US 2017/0170505 Al  4  Jun.  15,2017  [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:  [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:  [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  [0088]  block copolymers with OH groups containing  blocks and basic groups containing blocks.  [0087]  block copolymers with OH groups containing  blocks and acidic groups containing blocks;  [0086]  block copolymers from acidic blocks containing  cation exchange groups and blocks containing basics  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);  [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;  [0083]  block copolymers made from OH group modi› fied blocks and from unmodified block;  [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;  [0080]  polyaniline and copolymers  [0079]  poly(phtalazinone) and copolymers  [0078]  poly(benzthiazole) and copolymers  [0077]  poly(benzoxazole) 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.  [0075]  polyphenylensulfide and copolymers  [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)  [0073]  polyethersulfone like polysulfone Ude!fi,  polyphenylsulfone Radel Rfi, polyetherethersulfone  Radel Afi, polyethersulfone PES Victrexfi  [0072]  PEEKK,  polyetherketoneetherketoneketone  PEKEKK Ultrapekfi  [0071]  polyetherketones like polyetherketone PEK  Victrexfi, polyetheretherke one PEEK Victrexfi,  polyetherketoneketone  PEKK,  polyetheretherke› toneketone  [0070]  (het)aryl main chain polymers like:  [0069]  sulfonated PVDF and/or the SO$_{2}$Hal-precursor,  whereby Hal represents fluorine, chlorine, bromine or  iodine  [0068]  perfluorinated ionomers like Nafionfi or their  SO$_{2}$Hal precursor of Nafionfi  (Hal=F, CI, Br, I),  Dowfi-membrane, GoreSelectfi-membrane 