CZ2008809A3 - Polymeric aliphatic ion-exchange materials and method of using the same - Google Patents

Abstract

The present invention relates to polymeric ion exchange materials based on copolymers of phosphonic acids (I) and diphosphonic acids (II) with an unsaturated polymerizable bond C = C or a derivative thereof containing an unsaturated polymerizable bond C = C and a monomer or multiple polymerizable C = C linkages selected from the group of vinylhalogen , vinylidene halogen, vinyl ester, vinyl lactam, acrylic acid and methacrylic acid, their halogenated derivative, acrylic and methacrylic acid nitrile and nitrile derivatives thereof and halogenated derivatives thereof. The materials of the present invention are intended for the preparation of homogeneous and heterogeneous membranes for use in membrane fuel cells and other ion exchange materials and processes.

Description

1 (Polymeric aliphatic ion exchange materials and methods of their use

Field of technology

The present invention relates to polymeric aliphatic ion exchange and ionically conductive materials and methods for their use.

j State of the art

Ion exchange membranes are currently used on a laboratory and industrial scale. The most important applications include electrochemical desalination of seawater and brackish water, separation of electrolytes from non-electrolytes, cleaning of pharmaceutical preparations such as solid electrolytes and use in other processes,

Ion exchange membranes are currently produced either as homogeneous membranes, which are single-phase ion exchange systems, or as heterogeneous membranes, which consist of a dispersion of ion exchange particles in a hydrophobic polymeric binder (J. Membr. Sci. 250 (2005) 151). Most current cation exchange membranes are prepared from polymers bearing sulfo groups, phospho groups,

Karboxy5 carboxy groups or other water-dissociable acid groups in the rtf 'side chains (J. Membr. Sci. 259, (2005) 10). These membranes are ionically conductive in the hydrated state, i.e. after dissociation of the acidic functional group. Nowadays, most often like

IK membrane polymer electrolytes in fuel cells operating below the boiling point

These waters use perfluorinated homogeneous membranes (U.S. Pat. No. 6,692,569). These are characterized by high ionic conductivity, suitable water sorption (absorbency), good

Mechanical properties and exceptional oxidation resistance during operation in

- 23 fuel cell. Oxidation leads to embrittlement of the membrane electrolyte and possibilities

- 23 membrane rupture and also to reduce fuel cell performance (J. Membr. Sci. 243,

- 24 (2004) 327). As an alternative to these perfluorinated materials, partially fluorinated ion exchange materials (U.S. Pat. No. 5,422,411) and non-fluorinated materials are used and developed.

polymeric ion exchange materials. The most important of these are sulfonated aromatic polymers based on sulfonated poly (ether ketone) (DE 4219077) sulfonated poly (sulfone) (J. Membr. Sci. 83, (1993) 211) sulfonated poly (phenylene sulfides) (Patent DE 19527435) .

These materials are often characterized by very low oxidation resistance when operating in a fuel cell (oxidative stability) and high methanol permeability when used in a fuel cell.

