EP1984430A2

EP1984430A2 - Phosphonic acid-containing blends and phosphonic acid-containing polymers

Info

Publication number: EP1984430A2
Application number: EP07711177A
Authority: EP
Inventors: Thomas HÄRING; Jochen Kerres; Frank SCHÖNBERGER; Martin Hein
Original assignee: Institut fuer Chemische Verfahrenstechnik Universitaet Stuttgart
Current assignee: HAERING, THOMAS; Institut fuer Chemische Verfahrenstechnik Universitaet Stuttgart
Priority date: 2006-02-03
Filing date: 2007-02-05
Publication date: 2008-10-29
Also published as: US20170170505A1; WO2007101415A2; JP2016145351A; WO2007101415A3; US20090220843A1; DE112007000280A5; JP2013177598A; US8637174B2; JP2009525360A; US20140213672A1

Abstract

The invention relates to blends and blend membranes from low-molecular hydroxymethylene-oligo-phosphonic acids R-C(PO3H2)x(OH)y and polymers, the group R representing any organic group and the polymers containing the following functional groups: cation exchanger groups or their nonionic precursors of the type SO2X, X = HaI, OH, OMe, NR1R2, OR1 with Me = any metal cation or ammonium cation, R1, R2 = H or any aryl- or alkyl group, POX2, COX and/or basic groups such as primary, secondary or tertiary amino groups, imidazole groups, pyridine groups, pyrazole groups etc. and/or OH groups. Low molecular hydroxymethylene-oligo-phosphonic acids R-C(PO3H2)x(OH)y are preferred in which x = 2 and y = 1. The invention also relates to low-molecular hydroxymethylene-oligo-phosphonic acids R-C(PO3H2)2(OH)1 and polymers, wherein the group R of the hydroxymethylene-oligophosphonic acid contains an aliphatic or aromatic basic group which ionically interacts with the acidic groups of the polymer or of the polymer mixture. The invention further relates to blends and blend membranes from low-molecular hydroxymethylene-oligo-phosphonic acids R-C(PO3H2)2(OH)1 and polymers, wherein the OH groups of the low-molecular hydroxymethylene-1,1-bisphosphonic acid are covalently cross-linked with each other or optionally with OH groups of the polymer. The invention also relates to polymers that are modified with the 1-hydroxymethylene-1,1-bisphosphonic acid group. The polymers are produced by reacting polymers which contain carboxylic acid groups or carboxylic halide groups -COHal (Hal=F, Cl, Br, I) with phosphite compounds or by reacting polymeric aldehydes or polymeric keto compounds with phosphite esters while carrying out an amine catalysis, an oxidation of the intermediary hydroxyphosphonic acid with MnO2 or any other oxidant. The invention finally relates to methods for producing the aforementioned materials and to the use of membranes of the aforementioned materials in membrane processes and especially in fuel cells, even at temperatures of >100°C.

Description

State of the art

Commercially available perfluorinated sulfonic acid-based ionomer membranes can operate at temperatures below 100 ⁰ C in electrochemical cells, particularly fuel cells are used, and in this temperature range show good H ⁺ - conductivity and high (electro) chemical stability. However, they are not usable at temperatures above 100 ⁰ C, since they then dry out and therefore their proton conductivity decreases by several orders of magnitude ¹ , ² . However, it is useful to operate fuel cells at temperatures above 100 ⁰ C, since in this temperature range, the CO tolerance of the fuel cell reaction due to faster electrode kinetics is significantly greater than below 100 ⁰ C ³ . As stated above, however, is not at temperatures of about 100 ⁰ C, the use of sulfonated ionomer membranes in fuel cells in the unpressurized operation and without membrane humidification possible. In the literature there are different approaches for alternative proton conductors in the temperature range of about 100- 200 ⁰ C. One of these approaches is the interference of substances into the sulfonated Bremistoffzellenmembran that are able to water at temperatures higher than 100 ⁰ C in the fuel cell membrane to store and thus ensure sufficient proton conductivity of sulfonated fuel cell membranes in this temperature range. Such materials include micrometer to nanometer size microporous particles, which may be inorganic hydroxides, oxides or salts, or inorganic / organic hybrid compounds, such as SiO ₂ , ⁵ , ⁶ , TiO ₂ , ZrO ₂ ⁷ , or layer phosphates or zirconium sulfophenyl phosphonates , wherein the layer phosphates such as zirconium or

Zirconiumsulfophenylphosphonat also have a Eigenprotonenleitfähigkeit,. Another approach is the incorporation of phosphoric acid into basic polybenzimidazole membranes, with the phosphoric acid acting as the proton conductor, since phosphoric acid can function both as a proton donor and as a proton acceptor. These membranes

¹ KT Adjemian, S. Srinivasan, J. Benziger, AB Bocarsly, J. Power Sources 2002, 109 (2), 356-364

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⁵ KT Adjemian, SJ Lee, S. Srinivasan, J. Benziger, AB Bocarsly, J. Electrochem. Soc. 2002, 149 (3), A256-A261

⁶ 1. Honma, H. Nakajima, O. Nishikawa, T. Sugimoto, S. Nomura, J. Electrochem. Soc. 2002, 149 (10), A1389-A1392

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⁹ G. Alberti, M. Casciola, Annu. Rev. Mater. Res. 2003, 33 (1), 129-154 Can be used in fuel cells at temperatures up to about 200 ⁰ C ¹⁰ , ¹ W ³ - Since these membranes can bleed the phosphoric acid at temperatures <100 ° C from the membrane (due to the formation of liquid product water) were membranes with the self-proton conductive phosphonic acid developed. From the literature a number of works for the production of phosphonated ionomer membranes are known. They include perfluorinated phosphonated membranes, phenylphosphonic acid modified polyaryloxyphosphazenes ¹⁵ or aryl backbone polymers such as polysulfone udle ¹⁶ , ¹⁷ or polyphenylene oxide ¹⁸ based membranes. Investigations

Model compounds containing phosphonic acid groups have given significant intrinsic proton conductivity even under reduced humidification ¹⁹ . However, polymers modified with phosphonic acid groups have the following disadvantages which have hitherto prevented their use in fuel cells:

■ Experimentally, only low degrees of phosphonation could be achieved

(about one phosphonic acid group per polymer repeat unit) '' '

■ No (anhydrous) conductivity data of phosphonated polymers are available from the literature (conductivity data are only documented for phosphonated oligomers ¹⁹ )

■ Non-fluorinated arylphosphonic acids are generally only medium-strength acids (pKs «

2)

=> it will be in the hitherto synthesized phosphonated ionomers only low

Proton conductivities achieved

^■ So far, phosphonic acids can only be incorporated as esters into polymers (Michaelis-Arbusov ¹⁷ or Michaelis-Becker reaction ¹⁸ , or about lithiation ²⁰ ^'16 ).

