Phosphonic acid-containing blends and phosphonic acid-containing polymers

Abstract

A blend or blend membrane formed from a hydroxymethylene-oligo-phosphonic acid R-C(P0 3 H 2 ) x (OH) y and a polymer, in which the radical R is any organic radical, x and y are integers, the hydroxymethylene-oligo-phosphonic acid is a product of a reaction involving a carbonic acid, a carbonic acid halide or a carbonic acid anhydride, and the polymer includes a functional group selected from the group consisting of (i) suitable cation exchange groups or their non-ionic precursor and (ii) suitable basic groups.

1 . (canceled) 
     
     
         2 . A blend or blend membrane formed from a hydroxymethylene-oligo-phosphonic acid R-C(P0 3 H 2 ) x (OH) y  and a polymer, in which the radical R is any organic radical, x and y are integers, the hydroxymethylene-oligo-phosphonic acid is a product of a reaction involving a carbonic acid, a carbonic acid halide or a carbonic acid anhydride, and the polymer includes a functional group selected from the group consisting of:
 (i) cation exchange groups or their non-ionic precursor of the type —SO 2 X, —POX 2 , or —COX, where X represents a halogen —OH, —OMe, —NR 1 R 2 , or —OR 1 , where Me represents a metal cation or a transition metal cation, and where R 1  and R 2  represent —H, an aryl radical or an alkyl radical; and   (ii) basic groups selected from the group consisting of primary, secondary or tertiary amino groups, imidazole groups, pyridine groups, pyrazole groups and —OH groups.   
     
     
         3 . The blend or blend membrane of  claim 2 , wherein the transition metal cations comprises ZrO 2+  or TiO 2+  or ammonium cation 
     
     
         4 . The blend or blend membrane of  claim 2 , wherein the hydroxymethylene-oligo-phosphonic acid is formed by reacting either (a) the carbonic acid with PCl 3 /H 3 PO 3  and subsequent hydrolysis with H 2 O; or (b) the carbonic acid, the carbonic acid halide, or the carbonic acid anhydride with tris (trimethyl silyl phosphite) with subsequent hydrolysis by methanol. 
     
     
         5 . The blend or blend membrane of  claim 2 , wherein the radical R of the hydroxymethylene-oligo phosphonic acid contains an aliphatic or aromatic basic group, which interacts ionically with an acidic group in the polymer. 
     
     
         6 . The blend or blend membrane of  claim 5 , wherein the aliphatic or aromatic basic group is selected from the group consisting of: primary, secondary and tertiary basic amino groups, quaternary ammonium salts, imidazole groups, pyrazole groups, pyridyl radicals, and other basic heterocyclic and heteroaromatic radicals. 
     
     
         7 . The blend or blend membrane of  claim 2 , wherein molecules of the hydroxymethylene-oligo phosphonic are covalently cross-linked with each other at the OH groups, or with OH groups in the polymer. 
     
     
         8 . The blend or blend membrane of  claim 7 , wherein cross-linking is achieved by: (a) addition of AgNO 3  under hydrothermal conditions and reduction of AgNO 3  to elemental silver nanoparticles and liberation of HNO 3 ; (b) using epichlorohydrine as cross-linker; (c) by addition of glutaraldehyde or other di-aldehydes; (d) addition of melamine-formaldehyde-cross-linkers; (e) by reacting the OH groups with cinnamon acid chloride under UV light; (f) addition of α,β-dihalogen alkanes, dihalogen aromates, or Hal-R-Hal, where Hal represents a halogen. 
     
     
         9 . The blend or blend membrane of  claim 8 , wherein the cross-linking is achieved by further including a deprotonation agent for the OH groups. 
     
     
         10 . The blend or blend membrane of  claim 2 , wherein the hydroxymethylene-oligo phosphonic acid comprises a modified polymer formed by either (a) reacting a phosphite compound with a polymer containing functional groups selected from the group consisting of carbonic acid groups and carbonic acid halide groups; or (b) (i) reacting a polymeric aldehyde with phosphorous acid ester under amine catalysis, and (ii) oxidizing an intermediate hydroxyphosphonic acid therefrom with MnO 2  or another oxidation agent. 
     
     
         11 . A process for producing an ionically cross-linked blend from the hydroxymethylene-oligo phosphonic and a sulfonated aryl main chain polymer, comprising:
 (a) dissolving the sulfonated aryl main chain polymer in a salt form in a dipolar-aprotic solvent;   (b) dissolving the hydroxymethylene-oligo phosphonic acid in a dipolar-aprotic solvent;   (c) mixing the solutions of (a) and (b) and coating the mixture on a glass plate to a thin film at a temperature between 50 and 150° C.;   (d) evaporating the solvent under a pressure between 10 and 800 mbar;   (e) removing the polymer film under water from the glass plate;   (f) at a temperature between 0° C. to 100° C., post-treating the polymer film (i) in a 1 to 50% base; (ii) in a 0.1 to 90% mineral acid; (iii) in 0.1 to 10 molar ZrOCl 2  solution; and (iv) in 0.1 to 90% H 3 PO 4 , wherein after each of steps (i)-(iv) the polymer film is rinsed in deionised water.   
     
     
         12 . The process of  claim 11 , wherein the dipolar-aprotic solvent comprises DMSO as a 1 to 20% solution. 
     
     
         13 . The process of  claim 11 , wherein the base is selected from the group consisting of NaOH, KOH, LiOH, Ba(OH) 2 , Ca(OH) 2 , aqueous ammonia, aqueous primary, secondary or tertiary amines, and quaternary ammonium salts. 
     
     
         14 . The process of  claim 11 , further comprising including in the mixture a cross-linker. 
     
     
         15 . The process of  claim 14 , wherein the cross-linker comprises glutaraldehyde. 
     
     
         16 . The process of  claim 11 , wherein the hydroxymethylene-oligo phosphonic acid is formed by:
 (a) reacting a carboxylated polymer with a thionyl chloride to form a carbonic acid chloride;   (b) dissolving the polymeric acid chloride in an ether solvent to a 0.1 to 5% solution;   (c) transferring the polymeric acid chloride solution into a previously silylated, dried glass vessel under argon and cooled under argon to a temperature between 0° C. and −78° C.;   (d) under stirring, introducing tris into the glass vessel to provide a silyl ester;   (e) hydrolyzing the silyl ester in methanol;   (f) evaporating the solvent;   (g) precipitating a polymer precipitate in HCl;   (h) filtering and washing the polymer precipitate in HCl;   (i) dissolving the washed polymer precipitate in water; and   (j) evaporating the water and drying a resulting polymer over P 4 O 10 .   
     
     
         17 . The process of  claim 16 , wherein the ether solvent comprises THF or diethylether.