-2direct methanol fuel cells (Chem. Mater. 8, (1996) 610). The advantage of polymeric ion exchange and ionically conductive materials based on aliphatic copolymers of phosphonic and diphosphonic acids and their derivatives containing the polymerizable OC bond according to the invention over aromatic sulfonated polymers is their increased oxidation resistance, their good mechanical properties and excellent resistance to thermal degradation. The disadvantage of low-temperature fuel cells (operating below the boiling point of water) is that near the boiling point of water, the membrane dries out and loses ionic conductivity. Polymeric membrane fuel cells operating above the boiling point of water, 100 ° C - 200 ° C (medium temperature fuel cells) use basic polymers doped with mineral acids as electrolytes. These are mainly poly (benzimidazole) and its derivatives doped with phosphoric acid, which ionically conduct at temperatures above 100 ^Q C. (Patent WO 096/13872). The advantage of medium-temperature fuel cells is their higher tolerance to possible catalytic poisons in the fuel (J. Appl. Elchem. 31, (2001) 773), especially carbon monoxide, high-potential heat gain and higher cell performance. They do not need to moisturize the fuel and oxidant. However, their disadvantage is the leaching of phosphoric acid from the membrane by the water formed by the reaction in the fuel cell, especially when starting and stopping the fuel cell. To increase ionic conductivity, ionically conductive fillers are commonly added to membranes. These are, for example, sulphates, phosphates, zeolites and heteropolyacids (J. Membr. Sci. 226, (2003) 169). Prior art reports the preparation of phosphonic acid-based ion-exchange polymeric polymeric materials by mixing a polymer with phosphonic acid-containing vinyl, preparing a two-dimensional structure (membrane) on a support, and then polymerizing vinyl-containing phosphonic acids (Patent US2005147859) or plasma polymerized vinylphosphonic acid on PTFE. carriers to obtain a graft copolymer (Chemical Engineering Communications 190, (2003) 1085). The materials prepared in this way are heterogeneous at the macro or micro level. These are interpolymers or graft copolymers. Prior art also reports the preparation of ion-exchange polymeric materials based on phosphonic acids containing vinyl by mixing poly (vinylphosphonic acid) with nitrogenous herocyclic compounds, such as imidazole (Polymer 45 (2005) 2986). However, this system is water soluble and therefore unsuitable for low temperature fuel cells. Copolymerization of vinyl-containing phosphonic acids with water-soluble monomers yields a water-soluble copolymer (Solid State Ionics 164, (2003) 169). This solution has the disadvantage of the solubility of this system in water, so it is unsuitable for low-temperature fuel cells. The water-soluble ion exchange polymer is suitable for the preparation of solid

-3 ⁶ ?

τ of electrolyte only after crosslinking in the form of a membrane. Current scientific and technical knowledge indicates the preparation of random copolymers of vinylphosphonic acid esters with styrene, which, however, have poor mechanical properties and are almost ionically non-conductive after hydrolysis (J. Appl. Polym. Sci. 74 (1999) 83). Prior art does not disclose the preparation of ionically conductive polymers based on ungrafted, random copolymers or polymer blends of which at least one polymer carries phospho groups as substituents on the backbone or side chain that would be soluble without the use of a multifunctional comonomer, film-forming from a polymer solution, they were highly ionically conductive, had good mechanical properties, had high oxidative stability to radicals, and were useful in applications for ion exchange materials, especially as electrolytes in fuel cells.

-4 Summary of the Invention

The present invention relates to polymeric aliphatic ion exchange materials based on copolymers of phosphonic and diphosphonic acids and their derivatives containing a polymerizable C = C bond which are conductive to ions, either directly or after chemical treatment, which usually involves reesterification and subsequent hydrolysis, or by direct hydrolysis. hydrolysis of the phosphonic or diphosphonic acid ester or amide. The materials of the present invention are intended for the preparation of homogeneous and heterogeneous membranes and for use in membrane fuel cells and other processes using ion exchange materials. Their essence lies in the fact that they consist of polymers bearing phospho groups as substituents on the main chain or in the side chain. The preparation of the material according to the present invention consists of solution, emulsion, suspension or block polymerization of phosphonic acid (I) or diphosphonic acid (II) or their derivatives containing a polymerizable bond of type C = C,

R; R ₃ R c = cc = cr ₂ PO ₃ R ₄ R ₅ r ₇ PO ₃ R ₄ R ₅ (1) (Π) where R 1 is a substituent from the group (-H, -F, -Cl, -Br,) ,

R ₂ is a substituent from the group (-H, -F 3),

R 1 is a substituent from the group (-H, -F, -Cl, -Br, -I, -COOR 9 -COCl, CON R 1 R 8), R 4 is a substituent from the group (-H, substituted alkyl, -unsubstituted alkyl, substituted aryl , -unsubstituted aryl),

R ₅ is a substituent from the group (-H, -substituted alkyl, -unsubstituted alkyl, substituted aryl, -unsubstituted aryl),

Re is a substituent from the group (-H, -F),

R7 is a substituent from the group (-H, -F),

R e is a substituent from the group (-H, -substituted alkyl, -unsubstituted alkyl, substituted aryl, -unsubstituted aryl) with another comonomer containing a polymerizable C = C bond. For the preparation of the material according to the present invention it can be used as a phosphonic acid derivative (I) or diphosphonic acid (II) containing a polymerizable C = C bond, also any inorganic or organic salt thereof or chlorides or fluorides.