■ Hydrolysis of the phosphonic acid esters to the free phosphonic acid has been achieved only partially so far ²⁰

¹⁰ RF Savinell; MH Litt; US 5,525,436, June 11, 1996

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²¹ Miyatake and Hay, J. Polym. Be. 2001, 39, 3770 Problematic solubility behavior of the polymeric phosphonic acids (poorly soluble in the "classical" solvents for ionomers such as NMP, DMAc or DMF)

Polymeric phosphonic acids have poor film-forming properties (are very brittle)

Many Phosphoiiierungsverfahren are not yet transferable from low molecular weight compounds to high molecular weight, z. T. due to solution problems in the solvents used for these reactions

Z. T. polymer degradation during phosphonation or during the hydrolysis of

Phosphonic acid ester to the free phosphonic acid (in the laboratory experiment, polymer degradation from 20,000 g / mol to 2,000 g / mol was observed) ²²

Phosphonic acids tend to condense at temperatures around 12O ⁰ C, which is their

Application in fuel cells in the temperature range> 100 ° C so far impossible.

task

The object of the present invention consists in the preparation of 1-hydroxymethylene-l, l-bisphosphonic acid-containing polymer blends having the following properties:

^{■ the highest} possible acidity of the phosphonic acid group

^{■ the highest} possible content of phosphonic acid groups

^■ Suppression of the condensation of the phosphonic acid group

■ Highest possible proton conductivity even under reduced humidification and at temperatures up to 180 ^° C

^■ Prevent bleeding of the polymer blends when blends according to the invention of polymers with low molecular weight 1-hydroxymethylene-1,1-bisphosphonic acids are used in membrane applications.

Another object of the invention are processes for preparing the polymer mixtures containing phosphonic acid groups (blends).

Finally, the object of the invention is the use of polymer mixtures containing phosphonic acid groups (blends) in membrane processes such as gas separation, pervaporation, perstraction, PEM electrolysis and secondary batteries such as PEM and direct methanol fuel cells, in particular under conditions of reduced humidification (0

22 J. Kerres, F. Schönberger, unpublished results to 50%) and elevated temperature (temperatures of 60 to 180 ⁰ C ₅ especially temperatures of 80-180 ⁰ C, and especially temperatures of 100 to 130 ⁰ C).

description

It has surprisingly been found that the object of the invention can be achieved by: 1. Preparation of optionally physically, ionically or covalently crosslinked Blenάs and blend membranes of low molecular weight hydroxymethylene-oligophosphonic RC (POsH ₂ ) _x (OH) _y with polymers which contain the following functional groups:

Cation exchange groups or their nonionic precursors of the type

SO ₂ X ₃ X = Hal, OH, OMe, NRiR ₂ , OR ₁ with Me = any metal cation or ammonium cation, R ₁ , R ₂ = H or any aryl or alkyl radical, POX ₂ COX and / or

Basic groups such as primary, secondary or tertiary amino groups, imidazole groups, pyridine groups, pyrazole groups etc. and / or

OH groups

Preferred erfmdungsgemäße low molecular weight 1-hydroxymethylene

, Phosphonic acids, for example, produced from carboxylic acids by reaction with

PCl ₃ ZH ₃ PO ₃ and subsequent hydrolysis with H ₂ O ²³ ' ²⁴ ' ²⁵ ^'26 " ²⁷ are shown in Figure 1. Further, preferred low molecular weight according to the invention.

, Hydroxymethylenbisphosphonsäuren, producible by reaction of

, Carboxylic acid chlorides with tris (trimethylsilylphosphate) ²⁸ ' ²⁹ ' ³⁰ ^'31 , production process

²³ Gerard R. Kieczykowski, Ronald B. Jobson, David G. Melillo, Donald F. Reinhold, Victor J. Grenda, and Ichiro Shinkai, J. Org Chem. 1995, 60, 8310-8312

²⁴ Blum, H .; Worms, K. US Pat. No. 4,327,039, 1982

²⁵ Blum, H .; Worms, K. US. 4,407,761, 1983

²⁶ Rosini, S .; Staibano, G.U.S. 4,621,077, 1986.

²⁷ Jary, J .; Řiháková, V .; Zobacova, A.US. 4,304,734, 1981

²⁸ Marc Lecouvey, Isabelle Mallard, Theodorine Bailly, Ramon Burgada and Yves Leroux, Tetrahedron Letters 2001, 42, 8475-8478

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³¹ sec., M.; Okimoto, K.; Yamada, K.; Hata, TJ Org. Chem. 1981, 46, 2097-2107 see Figure 2, are shown in Figure 3, Figure 4, Figure 5, Figure 6 and Figure 7. Another process for the preparation of 1-hydroxymethylene-1,1-bisphosphonic acids consists in the reaction of tris (trimethyl phosphite) with acid anhydrides, for example phthalic anhydride ³² .

A particular embodiment of these blends consists in the fact that ionic crosslinking sites can exist between the polymers and the low molecular weight phosphonic acids, for example between the cation exchange groups of the polymer with a basic group (eg pyridine radical) of the low molecular weight phosphonic acid compound, see Figure 8. Another possibility the binding of the low molecular weight Hydroxymethylenphosphonsäuren to the polymers consists in covalent crosslinking, such as by crosslinking of the OH group of the phosphonic acid compound with an OH group of the polymer by means of an α, ω-Dihalogenalkans, see Figure 9. Further possible crosslinking reactions for the OH group of l-hydroxymethylene-l, l-bisphosphonic acid grouping and optionally with OH groups of polymers according to the invention are:

^■ crosslinking by addition of AgNO ₃ to the OH groups-containing mixture of l-hydroxymethylene-l, l-bisphosphonic acid and optionally OH-group-containing polymer under hydrothermal conditions and reduction of AgNO ₃ to elemental silver nanoparticles and release of HNO ₃ ³ ( Figure 10 for the cross-linking of the OH groups of different 1-hydroxymethylene-1, 1-bisphosphonic acid molecules, optionally forming infinite 3D networks when using molecules with several 1-hydroxymethylene-1, 1-bisphosphonic acid groups);

