. Dai, Journal of Polymer Science, Part A. Polymer Chemistry 2001, 39, 675-682 

$^{46 }$J. Kerres, A. Ullrich, T. Haring. U.S. Pat. No. 6,590,067; granted at Aug. 7, 2003; European Patent EPl 105 433 Bl; granted at 27 Oct. 2004 

[0061] In principal all common polymers containing the functional groups as mentioned in part 1 can be used. 

[0062] The following polymers are preferred: 

[0063] polyolefines like polyethylene, polypropylene, polyisobutylene, polynorbornene, polymethylpentene, polyisoprene, poly(l ,4-butadiene ), poly(l ,2-butadiene) 

[0064] styrene( co )polymers like polystyrene, poly(m› ethylstyrene ), poly( a,~,~-trifluorstyrene ), poly(penta› fluorostyrene) 

[0065] polyvinylalkohols and their copolymers 

[0066] polyvinylphenols and their copolymers 

[0067] poly( 4-vinylpyridine ), poly(2-vinylpyridine) and their copolymers 

[0068] perfluorinated ionomers like Nafionfi or their SO$_{2}$Hal precursor of Nafionfi (Hal=F, CI, Br, I), Dowfi-membrane, GoreSelectfi-membrane 

[0069] sulfonated PVDF and/or the SO$_{2}$Hal-precursor, whereby Hal represents fluorine, chlorine, bromine or iodine 

[0070] (het)aryl main chain polymers like: 

[0071] polyetherketones like polyetherketone PEK Victrexfi, polyetheretherke one PEEK Victrexfi, polyetherketoneketone PEKK, polyetheretherke› toneketone 

[0072] PEEKK, polyetherketoneetherketoneketone PEKEKK Ultrapekfi 

[0073] polyethersulfone like polysulfone Ude!fi, polyphenylsulfone Radel Rfi, polyetherethersulfone Radel Afi, polyethersulfone PES Victrexfi 

[0074] poly(benz)imidazole like PBI Celazolfi and other oligomers and polymers containing the (benz) imidazole building block whereby the (benz)imida› zole group can be in the main chain or in the polymer side chain polyphenyleneether like e.g. poly(2,6- dimethyloxyphenylene ), poly(2,6-diphenylox-yphe› nylene) 

[0075] polyphenylensulfide and copolymers 

[0076] poly(l ,4-phenylene) or poly(l ,3-phenylene ), which can be modified in the side chain if necessary in with benzoyl-, naphtoyl- or o-phenyloxy-1,4-ben› zoyl groups, m-phenyloxy-1,4-benzoylgroups or p-phenyloxy-1,4-benzoyl groups. 

[0077] poly(benzoxazole) and copolymers 

[0078] poly(benzthiazole) and copolymers 

[0079] poly(phtalazinone) and copolymers 

[0080] polyaniline and copolymers 

[0081] In principle all polymers especially all aryl main chain polymers are possible as base polymers for the poly› mers and polymer mixtures according to the invention. Also all possible block copolymers from these polymers, espe› cially from aryl main chain polymers are possible, whereby the following types of block copolymers are preferred: 

[0082] block copolymers made from cation exchange group modified blocks (-COX, POX$_{2}$ , SO $_{2}$X with X=OH, OMet, NR$_{2}$ , Met=metal cation, ammonium ion, OR with R=alkyl or aryl) and from unmodified blocks; 

[0083] block copolymers made from OH group modi› fied blocks and from unmodified block; 

[0084] block copolymers made from blocks containing basic groups and from unmodified block; thereby the choice of basic groups is not limited, however preferred are heterocyclic or heteroaromatic, e.g. pyridyl-, imi› dazolyl-, benzimidazolyl- or pyrazolyl groups; 

[0085] block copolymers, made from blocks modified with hydrophobic groups ( e.g. trimethylsilyl -Si(CH$_{3}$ ) 3 , trifluormethyl -CF$_{3}$ , fluoride -F) and from blocks modified with cation exhcange groups (-COX, -POX$_{2}$ , -SO$_{2}$X withX=OH, OMet, NR$_{2}$ , Met=metal cation, ammonium ion, OR with R=alkyl or aryl); 

[0086] block copolymers from acidic blocks containing cation exchange groups and blocks containing basics groups; 

[0087] block copolymers with OH groups containing blocks and acidic groups containing blocks; 

[0088] block copolymers with OH groups containing blocks and basic groups containing blocks. 