-5 of these acids. Acrylates, methacrylates, branched vinyl esters, acrylonitrile, methacrylonitrile, vinyl halides, vinyl idene halides can be used as comonomers, but this group of comonomers is not limited. The use of acrylonitrile and methacrylonitrile is particularly preferred. When using monomers containing more polymerizable unsaturated bonds in a polymerization mixture containing 0.1 mol. - 10 mol. % and higher, branched or crosslinked usually insoluble products are obtained. Due to their insolubility, such systems must be polymerized in the form in which the final polymer will be. The polymerization can be carried out in the form of a thin film, in which the material is prepared and processed into a membrane in one step. Chemical radical initiators, UV radiation, photoinitiators, electron beam, electrochemical initiation, and other conventional polymerization initiation methods can be used as polymerization initiators. Polar solvents such as dimethyl sulfoxide (DMSO), dimethylformamide (DMF), dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), N-methylimidazole (NMI), phosphoric acid (H3PO4) and other solvents in which the resulting polymer dissolves can be used as solvents. . The use of non-toxic DMSO and H 3 PO 4 is particularly preferred. Solvent-precipitant mixtures may also be used in such a ratio that the resulting polymer is soluble in such a mixture. The use of a polar solvent-water mixture with a water content of up to 10% is preferred. The use of water in a content of 3-7% is particularly advantageous, since some salts of phosphonic and diphosphonic acids are dissolved in such a mixture. Polar substituted hydrocarbons, such as aliphatic lower alcohols, or ketones and other solvents in which the resulting polymer does not dissolve, can be used as the solvent for the precipitation polymerization. It is particularly advantageous to use water in an amount of more than 15 times that of acrylonitrile, since acrylonitrile is soluble in such an amount of water. Isolation of the polymer from solution can be accomplished by evaporating the solvent, or by precipitating the polymer in a precipitant in the case of solution polymerization. In the case of precipitation polymerization, the polymer is obtained by filtration or evaporation of the solvent (precipitant). The process for preparing polymeric membranes consists in dissolving the polymer according to the invention bearing phospho groups as substituents on the main chain or in the side chain, pouring the film solution on an inert support, evaporating the solvent and removing the membrane from the inert support. Another method of preparing polymeric membranes consists in dissolving a homopolymer or copolymer bearing phospho groups and prepared according to the invention in a solvent for the polymer and mixing with an ionically non-conductive polymer dissolved in the same solvent as the ionically conductive polymer, mixing solutions and casting the resulting solution in in the form of a film on an inert support, evaporating the solvent and removing the resulting membrane from the inert support. Another method of preparing polymeric membranes consists in dispersing ground ionically conductive particles with a size of 1 to 100 μm, preferably 20 - 80 μm, into an ionically non-conductive polymer above the melting point of the ionically non-conductive polymer and subsequent pressing, injection, calendering or other conventional polymer processing technology. . It is preferred that the content of u in the membrane is between 40 wt. % - 75 wt. %. The material of the invention may also be processed by other conventional polymer processing techniques. Material processing is not limited to membrane processing. Another possible example is processing into spherical particles with a size of micrometers to millimeters for use as ion exchange resins. The following is a list of examples of the preparation of the material and its processing according to the invention, without being limited to these examples.