■ Crosslinking of 1-hydroxymethylene-1,1-bisphosphonic acids with OH-containing polymers using epichlorohydrin as crosslinker (Figure 11) ^H35 ;

■ crosslinking of the OH groups of the 1-hydroxymethylene-1,1-bisphosphonic acids and optionally the OH groups of the polymer with glutaraldehyde ³⁶ ;

³² Guenin, E .; Degache, E .; Liquier, J., Lecouvey, M. Eur. J. Org. Chem. 2004, 2983-2987

³³ Luo, L.-B. ; Yu, S.-H. ; Qian, H.-S. ; Zhou, TJ Am. Chem. Soc. 2005, 127, 2822

³⁴ Wang, Z .; Luo, J .; Zhu, XX; Jin, S .; Tomaszewski, MJJ Comb. Chem. 2004, 6, 961-966

³⁵ Wan, Y .; Huang, WQ; Wang, Z .; Zhu, XX Polymer 2004, 45 (1), 71-77

³⁶ Zhao, D .; Liao, G .; Gao, G .; Liu, F. Macromolecules 2006, pubished on Web 1/12/2006, http://pubs.acs.org/cgi-bin/asap.cgi/mamobx/asap/pdß'ma0524191.pdf ^■ crosslinking of the OH groups of the l-hydroxymethylene-l, l-bisphosphonic acids and optionally of the OH groups of the polymer with melamine-formaldehyde crosslinkers ³⁷ ;

■ crosslinking of the OH groups of the l-hydroxymethylene-l, l-bisphosphonic acids and optionally of the OH groups of the polymer after reaction of the OH groups with cinnamic acid chloride by photocrosslinking (cycloaddition) under the action of UV light ³⁸ ;

■ Crosslinking of the OH groups of the l-hydroxymethylene-l, l-bisphosphonic acids and optionally the OH groups of the polymer with polyvalent cations, for example Ca ^{2 + 39} ;

^In principle, however, all crosslinking reactions are applicable to the inventive l-hydroxymethylene-l, l-bisphosphonic acids and optionally OH-containing polymers which are based on crosslinking reactions of the OH groups.

The covalent cross-linking prevents outdiffusion of the phosphonic acid compound from the polymer and improves the mechanical stability of the blend films.

By means of the covalent crosslinking processes described above, it is also possible to build up interpenetrating networks (IPN) of very different structure and composition. An example of this is given below. For example, the following components are dissolved in a dipolar aprotic solvent such as N-methylpyrrolidinone (NMP), N, N-dimethylacetamide (DMAc), N, N-dimethylformamide (DMF) or dimethyl sulfoxide (DMSO): a polymer having sulfochloride groups, a crosslinker for Sulfochloridgruppen such. B. 4,4'-Diaminodiphenylsulfon ⁴⁰ , a bifunctional l-hydroxymethylene-l, l-bisphosphonic acid such as l, 4-bis (l-hydroxymethylene l, l-bisphosphonic) benzene and a crosslinker for the OH groups of the 1- Hydroxymethylene 1,1-bisphosphonic acid groups such. As glutaraldehyde. After a homogeneous solution of all components has been prepared, the solution is spread out on a pad and the solvent is evaporated. The result is an IPN from the network of sulfochlorinated polymer with the difunctional amine and the network of l, 4-bis (l-hydroxymethylene-l, l-bisphosphonic) benzene and glutaraldehyde, which still by mineral acid (H ₂ SO ₄ of

³⁷ Benson, MT Ind. Eng. Chem. Res. 2003, 42, 4147-4155

³⁸ Hu, Y .; Gamble, V .; Painter, PC; Coleman, MM Macromolecules 2002, 35, 1289-1298

³⁹ Bonapasta, AA; Buda, F _.: Colombet, P .; Guerrini, G. Chem. Mater. 2002, 14, 1016-1022

⁴⁰ R. Nolte, K. Ledjeff, M. Bauer, R. Mülhaupt, R., J. Memb. Be. 1993, 83, 211-220 0.1 to 80% concentration, HCl from 0.1 to 37% concentration or phosphoric acid from 0.1 to 85% concentration) and optionally subsequent storage in water to remove excess mineral acid can be post-treated. An example of a hybrid polymer network (HPN) is for example: in a dipolar aprotic solvent (see above) the following components are dissolved: a polymer with sulfonate groups (-SO ₃ Me) and sulfinate groups (-SO ₂ Me) in the salt form with Me = Alkali metal cation, alkaline earth metal cation, any ammonium ion, Ag ⁺ ion, 3- (1-hydroxy-1,1-bisphosphonic acid) -pyridine, an α, ω-dihaloalkane, for example 1,4-diiodobutane as crosslinker for the sulfinate groups (S- Alkylation of the sulfate group ⁴¹ ) and as a crosslinker for the OH groups of l-hydroxymethylene-l, l-bisphosphonic acid groups z. Glutaraldehyde ³⁶ . After a homogeneous solution of all components has been prepared, the solution is doctored on a pad and the solvent is evaporated. The resulting HPN can still be post-treated as follows: 1. Post-treatment in mineral acid (H ₂ SO ₄ from 0.1 to 80% concentration, HCl from 0.1 to 37% concentration or phosphoric acid from 0.1 to 85% concentration) and optionally 2. subsequent storage in water to remove excess mineral acid. The resulting HPN consists of the covalent network of the polymer having the sulfinate and sulfonate groups ⁴² , the sulfinate groups having been cross-linked by S-alkylation using the 1,4-diiodobutane, and the network of 3- (l-hydroxy-l, l-bisphosphonic acid) pyridine and glutaraldehyde. In addition, ionic interactions between the two networks additionally exist via the pyridine moiety of 3- (1-hydroxy-1,1-bisphosphonic acid) -pyridine and the sulfonate moieties of the sulfonated polymer. In addition, the 1,4-diiodobutane crosslinker can also crosslink a portion of the pyridine groups by alkylation, whereby mixed crosslinking bridges between sulfinate groups and pyridine groups can arise ⁴³ .