156 Examples of embodiments of the invention

Example 1

A polymerization mixture was prepared consisting of 12.04 g of vinylphosphonic acid with a purity of 84.9% (0.095 mol), 18.07 g (0.34 mol) of acrylonitrile 0.2015 g (0.001227 mol), initiator 2.2 azobis (2-methylpropionitrile) and 70.00 g (0.90 mol) of dimethyl sulfoxide (DMSO). The mixture was deoxygenated by bubbling in inert gas for 10 minutes, sealed and polymerized at 70 ° C for 5 hours. Subsequently, the mixture was diluted with 50 g of DMSO and the polymer was precipitated in 2 l of ethanol with stirring. The polymer was filtered off and washed with 4 x 0.5 liters of ethanol for 4 x 0.5 hours with stirring. The polymer was dried at 25 ° C at atmospheric pressure to constant weight. For elemental analysis, a zDMF membrane was prepared, which was dried at atmospheric pressure at 70 ° C and dried at atmospheric pressure at 160 ° C for 0.5 hour. Elemental analysis of the polymer in the H ⁺ phase: C: 55.53 wt. %, H: 6.10 wt. %, N: 18.61 wt., P: 5.04 wt. %. The ion exchange capacity of the polymer according to the content of phosphorus is 3.25 meq / g.

171 Example 2

1 (72 A polymerization mixture was prepared consisting of 15.00 g (0.064 mol) of bis (2173 chloroethyl vinyl phosphonate) and 15.00 g (0.15 mol) of methyl methacrylate, 0.1078 g (0.0006565 174 mol) of initiator 2, 2'-azobis (2-methylpropionitrile) and 60.00 g (0.82 mol) of 1175 dimethylformamide (DMF) The mixture was deoxygenated by bubbling in inert gas for 10 minutes, sealed and polymerized at 70 ° C for 13 minutes. The polymer was precipitated in 2 liters of demineralized water, the polymer was filtered and washed with 4 x 178 0.5 liters of demineralized water for 4 x 0.5 hours with stirring, and the polymer was dried at 25 ° C under atmospheric pressure until For elemental analysis, a DMF membrane was prepared, which was dried at atmospheric pressure 181 at 70 ° C and dried at atmospheric pressure at 160 ° C for 0.5 182 hours. : 51.45 wt.%, H: 7.22 wt.%, P: 183 3.82 wt.%, Cl: 7.79 wt.%.

and

184 Example 3

185 A polymerization mixture was prepared consisting of 3.08 g of vinylphosphonic acid with a purity of 84.9% (0.024 mol), 3.05 g of methyl methacrylate (0.030 mol), 0.0507 g (0.0003088

-8 mol) of 2,2'-azobis (2-methylpropionitrile) initiator and 100.00 g of 85% phosphoric acid of pa purity (0.87 mol). The mixture was deoxygenated by bubbling for 10 min. inert gas, sealed and polymerized at 80 ° C for 16 hours. The polymer is precipitated in 2 liters of demineralized water. The polymer was filtered off and washed with 4 x 0.5 liters of demineralized water for 4 x 0.5 hours with stirring. The polymer was dried at 25 ° C at atmospheric pressure to constant weight. For elemental analysis, a DMF membrane was prepared, which was dried at atmospheric pressure at 70 ° C and dried at atmospheric pressure at 160 ° C for 0.5 hour. Elemental analysis of the polymer in the H ⁺ phase: C: 58.28 wt. %, H: 7.94 wt. %, P: 0.78 wt. %. The ion exchange capacity of the polymer according to the phosphorus content is 0.50 meq / g.

198 Example 4

A polymerization mixture was prepared consisting of 4.10 g (0.015 mol) tetrasodium (ethene-1,1-diyl) bisphosphonate, 6.00 g (0.11 mol) acrylonitrile, 0.2068 g (0.001259 mol) initiator 2,2'-azobis (2-methylpropionitrile) and 30.00 g of 85% phosphoric acid (0.26 mol). The mixture was deoxygenated by bubbling for 10 min. inert gas, sealed and polymerized at 70 ° C for 3 hours. The polymer is precipitated in 2 liters of demineralized water. The polymer was filtered and washed with 4 x 0.5 liters of demineralized water for 4 x 0.5 hours with stirring. The polymer was dried at 25 ° C at atmospheric pressure to constant weight. For elemental analysis, a DMF membrane was prepared, which was dried at atmospheric pressure at 70 ° C and dried at atmospheric pressure at 160 ° C for 0.5 hour. Elemental analysis of the polymer in the H ⁺ phase: C: 59.64 wt. %, H: 5.65 wt. %, N: 21.49 wt. %, P: 3.31 wt. %. The ion exchange capacity of the polymer according to the phosphorus content is 2.13 meq / g.

212 Example 5> 13 A polymerization mixture was prepared consisting of 9.04 g (0.071 mol) of vinylphosphonic acid> 14 with a purity of 84.9%, 6.01 g (0.090 mol) of methacrylonitrile, 0.2041 g (0.001243 mol ) 215 2,2'-azobis (2-methylpropionitrile) initiator and 30.00 g (0.41 mol) of dimethylformamide 216 (DMF). The mixture was deoxygenated by bubbling for 10 min. inert gas, airtight SI 7 sealed and polymerized at 70 ° C for 6 hours. The polymer was precipitated in 2 liters of a 1: 1 mixture of butan-1-ol / diethyl ether. The polymer was filtered and washed with 4 x 0.25 liters of mixture

-9-butan-1-ol / diethyl ether 1: 1 for 4 x 0.5 hours with stirring. The polymer was dried at 25 ° C at atmospheric pressure to constant weight. For elemental analysis, a DMF membrane was prepared, which was dried at atmospheric pressure at 70 ° C and dried at atmospheric pressure at 160 ° C for 0.5 hour. Elemental analysis of the polymer in the H ⁺ phase: C: 59.19 wt. %, H: 7.25 wt. %, N: 15.75 wt. %, P: 6.19 wt. %. The ion exchange capacity of the polymer according to the content of phosphorus is 4.00 meq / g.

Example 6

A polymerization mixture was prepared consisting of 10.23 g (0.080 mol) of vinylphosphonic acid with a purity of 84.9%, 10.02 g of vinylidene chloride (0.10 mol), 0.2022 g (0.001231 mol) of 2.2 ' -azobis (2-methylpropionitrile) and 20.00 g (0.27 mol) of dimethylformamide (DMF). The mixture was deoxygenated by bubbling for 10 min. inert gas, sealed and polymerized at 70 ° C for 4 hours. Polymer precipitated in 2 liters of water. The polymer was filtered and washed with 4 x 0.5 liters of water for 4 x 0.5 hours with stirring. The polymer was dried at 25 ° C at atmospheric pressure to constant weight. A DMF membrane was prepared for elemental analysis and dried under vacuum at 70 ° C to constant weight. Elemental analysis of the polymer in the H ⁺ phase: C: 26.97 wt. %, H: 2.84 wt. %, Cl: 53.49 wt. %, P: 5.82 wt. %. The ion exchange capacity of the polymer according to the phosphorus content is 3.75 meq / g.

Example 7

A polymerization mixture was prepared consisting of 7.50 g (0.059 mol) of vinylphosphonic acid of 84.9% purity, 7.55 g of vinyl neodecanoate (0.038 mol), 0.2006 g (0.001221 mol) of 2,2'-azobis (2-methylpropionitrile) and 30.00 g (0.41 mol) of dimethylformamide (DMF). The mixture was deoxygenated by bubbling for 10 min. inert gas, sealed and polymerized at 70 ° C for 4 hours. The polymer was precipitated in 2 liters of acetonitrile / diethyl ether 9: 1. The polymer was filtered and washed with 4 x 0.25 L of acetonitrile / diethyl ether 9: 1 for 4 x 0.5 h with stirring. The polymer was dried at 25 ° C at atmospheric pressure to constant weight. For elemental analysis, a DMF membrane was prepared, which was dried at atmospheric pressure at 70 ° C and dried at atmospheric pressure at 160 ° C for 10 minutes. Elemental analysis of the polymer in the H ⁺ phase: C: 41.11 wt. %, H: 4.66 wt. %,

-ΙΟΝ; 10.71 wt. %, P: 6.19 wt. %. The ion exchange capacity of the polymer according to the phosphorus content is 4.00 meq / g.