2. Preparation of polymeric l-hydroxymethylene-l, l-bisphosphonic acids from carboxylated

polymers

As already mentioned under point 1, it is known that l-hydroxymethylene-1,1-bisphosphonic acids, for example, by reaction of acid chlorides R-COCl or acid anhydrides with tris (trimethylsilyl) phosphite and subsequent hydrolysis of the silyl compound or by reaction of carboxylic acids with phosphorus trichloride in

⁴¹ Kerres, J .; Cui, W .; Junginger, MJ Memb. Be. 1998, 139, 227-241

⁴² Kerres, J .; Zhang, W .; Cui, WJ Polym. Be: Part A: Pofym. Chem. 1998, 36, 1441-1448

⁴³ Keires, J .; Zhang, W .; Tang, CM US Patent 6,767,585; granted at 27-07-2004 Phosphorous acid can be represented. Surprisingly, it has been found that these reactions also succeed with polymeric carboxylic acids / polymeric carboxylic acid halides. Polymers modified with the 1-hydroxymethylene-1,1-bisphosphonic acid group are also content of this invention. Figure 12 shows the preparation of polysulfone Udel® from PSU carboxylic acid chloride modified with l-hydroxymethylene-1,1-bisphosphonic acid groups. In principle, all carboxylated polymers can be converted into polymers having the 1-hydroxymethylene-1, 1-bisphosphonic acid grouping using this synthesis method.

Semiempirical calculations using the software ACD Laboratories ( ^pk _s module) have surprisingly revealed that the acidity of l-hydroxymethylene-l, l-bisphosphonic acids of the type RC (PO ₃ H ₂ ) _x (OH.) Shown in Figure 13 and Figure 14 ) _y (here x = 2 and y = l) have a high acidity for phosphonic acids around p _k ^{S ==} 0 to even around p _k ^{S =} -l. Semiempirical calculations with the ACD Laboratories software (p ^k _s module) on polymer model components containing the 1-hydroxymethylene-1,1-bisphosphonic acid group have surprisingly revealed that the phosphonic acid groups of the corresponding polymers also have a high acid strength for phosphonic acids P _k ^{S =} 0 (Figure 15).

3. Preparation of polymeric 1-hydroxymethylene-1, 1-bisphosphonic acids from polymers containing carbonyl groups (aldehyde or keto groups)

There is a work in the literature describing the preparation of 1-hydroxymethylene-1,1-bisphosphonic acids from aldehydes ⁴⁴ . It has surprisingly been found that this reaction can also be applied to polymers which carry aldehyde groups. The reaction is shown in Figure 16 by way of example for an aldehyde-modified polythioethersulfone which can be prepared from lithiated polythioethersulfone by reaction with N ₅ N-dimethylformamide (DMF) ⁴⁵ . It was likewise surprising that polymers which carry keto groups (preparable, for example, according to ⁴⁶ ) can also be modified with 1-hydroxymethylene-1,1-bisphosphonic acid groups by this method. An example of such a reaction is given in Figure 17.

⁴⁴ YL Xie, Q. Zliu, XR Qin, YY Xie, Chinese Chemical Letters 2003, 14 (1), 25-28

⁴⁵ MD Guiver, H. Zhang, GP Robertson, Y. Dai, Jonmal of Polymer Science, Part A: Polymer Chemistry 2001, 39, 675-682

⁴⁶ J. Kerres, A. Ullrich, T. Haring, US Patent 6,590,067; granted at 8.7.2003; European Patent EP 105 433 B1; granted at 27-10-2004 In principle, all common polymers can be used as polymers having the functional groups listed in item 1. The following polymers are preferred here:

Polyolefins such as polyethylene, polypropylene, polyisobutylene, polynorbornene,

Polymethylpentene, polyisoprene, poly (1,4-butadiene), poly (1,2-butadiene)

Styrene (co) polymers such as polystyrene, poly (methylstyrene), poly (α, ß, ß-trifluorstyiOl),

Poly (pentafluorostyrene)

Polyvinyl alcohol and its copolymers

Polyvinylphenol and its copolymers

Poly (4-vinylpyridine), poly (2-vinylpyridine) and their copolymers perfluorinated ionomers such as Nafion® or the SO ₂ Hal precursor of Nafion® (HaI = F,

Cl, Br, I), Dow® membrane, GoreSelect® membrane sulfonated PVDF and / or the SO ₂ Hal precursor, where Hal is fluorine, chlorine, bromine or iodine

(Het) aryl backbone polymers such as:

Polyether ketones such as polyether ketone PEK Victrex®, polyetheretherketone

PEEK Victrex®, polyether ketone ketone PEKK, polyetherether ketone ketone

PEEKK, polyether ketone ether ketone ketone PEKEKK Ultrapek®

Polyethersulfones such as Polysulfone Udel®, Polyphenylsulfone Radel R®,

Polyether ether sulfone Radel A®, polyethersulfone PES Victrex®

Poly (benz) imidazoles such as PBI Celazol® and others the (benz) imidazole

Building block containing oligomers and polymers, wherein the

(Benz) imidazole group may be present in the main chain or in the polymer side chain

Polyphenylene ethers such. Poly (2,6-dimethyloxyphenylene), poly (2,6-diphenyloxyphenylene)

Polyphenylene sulfide and copolymers

Poly (1,4-phenylene) or poly (1,3-phenylene), which may be in the side group with

Benzoyl, naphthoyl or o-phenyloxy-1,4-benzoyl groups, m-phenyloxy-

1,4-benzoyl groups or p-phenyloxy-l, 4-benzoyl groups. can.

Poly (benzoxazoles) and copolymers

Poly (benzthiazoles) and copolymers Poly (phtalazinone) and copolymers

Polyaniline and copolymers

In principle, all in particular all aryl main chain polymers are possible as base polymers for the polymers and polymer mixtures according to the invention. All possible block copolymers of the polymeric, in particular aryl main chain, polymers are also possible, the following types of block copolymers being preferred:

Block copolymers made up of cation exchange-group-modified blocks (-COX, POX ₂ , SO ₂ X with X = OH ₅ OMet, NR ₂ , Met = metal cation, ammonium ion, OR with R = alkyl or aryl) and from unsaturated blocks; Block copolymers composed of OH group-modified blocks and unmodified blocks;

Block copolymers composed of blocks containing basic groups and of unmodified blocks; while the choice of basic groups is not limited, but there are heterocyclic or heteroaromatic, z. For example, pyridyl, imidazolyl, benzimidazolyl or pyrazolyl groups; Block copolymers consisting of blocks modified with hydrophobic groups (for example trimethylsilyl-Si (CH ₃ ) ₃ , trifluoromethyl-CF ₃ , fluoride -F) and of 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);

Block copolymers of acidic (cation exchange group-containing) blocks and blocks containing basic groups;

Block copolymers with blocks containing OH groups and blocks containing acid groups;

Block copolymers with OH-containing blocks and blocks containing basic groups.