Example 8

A polymerization mixture was prepared consisting of 5.02 g (0.039 mol) of vinylphosphonic acid with a purity of 84.9%, 5.03 g of acrylonitrile (0.094 mol), 0.0100 g (0.00006090 mol) of 2,2'-azobis (2-methylpropionitrile) and 50.00 g (1.09 mol) of ethanol. The mixture was deoxygenated by bubbling for 10 min. inert gas, sealed and polymerized at 70 ° C for 24 hours. The polymer was filtered and washed with 4 x 0.25 liters of ethanol for 4 x 0.5 hours with stirring. The polymer was dried at 25 ° C at atmospheric pressure to constant weight. For elemental analysis, a zDMF membrane was prepared, which was dried at atmospheric pressure at 70 ° C and dried at atmospheric pressure at 160 ° C for 10 minutes. Elemental analysis of the polymer in the H ⁺ phase: C: 55.67 wt. %, H: 5.94 wt. %, N: 17.93 wt. %, P: 5.46 wt. %. The ion exchange capacity of the polymer according to the phosphorus content is 3.52 meq / g.

Example 9

A polymerization mixture was prepared consisting of 5.03 g (0.039 mol) of vinylphosphonic acid with a purity of 84.9%, 5.02 g of acrylonitrile (0.095 mol), 0.0103 g (0.00006276 mol) of 2,2'-azobis (2-methylpropionitrile) and 50.00 g (0.86 mol) of acetone. The mixture was deoxygenated by bubbling for 10 min. inert gas, sealed and polymerized at 70 ° C for 24 hours. The polymer was filtered and washed with 4 x 0.25 liters of ethanol for 4 x 0.5 hours with stirring. The polymer was dried at 25 ° C at atmospheric pressure to constant weight. For elemental analysis, a zDMF membrane was prepared, which was dried at atmospheric pressure at 70 ° C and dried at atmospheric pressure at 160 ° C for 10 minutes. Elemental analysis of the polymer in the H ⁺ phase: C: 43.49 wt. %, H: 5.66 wt. %, N: 12.42 wt.%, P: 12.93 wt. %. The ion exchange capacity of the polymer according to the phosphorus content is 8.34 meq / g.

Example 10

The suspension polymerization was carried out in a polymerization mixture consisting of 5.04 g (0.022 mol) of bis (2-chloroethyl vinyl phosphonate), 5.03 g of methyl methacrylate (0.050 mol).

-11 0.3020 g (0.001323 mol) ammonium persulphate and 10.23 g (0.57 mol) water. The mixture was deoxygenated by bubbling for 10 min. inert gas, airtight and polymerized at 70 ° C for 8 hours with constant stirring with a mechanical stirrer at 700 rpm. The polymer was dried at 120 ° C at atmospheric pressure to constant weight. The polymer thus prepared was analyzed for elemental element content. Elemental analysis of the polymer in the H ⁺ phase: C: 45.50 wt. %, H: 6.38 wt. %, P: 5.50 wt. %, Cl: 14.06 wt. %.

They added

Redox initiation precipitation polymerization was performed in a polymerization mixture consisting of 5.02 g (0.039 mol) of vinylphosphonic acid 84.9% pure, 5.07 g of acrylonitrile (0.096 mol), 0.2400 g of sodium persulphate (0.001052 0.2200 g of sodium metabisulfite (0.001157 mol) and 15.00 g (8.33 mol) of water. The mixture was deoxygenated by bubbling for 10 min. inert gas, sealed and polymerized at 70 ° C for 24 hours. The polymer was filtered and washed with 2 x 0.5 liters of demineralized water for 2 x 0.5 hours with stirring. The polymer was dried at 120 ° C at atmospheric pressure to constant weight. The polymer thus prepared was analyzed for elemental element content. Elemental analysis of the polymer in the H ⁺ phase: C: 59.07 wt. %, H: 5.84 wt. %, N: 21.54 wt. %, P: 2.87 wt. %. The ion exchange capacity of the polymer according to the content of phosphorus is 1.85 meq / g.

Example 12

The photopolymerization was carried out using a polymerization mixture consisting of 5.00 g (0.039 mol) of vinylphosphonic acid with a purity of 84.9%, 5.04 g of N-vinylpynolidone (0.045 mol), 0.3002 g (0.001249 mol) of benzoin ethyl ether. 51 g of N, N'-methylene-bisacrylamide (0.0033 mol) and 6.50 g (0.066 mol) of NMP. The mixture was deoxygenated by bubbling for 10 min. inert gas, cast on a glass substrate, sealed and polymerized in the absence of air at 25 ° C for 60 minutes with UV light at a wavelength of 354 nm from a distance of 7 cm from the radiation source, through 4 mm thin glass. A Spectroline UV lamp was used as the UV radiation source. A polymer membrane was obtained which was immersed in 50% H 3 PO 4 for 1 hour, then washed with 2 x 0.5 liters of demineralized water for 2 x 0.5 hours with stirring. The obtained membrane was dried at 120 ° C at atmospheric pressure to constant weight. Results of elemental analysis of the polymer in the H ⁺ phase: C: 40.60 wt. %, H: 6.25 wt. %, N: 6.45

-12 wt. %, P; 14.32 wt. %. The ion exchange capacity of the polymer according to the phosphorus content is 9.25 meq / g.

Example 13

The water-soluble polymer was prepared from a polymerization mixture consisting of 5.05 g (0.040 mol) of vinylphosphonic acid with a purity of 84.9%, 5.02 g of N-vinylpyrrolidone (0.045 mol), 0.1002 g (0.0006102 mol) of 2 , 2'-azobis (2-methylpropionitrile) and 50.00 g (0.50 mol) of NMP. The mixture was deoxygenated by bubbling for 10 min. inert gas, sealed and polymerized at 70 ° C for 58 hours. The polymer is precipitated in 0.5 liters of acetone. The polymer was filtered and washed with 2 x 0.5 liters of acetone for 2 x 0.5 hours with stirring. The polymer was dried at 120 ° C at atmospheric pressure to constant weight. The polymer thus prepared was analyzed for elemental element content. Elemental analysis of the polymer in the H ⁺ phase: C: 36.71 wt. %, H: 6.06 wt. %, N: 4.45 wt. %, P: 18.78 wt. %. The ion exchange capacity of the polymer according to the content of phosphorus is 12.12 meq / g.

Example 14

The emulsion polymerization was carried out in a reaction mixture consisting of 10.8 g (0.085 mol) of vinylphosphonic acid with a purity of 84.9%, 90.1 g (0.90 mol) of methyl methacrylate, 8.41 g of a 24% solution of dodecylsulfonate as emulsifier 1.00 g (0.0044 mol) of ammonium persulphate initiator and 230 g (12.76 mol) of water. The mixture was deoxygenated by bubbling min with inert gas. The synthesis was performed in a reaction kettle with a volume of about 400 ml. 20% of the total water content was charged to a reaction kettle heated to 80 ° C and maintained under an inert argon atmosphere. The remaining amount of water was intensively mixed with the monomers emulsifier and 0.4 g of ammonium persulfate to form an emulsion of the monomers. 0.1 g of ammonium persulphate was added to the reaction kettle just before the monomer emulsion was metered in. The emulsion was metered in two steps, 1. metering the 10% emulsion into a reaction kettle to form a seed. After 1 hour, step 2 was dosed by gradually dropping the emulsion over a period of three hours. After the emulsion drip was completed, the remainder of the ammonium persulfate initiator was charged to the reaction kettle, and the reaction temperature was raised to 90 ° C, this phase lasted 2 h. The resulting emulsion was coagulated. The polymer was dried at room temperature. For elemental analysis, a zDMF membrane was prepared, which was dried at atmospheric pressure at 70 ° C and dried at atmospheric pressure at 70 ° C.

-13160 ° C for 10 minutes. Elemental analysis of the polymer in the H ⁺ phase: C: 61.83 wt. %, H: 8.52 wt. %, P: 0.36 wt. %. The ion exchange capacity of the polymer according to the phosphorus content is 0.21 meq / g.

Example 15

The polymer prepared according to Example 1 was dissolved in a 10% solution in dimethylformamide (DMF) and cast on glass as a thin film. The solvent was evaporated at 70 ° C and the membrane was removed by immersion in demineralized water. The ion exchange capacity of the membrane according to the phosphorus content in the polymer is 3.25 meq / g.