Any combinations of the block copolymers listed above are possible.

Particularly preferred polymer assemblies and polymers are shown in Figure 18, Figure 19, Figure 20, Figure 21, Figure 22, Figure 23, Figure 24, Figure 25, Figure 26, Figure 27, Figure 28, Figure 29, Figure 30, Figure 31, Figure 32 and Figure 33 are listed. For the phosphonation ,. Carboxylation and / or sulfonation of the polymers can be carried out using all customary processes. The main procedures are listed below:

sulfonation:

Method via metallation: first metallation (eg with n-butyllithium) ₃ then reaction with an S-electrophile (SO ₂ , SO ₃ , SOCl ₂ , SO ₂ Cl ₂ ), then optionally conversion to

Sulfonic acid (from the reaction of the lithiated polymer with SO ₂ arise Sulfmate, which can be reacted with an oxidizing agent such as H ₂ O _2, NaOCl, KMnO _4, etc. to the respective sulfonates ^47, wherein the reaction of the lithiated polymer with SO ₂ Cl ₂ arise

Sulfochlorides which are hydrolyzed with water, acids or alkalis to the corresponding sulfonic acids ⁴⁸ ).

Process via electrophilic sulfonation: reaction of the polymer with concentrated

Sulfuric acid ⁴⁹ , ⁵⁰ H ₂ SO ₄ -SO ₃ ⁵¹ , ⁵² Chlorosulfonic acid, SO ₃ -Triethylphosphat, SO ₃ -pyridine o. Other common S-electrophiles.

Other, not explicitly listed here Sulfonierungsverfahren can for the

Einfülirung the sulfonic acid group can be used.

It is also possible to use polymers according to the invention in which sulfonated

Monomers are polymerized / polycondensed, such as. In McGrath et al., ⁵³ , ⁵⁴ , ⁵⁵ .

Phosphonating

For this purpose, besides the process according to the invention for the reaction of carboxylic acid groups or carboxylic acid derivatives such as carboxylic acid chloride or carboxylic anhydride with phosphorous acid derivatives, we can use PCI ₃ , phosphorous acid, phosphorous acid esters or tris (trimethylsilyl) phosphite, the customary processes

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⁵² J. Kerres, CM. Tang, C. Graf, Ind. Eng. Chem. Res. 2004, 43 (16), 4571-4579 (available via URL: http://pubs.acs.org/cgibin/asap.cgi/iecred/asap/pdfyie030762d.pdf)

⁵³ YS Kim, F. Wang, M. Hickner, TA Zawodzinski, JE McGrath, J. Membr. Be. 2003, 212, 263

⁵⁴ WX. Harrison, F. Wang, JB Mecham, VA Bhanu, M. Hill, YS Kim, JE McGrath, J. Polym. Be, Part A: Polym. Chem. 2003, 41, 2264

⁵³ YS Kim, MA Hickner, L. Dong, BS Pivovar, JE McGrath, J. Membr. Be. 2004, 243, 317 (Phosphonation of the polymers,, or phosphonation of monomers followed by polymerization / polycondensation ¹⁴ ). The most common name reactions applicable to the phosphonation of polymers are the Michaelis-Arbusov reaction or the Michaelis-Becker reaction. Other, not explicitly listed here phosphonation can be used for the introduction of the phosphonic acid group. One possible method is the metallation of the polymer and the subsequent reaction of the metalated polymer with a halogenated phosphoric or phosphonic esters (examples: Chlorphosphorsäurediaryl ¹⁶ - or alkyl ester, 2- Bromethanphosphonsäuredialkylester, 3-dialkyl phosphonate -Brompropan etc.).

carboxylation

For the carboxylation of the polymers, all common methods can be used. Likely here are the carboxylation of polymers via lithiated intermediates, for example the lithiation of polysulfone PSU Udel or the lithiation of polyphenylene oxide with subsequent reaction of the lithiated intermediate with solid or gaseous CO ₂ ⁵⁶ ^'57 . The corresponding acid chloride can be prepared from the polymeric carboxylic acid by reaction with thionyl chloride (for further reaction with, for example, tris (timethylsilyl) phosphite to give the corresponding 1-hydroxymethylene-1,1-bisphosphonic acid). The nucleophilic substitution reaction of electron-poor halogenated aromatics with KCN and subsequent saponification of the CN group to the COOH group are also mentioned here. In addition, methyl aromatics can be reacted with potassium permanganate to the corresponding aromatic carboxylic acids, for example, the 2-, 3- or 4-methylpyridines. Aliphatic carboxylic acids are also accessible by oxidation of aliphatic alcohols or aldehydes.

⁵⁶ Guiver, MD Ph.D. Dissertation, Carletown University 19S7, Ottawa-Ontario, Canada

⁵⁷ Beihoffer, TW; Glass, JE Polymer 1986, 27, 1626-32 applications

1, Preparation of an ionically crosslinked blend of a pyridine group containing l-hydroxymethylene-l, l-bisphosphonic acid and a sulfonated

Arylene main chain polymer (general regulation)

3 g of the sulfonated Axyl main chain polymer in the SC ^ Na form are dissolved in DMSO to a 10% solution. As much of a pyridine radical-containing 1-hydroxymethylene-1,1-bisphosphonic acid in the Na ⁺ form in DMSO is dissolved in a 10% solution such that a sulfonate group of the polymer has a pyridine group of the basic 1-hydroxymethylene-1 -Bisphosphonatverbindung comes. Then the two solutions are combined. The combined solution is doctored onto a glass plate to a thin film. Thereafter, the DMSO is removed by evaporation at temperatures of 50 to 150 ⁰ C and optionally negative pressure of 800-10mbar. Thereafter, the glass plate is removed with the polymer film under water from the glass plate. The polymer film is subsequently aftertreated:

1. In oil, to 50% caustic (alkali metal such as NaOH, KOH ₅ LiOH etc., alkaline earth liquor such as Ba (OH) ₂₅ Ca (OH) ₂ , aqueous ammonia or aqueous primary, secondary or tertiary amines or quaternary ammonium salts) at temperatures from O to 10O ⁰ C for 1 to 480 hours;

2. in 0.1 to 90% mineral acid (HCl, HBr, H ₂ SO ₄ , H ₃ PO ₄ ) at temperatures of from 0 to 10O ⁰ C for 2 to 480 hours;

3. in demineralised water at temperatures from 0 to 10O ⁰ C for 2 seconds to 480 hours;

4. in 0.1 to 10 molar ZrOCl ₂ solution at temperatures from 0 to 100 ⁰ C for 2 to 480 hours;

5. in demineralized water at temperatures from 0 to 100 ° C for 2 seconds to 480 hours;

6. in 0.1 to 90% H ₃ PO ₄ at temperatures of 0 to 100 ⁰ C for 2 to 480 hours;

7. in demineralized water at temperatures from 0 to 100 ⁰ C for 2 seconds to 480 hours.