Example 16

The polymer prepared according to Example 1 was ground in a ball mill and passed through a 63 .mu.m sieve. The particle fraction <63 μm was isolated and 35 g of a mixture of 66% by weight polymer particles with 34% by weight LLDPE was kneaded at 150 ° C in a Brabender Tires - Corder PLE 651, at 30 rpm and for ⁵ minutes from time when the torque reached 25 Nm. Subsequently, the mixture was pressed into 0.2 mm thick films between the polyester films, using a press force of 175 kN, a temperature of 150 ° C, a two-minute preheating and a two-minute after-pressing. The area of the membrane thus prepared was 315 cm ² . The ion exchange capacity of the membrane according to the phosphorus content in the polymer is 2.15 meq / g.

He added?

The polymer prepared according to Example 1 was ground in a ball mill and a fraction <63 .mu.m was isolated using a 63 .mu.m sieve. A 10 g solution of a 12% solution of poly (isobutylene) in toluene was prepared and 1.2 g of particles <63 .mu.m of the polymer according to the invention were dispersed therein and the mixture was cast on glass. The toluene was evaporated and the membrane was removed by immersion in water. The ion exchange capacity of the membrane according to the phosphorus content of the polymer is 1.63 meq / g.

Example 18

The polymer prepared according to Example 1 was dissolved in a 10% solution in dimethylformamide (DMF). 1 gram of this solution was mixed with 1 gram of a 10% solution of polyvinylidene fluoride in DMF and cast on glass in the form of a thin film. The solvent was evaporated at atmospheric pressure at 90 ° C and the film was dried at atmospheric pressure

14pressures at 160 ° C for 0.5 hours. The membrane was removed by immersion in demineralized water, the ion exchange capacity of the membrane according to the phosphorus content in the polymer is 1.63 meq / g.

Example 19

The membrane prepared according to Example 15 weighing 1.43 g in the dry state was immersed for 2 hours at 25 ° C in 50% phosphoric acid and then removed, wiped with pulp and dried at 110 ° C to constant weight. Absorbed amount of phosphoric acid 2.83 grams.

-15Industrial applicability of ion exchange membranes are currently used on a laboratory and industrial scale. The most important applications include electrochemical desalination of seawater and brackish water, separation of electrolytes from non-electrolytes, purification of pharmaceutical preparations, such as solid electrolytes, and use in other processes. The materials of the present invention are intended for the preparation of homogeneous and heterogeneous membranes and for use in membrane fuel cells and other processes using ion exchange materials.

Claims (7)

PATENT CLAIMS Ion-conductive polymeric ion-exchange materials, characterized in that they consist of non-grafted copolymers of phosphonic acids with a polymerizable C = C bond or their derivatives with a polymerizable C = C bond, and one or more comonomers with one or more polymerizable C = C bonds. 2. The polymeric non-grafted ion-conducting ion-exchange materials according to item 1, characterized in that the polymerizable phosphonic acid comprises substances of general formula (I) and (II) or chlorides, fluorides and amides derived from these acids. 3. Ion-conductive polymeric non-grafted ion-exchange materials according to items 1 and 2, characterized in that the comonomers with one or more C = C bonds are selected from the group consisting of vinyl halides, vinylidene halides, vinyl esters, vinyllactams, acrylic and methacrylic acids, their halogen derivatives, esters, amides and acrylic and methacrylic acid nitriles and their halogen derivatives. 4. Polymeric non-grafted ion-exchange materials conductive to ions according to items 1 to 3, characterized in that they contain 1.2-28 wt. % phosphorus. 5. Polymeric non-grafted ion-exchange materials conductive to ions according to items 1 to 4, characterized in that they physically sorb phosphoric acid. 6. Use of polymeric non-grafted ion-conductive ion-exchange materials according to items 1 to 5 in fuel cells or other electrochemical and ion-exchange applications. 7. Use of polymeric non-grafted ion-conducting ion-conducting materials according to items 1 to 6 in ion exchange columns, catalytic systems or electrochemical applications.