In this case, single and multiple steps of the aftertreatment can be omitted and / or the order of the aftertreatment steps can be reversed as desired. 2. Preparation of a covalently crosslinked blend of an aryl-l-hydroxymethylene-1,1-bisphosphonic acid and a polymer containing OH groups, wherein the niedermolelculare aryl-l-hydroxymethylene-l, l-bisphosphonic acid with a dialdehyde crosslinker to the polymer is bound (general requirement)

3 g of a polymer containing OH groups is dissolved in a dipolar aprotic or in a protic solvent, for example in DMSO. Thereafter, the low molecular weight aryl-l-hydroxymethylene-l, l-bisphosphonic acid is dissolved in the same solvent, either in the H form or in the Na ⁺ form. Glutaraldehyde is then added to the solution of the low molecular weight 1-hydroxymethylene-1,1-bisphosphonic acid, specifically per mole of OH groups of the low molecular weight aryl-1-hydroxymethylene-1,1-bisphosphonic acid, Vi mole of glutaraldehyde. Then the two solutions are combined. The combined solution is doctored onto a glass plate to a thin film. Thereafter, the DMSO at temperatures of 50 to 150 ⁰ C and optionally reduced pressure of 800-1 Ombar removed by evaporation. Thereafter, the glass plate is removed with the polymer film under water from the glass plate. The polymer film is aftertreated as follows:

1. In oil, to 50% caustic (alkali, such as NaOH, KOH, LiOH etc., alkaline earth liquor such as Ba (OH) ₂₅ Ca (OH) ₂ , aqueous ammonia or aqueous primary, secondary or tertiary amines or quaternary ammonium salts) at temperatures from 0 to 100 ° C for 1 to 480 hours;

3. in demineralized water at temperatures from 0 to 100 ⁰ C for 2 seconds to 480 hours;

4. in 0.1 to 10 molar ZrOCl ₂ solution at temperatures from 0 to 100 ° C for 2 to 480 hours;

6. in 0, 1 to 90% H ₃ PO ₄ at temperatures of 0 to 100 ° C for 2 to 480 hours;

In this case, single and multiple steps of the aftertreatment can be omitted and / or the order of the aftertreatment steps can be reversed as desired. 3. Preparation of a l ~ hydroxymethylene-l, l-bisphosphonic ~ groups modified polymer from a polymeric acid chloride using the example of PSU Udel

Carboxylated PSU with 2 carboxylic acid groups per repeat unit is prepared after ^5δ . To prepare the PSU diacid chloride, the PSU dicarboxylic acid is dissolved in a 9-fold excess of thionyl chloride, based on the mass of the polymer. A small amount of N, N-dimethylformamide is added to this mixture and refluxed for 72 hours. The PSU diacid chloride is precipitated in a large excess of isopropanol and excess thionyl chloride is washed out. The PSU-di-acid chloride is dried to zw constant weight. Thereafter, 10 g of the PSU diacid chloride are dissolved in 1000 ml of anhydrous tetrahydrofuran (THF) and charged into a previously silylated, dried 2000 ml glass flask under argon. Cool to -78 ° C under argon. Thereafter, with vigorous stirring, tris (trimethylsilyl) phosphite (per milliequivalent of acid chloride 1 millimole of tris (trimethylsilyl) phosphite) is injected via a septum. The mixture is stirred at this temperature for 2 hours and then allowed to warm slowly to -10 ° C. Thereafter, a 10-fold excess of methanol (to 1 millimole of tris (trimethylsilyl) phosphite 20 millimoles of methanol) is added to the polymer to hydrolyze the silyl ester. The reaction solution is concentrated to 1/10 of the original volume by evaporating off THF and then the polymer precipitates in 1 l 1 molar HCl. The polymer precipitate is filtered off, washed with 1 molar HCl and taken up in 250 ml of water. The aqueous mixture of the polymer is then dialyzed by dialysis tubing. Thereafter, the water of the dialyzate is evaporated and the polymer is dried over P ₄ O ₁₀ to constant weight under oil pump vacuum.

Claims

claims

Blends and blend membranes of low molecular weight hydroxymethylene-oligo-phosphonic acids RC (PO ₃ H ₂ ) x (OH) _y and polymers, characterized in that the radical R is any organic radical and that the polymers contain the following functional groups:

Cation exchange groups or their nonionic precursors of the type ^' .

SO ₂ X, X = Hal ₅ OH ₅ QMe, NR ₁ R ₂ , ORj with Me = any metal cation, transition metal cation such as ZrO ²⁺ or TiO ²⁺ or ammonium cation, R ₁ , R ₂ = H or any aryl or alkyl radical,

POX ₂

COX and / or

OH groups

Blends and blend membranes of low molecular weight hydroxymethylene-oligophosphonic acids RC (PO ₃ H ₂ ) _x (OH) _y and polymers according to claim 1, characterized in that x = 2 and y = l.

Blends and blend membranes of low molecular weight hydroxymethylene-oligophosphonic RC (PO ₃ H ₂ ) ₂ (OH) i and polymers according to claims 1 and 2, characterized in that the low molecular weight 1-hydroxymethylene-l, l-bis-phosphonic acids are produced from carboxylic acids by reaction with PC1 ₃ / H ₃ PO ₃ and subsequent hydrolysis with H ₂ O or by reaction of carbonyl chlorides or carboxylic anhydrides with tris (trimethylsilyl phosphite) with subsequent hydrolysis by means of methanol.

Blends and blend membranes of low molecular weight hydroxymethylene-oligophosphonic RC (PO ₃ H ₂ ) ₂ (OH) i and polymers according to claims 1 to 3, characterized in that the radical R of Hydroxymethylen- Oligophosphonsäure contains an aliphatic or aromatic basic group, which enters into an ionic interaction with the acidic groups of the polymer or the polymer mixture.

5. Blends and blend membranes of low molecular weight hydraxymethylene oligo-

Phosphonic acids RC (PO ₃ H ₂ ) ₂ (OH) ₁ and polymers according to claim 4, characterized in that the aliphatic or aromatic basic grouping. R of the hydroxymethylene-oligophosphonic acid is selected from primary, secondary or tertiary basic amino groups or from quaternary ammonium salts or from imidazole groups or from pyrazole groups or from pyridyl radicals or from other basic heterocyclic or heteroaromatic radicals

6. blends and blend membranes of low molecular weight hydroxymethylene-oligophosphonic RC (PO ₃ H ₂ ) ₂ (OH) i and polymers according to claims 1 to 4, characterized in that the OH group of the low molecular weight 1-hydroxymethylene-l, l Bisphosphonic acid is crosslinked covalently with OH groups of other low molecular weight l-hydroxymethylene-l, l-bisphosphonic acid molecules and optionally with OH groups of the polymer.

7. Blends and Blendmembranen of low molecular weight hydroxymethylene-oligophosphonic RC (PO ₃ H ₂ ) ₂ (OH) i and polymers according to claim 5, characterized in that the following compounds are used as a covalent crosslinker, optionally in admixture with each other: (a ) Crosslinking by addition of AgNO ₃ to the OH group-containing mixture of l-hydroxymethylene-l, l-bisphosphonic acid and optionally OH-containing polymer under hydrothermal conditions and reduction of AgNO ₃ to elemental silver nanoparticles and release of HNO ₃ ; (B) crosslinking of l-hydroxymethylene-l, l-bisphosphonic acids with OH-containing polymers. Use of epichlorohydrin as crosslinker; (c) crosslinking of the OH groups of the 1-hydroxymethylene-1,1-bisphosphonic acids and optionally the OH groups of the polymer with glutaraldehyde or other dialdehydes; (D) Crosslinking of the OH groups of the l-hydroxymethylene-l, l-bisphosphonic acids and optionally the OH groups of the polymer with melamine-formaldehyde crosslinkers; (e) crosslinking of the OH groups of the l-hydroxymetibylene-1,1-bisphosphonic acids and optionally of the OH groups of the polymer after reaction of the OH groups with cinnamic acid chloride by photocrosslinking (cycloaddition) under the action of UV light; (F) crosslinking by reaction of the OH groups of the low molecular weight l-hydroxymethylene-1,1-bisphosphonic acid and optionally the OH groups of the polymer with ot, co-. Dihaloalkanes or dihaloaromatics Hal-R-Hal with Hal = F, Cl, Br, I, optionally with the addition of a deprotonating agent for the OH groups.

8. Polymers modified with the 1-hydroxymethylene-1,1-bisphosphonic acid group, characterized in that they are prepared by reaction of polymers containing carboxylic acid groups or carboxylic acid halide groups - COHal (HaI = F, Cl, Br, I) with phosphite compounds Claim 3 or by reaction of polymeric aldehydes with phosphorous acid esters under amine catalysis, with oxidation of the intermediate hydroxyphosphonic acid with MnO ₂ or another oxidizing agent.

9. Polymers modified according to claim 8 with the l-hydroxymethylene-1,1-bisphosphonic acid group, characterized in that the following polymers are preferred as base polymers: polyolefins, such as polyethylene, polypropylene, polyisobutylene, polynorbornene, polymethylpentene, polyisoprene, poly (1, 4) butadiene), poly (1, 2-butadiene), styrene (co) ρolymere such as polystyrene, poly (methyl styrene), poly _(α? ß, ß-trifluorostyrene) ₅ poly (pentafluorostyrene), polyvinyl alcohol and its copolymers, polyvinyl phenol and its copolymers , Poly (4-vinyl-pyridine), poly (2-vinylpyridine) and their copolymers, perfluorinated ionomers such as Nation® or the SO ₂ Hal precursor of Nation® (HaI = F, Cl, Br, I), Dow® membrane, GoreSelect® membrane, sulfonated PVDF and / or the SO ₂ Hal precursor, where Hal is fluorine, chlorine, bromine or iodine, (Het) aryl main chain polymers such as polyether ketones such as polyether ketone PEK Victrex®, polyether ether ketone PEEK Victrex®, polyether ketone ketone PEKK, polyether ether ketone ketone PEEKK, Polyether ketone ether ketone acetone PEKEKK Ultrapek®, polyethersulfones such as phenyl sulfone Udel®, polyphenylsulfone Radel R®, polyether ether sulfone Radel A®, polyethersulfone PES Victrex®, poly (benz) imidazoles such as PBI Gelazol® and other oligomers and polymers containing the (benz) imidazole building block, where the (benz) imidazole group may be present in the main chain or • in the polymer side chain, polyphenylene etfine such as. Poly (2;, 6-dimethyloxyphenylene), poly (2,6-diphenyloxyphenylene),

Polyphenylene sulfide and copolymers, poly (1, 4-phenylene) or poly (1, 3-phenylene), which in the side group optionally with benzoyl, naphthoyl or o-phenyloxy-1,4-benzoyl groups, m-phenyloxy-l , 4-benzoyl groups or p-phenyloxy-1,4-benzoyl groups, poly (benzoxazoles) and copolymers, poly (benzthiazoles) and copolymers, poly (phtalazinones) and copolymers; Polyaniline and copolymers. In principle, all in particular all aryl main chain polymers are possible as base polymers for the inventive polymers and polymer blends. All possible block copolymers of the polymeric, in particular aryl main chain, polymers are also possible, the following types of block copolymers being preferred: block copolymers consisting of 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 are made up of unmodified blocks; Block copolymers composed of OH group-modified blocks and of unmodified blocks; Block copolymers composed of blocks containing basic groups and of unmodified blocks; In this case, the choice of basic groups is not limited, but there are heterocyclic, or heteroaromatic, z. For example, pyridyl, imidazolyl, benzimidazolyl or pyrazolyl groups; Block copolymers consisting of blocks modified with hydrophobic groups (eg trimethylsilyl-Si (CH ₃ ) ₃ , trifluoromethyl-CF ₃ , fluoride -F) and of 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); Block copolymers of ^'acid (cation exchange groups-containing) blocks and basic groups containing blocks; Block copolymers with OH-containing blocks and acid group-containing blocks; Block copolymers containing blocks containing OH groups and blocks containing basic groups. Any combinations of the block copolymers listed above are possible.

10. A process for producing an ionically crosslinked blend from a

Pyridine group-containing 1-hydroxymethylene-l ₃ l-bisphosphonic acid and a sulfonated Arylhauptkettenpolymer according to claims 1 to 9, characterized in that the sulfonated aryl main chain polymer in the salt form in a dipolar aprotic solvent such as DMSO is dissolved to a 1 to 20% solutionj a basic group containing 1-hydroxymethylene-l, l-bisphosphonic acid in the Na ⁺ form is dissolved in a dipolar aprotic solvent such as DMSO to a 1 to 20% solution, the two solutions are then combined, the combined solution a glass plate is doctored into a thin film, the solvent is removed by evaporation at temperatures of 50 to 150 ° C and optionally reduced pressure of 800- lmbar, the glass plate is dissolved with the polymer film under water from the glass plate, and the resulting polymer film is aftertreated as follows is (a) in 01, to 50% lye (alkali such as NaOH, KOH, LiOH etc ., Alkaline earth liquor such as Ba (OH) ₂₅ Ca (OH) ₂ , aqueous ammonia or aqueous primary, secondary or tertiary amines or quaternary ammonium salts) at temperatures of 0 to 100 ⁰ C for 1 to 480 hours; (b) in 0.1 to 90% mineral acid (HCl, HBr, H ₂ SO ₄ , H ₃ PO ₄ ) at temperatures of 0 to 100 ^° C. for 2 to 480 hours; (c) in deionized water at temperatures from 0 to 100 ° C for 2 seconds to 480 hours; (d) in 0.1 to 10 molar ZrOCl ₂ solution at temperatures of 0 to 100 ⁰ C for 2 to 480 hours; (e) in demineralized water at temperatures of 0 to 100 ° C for 2 seconds to 480 hours; (f) in O ₅ I to 90% H ₃ PO ₄ at temperatures from 0 to 100 ^° C. for 2 to 480 hours; (g) in demineralized water at temperatures from 0 to 100 ° C for 2 seconds to 480 hours. In this case, single and multiple steps of the aftertreatment can be omitted and / or the order of the aftertreatment steps can be reversed as desired.

11. A process for the preparation of a covalently crosslinked blend of an aryl-1-hydroxymetbylene-1, 1-bisphosphonic acid and a polymer containing .OH groups according to claims 1 to 9, characterized in that the polymer, the contains OH groups, aprotic dipolar-in or is dissolved in a proti ^'scheή solvent, for example in DMSO, the low molecular weight aryl-l-hydroxymethylene-l, l-bisphosphonic acid in the same solvent is resolved, either in the H form or in the Na ⁺ form, the crosslinker, such as glutaraldehyde, is added to the solution of the low molecular weight l-hydroxymethylene-l, l-bisphosphonic acid, the two solutions are combined, the combined solution is doctored on a glass plate to a thin film, the Solvent is removed by evaporation at temperatures of 50 to 150 ⁰ C and optionally negative pressure of 800- lmbar, the glass plate with the polymer film under water from the glass plate abgelö st., and the polymer film is aftertreated as follows: (a) in 01 to 50% caustic (caustic such as NaOH ₃ KOH, LiOH, etc., alkaline earth caustic such as Ba (OH) ₂₅ Ca (OH) ₂ , aqueous ammonia or aqueous primary , secondary or tertiary amines or quaternary ammonium salts) at temperatures of 0 to 100 ⁰ C for 1 to 480 hours; (b) in 0.1 to 90% mineral acid (HCl, HBr, H ₂ SO ₄ , H ₃ PO ₄ ) at temperatures of 0 to 100 ^° C. for 2 to 480 hours; (c) in deionized water at temperatures from 0 to 100 ° C for 2 seconds to 480 hours; (d) in 0.1 to 10 molar ZrOCl ₂ solution at temperatures of 0 to 100 ° C for 2 to 480 hours; (e) in demineralized water at temperatures of 0 to 100 ^° C. for 2 seconds to 480 hours; (f) in 0.1 to 90% H ₃ PO ₄ at temperatures from 0 to 100 ° C for 2 to 480 hours; (g) in demineralized water at temperatures from 0 to 100 ⁰ C for 2 seconds to 480 hours. In this case, single and multiple steps of the aftertreatment can be omitted and / or the order of the aftertreatment steps can be reversed as desired.

12. A process for the preparation of a polymer with l-hydroxymethylene-1,1-bisphosphonic acid groups from carboxylated polymers according to claims 8 and 9, characterized in that the carboxylic acid groups of the carboxylated polymer with thionyl chloride to carboxylic acid chloride groups after which the polymeric acid chloride in an ethereal solvent, for example THF or diethyl ether, is dissolved to a 0.1 to 5% solution and charged to a pre-silylated, dried 2000 ml glass flask under argon, under argon to 0 ^° C is cooled down to -78 ° C, then with vigorous stirring tris (trimethylsilyl) phosphite (per milliequivalent acid chloride 1 millimole of tris (trimethylsilyl) phosphite) is injected through a septum, stirred at this temperature for 1 minute to 2 hours and optionally to -1O ⁰ C is then heated, then the silyl ester is hydrolyzed by addition of methanol, then the reaction solution is concentrated to 1/10 of the original volume by rotary evaporation of THF, and then the polymer is precipitated in 1-molar HCl, the polymer precipitate is filtered off, with 1 molar HCl and then taken up in water, the aqueous mixture of the polymer by dialysis is dialyzed, the water of the dialysate is evaporated, and finally the polymer is dried over P ₄ O _1O to _constant weight under oil pump vacuum.

13. Use of the membranes according to claims 1 to 12 for the production of energy by electrochemical means.

14. Use of the membranes according to claims 1 to 12 as a component of Membranbrenαstoffzellen (H ₂ - or direct methanol fuel cells) at

Temperatures from -20 to + 180 ° C.

15. Use of the membranes according to claims 1 to 12 in electrochemical cells.

16. Use of the membranes according to claims 1 to 12 in secondary batteries.

17. Use of the membranes according to claims 1 to 12 in electrolysis cells.

18. Use of the membranes according to claims 1 to 12. in membrane trimer processes such as gas separation, pervaporation, perstraction, reverse osmosis, electrodialysis, and diffusion dialysis.

19. A polymer or membrane prepared according to at least one of claims 1 to 12.