DE19809119A1 - Preparation of polymer used for membrane in fuel cell in high yield at high speed - Google Patents

Abstract

Preparation of sulfohalogenated polymers (polymer-(SO2Hal)x) comprises reacting a solution of a metallized polymer (polymer-(Me)x) with sulfuryl halide (SO2Hal2) at -20 to -100 deg C Independent claims are included for: (i) the preparation of sulfohalogenated polymers (polymer-(SO2Hal)x(Electrophile)y) by reacting the metallized polymer with further electrophiles as well as SO2Hal2; (ii) the preparation of laminated membranes by applying a solution of the above polymer to a polymer membrane, removing solvent and hydrolyzing; (iii) a sulfohalogenated polymer made as above; and (iv) a membrane made as above.

Description

The invention relates to processes for the production of sulfohalogens nated polymers, to modify the new sulfohalogenated polymers, for the production of membranes containing the sulfochlorinated polymers, new polymers and membranes, sulfohalogenated polymers, membranes sulfohalogenated polymers, blend membranes, the sulfohalogenated poly contain mers, the sulfohalide groups optionally after the membrane position to be hydrolyzed to sulfonate groups, laminated membranes that contain at least one layer of sulfohalogenated polymer, e.g. B. bi polar membranes in which the sulfohalogenated polymer is based on anions exchanger polymer is applied, and the sulfohalogenated polymer there is hydrolyzed to the polymer containing sulfonic acid groups and Graft copolymers with sulfohalogenated polymers as macroinitiators.  

DM Vofsi, in: "The Chemistry of Suophonic Acids, Esters and their Derivati ves", Chapter 20: Polymers containing SO ₃ H and related groups, Ed .: S. Patai, Z. Rappoport, John Wiley and Sons Ltd., New York (1991) gives an overview of some ways of producing sulfohalogenated polymers. The most important manufacturing processes are briefly mentioned here:
Direct radical polymerization of vinylsulfonyl fluoride: W. Kern, R. Schultz, H. Schlessmann, Macromol. Chem. 39.1 (1960).

Simultaneous chlorination and sulfochlorination of low-density polyethylene using the Reed reaction (CF Reed, CL Horn, U.S. Patent 2,046,090 (1936) and A. Nersaian, D. Anderson, J. Appl. Polym. Sci. 6, 74 ( 1960)) under conditions such that a modified polymer with 18 Cl and an SO ₂ Cl group on 100 chains-C is formed (T. Ogawa, CS Marvel, J. Polym. Sci. 23, 1231 (1985)). Hypalon® material is commercially available from DuPont. The disadvantage of the above methods is that they are very special and only a limited number of polymers can be made by this method.

EP 0 574 791 A2 discloses a process for producing polymer electrolyte membranes based on sulfonated poly (ether ether ketone) (PEEK). It is the manufacture of sulfochlorinated PEEK from sulfonated PEEK by treatment with a chlorinating agent such as. B. PCl ₅ , SOCl ₂ described. The disadvantage of this method is that the sulfochlorinated form of the polymer must be prepared by reacting the sulfonated polymer with PCl ₅ , POCl ₃ , SOCl ₂ or similar, usually by the sulfonated polymer in an inert solvent (im Normally in a chlorinated solvent such as trichloromethane or dichloroethane) or in the sulfochlorination reagent. This procedure is very complex, dangerous and polluting because the aforementioned reagents are highly caustic and / or toxic and therefore difficult to handle, and environmentally harmful since excess sulfochlorinating agent must be neutralized, which creates large amounts of chlorides, phosphates and sulfates , and also, if necessary, chlorinated solvent must be disposed of.

The following reaction with low molecular weight components is known from the literature: H. Quast, F. Kees, Synthesis 1974, 489 (1974):

Sulfochlorination of organic compounds

It has now surprisingly been found that sulfochlorine reaction can also be carried out with dissolved, metallated polymers, without this or the solvent chemically from the sulfuryl halide be disturbed if the reaction is carried out at low temperatures (-20 to -100 ° C). All solvents are suitable as solvents in which organometallic reactions can be carried out. Typical Representatives are: ethers such as tetrahydrofuran, dioxane, glyme, diglyme, etc., or aromatic hydrocarbons such as toluene or benzene or xylene. Are there Ether preferred.

A first embodiment of the invention is given in claim 1. Preferred embodiments can be found in the related An sayings.

The metallized starting polymer can be produced in the following way:
Deprotonation of the polymer with an organometallic compound. The organometallic compound can be: alkyl lithium, aryllithium, Na organic compounds, K organic compounds, Grignard compounds, lithium diisopropylamide and other organic Li, Na and K amides. Alkyl lithium compounds are particularly preferred, among which butyl lithium is particularly preferred.

Deprotonation of the polymer with an alkali or alkaline earth metal. Be lithium is particularly preferred.

Halogen-metal exchange of a halogenated (fluorinated, chlorinated, brominated, iodinated) polymer in solution with an organometallic Compound or with an alkali metal.  

In principle, all metalized, dissolved polymers can be used as metalated polymer be used. Metallized aryl main chain poly are particularly preferred mers, including particularly preferably polyether sulfones or mixed Po ly (ether sulfone-co-ether ketone) s or polyphenylene oxides. Under the aryl head Chain polymers are particularly preferred polyether sulfones, including particular more preferably the poly (ether sulfone) Udel® from Amoco.

The metalated polymer can be reacted with sulfuryl halide (chloride, bromide, fluoride or mixed halides). It was surprisingly found that the sulfuryl halides react with high yield (80-100%) and very quickly (within seconds) with the metalated polymer to form the sulfonyl halide group -SO ₂ Hal on the polymer and that they react under certain conditions (low Temperature, -20 to -100 ° C, low polymer concentration, 0.5 to 5%) do not react with polymer carbanions still present with crosslinking according to the following reaction equation:

Polymer SO ₂ Hal + Li polymer - / → polymer SO ₂ polymer + Li⁺Hal⁻.

For this reason, in addition to the sulfuryl halide, other electrophiles (e.g. nitronium tetrafluoroborate, toluenesulfonic acid azide, alkyl halides, carbonyl compounds - in principle all electrophiles capable of reacting with the lithiated polymer) can be introduced into the solution of the metalated polymer. The various electrophiles can be added in various orders:
First addition of sulfuryl halide, then addition of the other electrophiles, which can be gaseous, liquid or solid.

First addition of the other electrophiles, which can be liquid or solid, then addition of sulfuryl halide or
Combined addition of sulfuryl halide and other (liquid or solid) electrophiles.

The particular advantage of the production process for sul fohalogenated polymers is due to the fact that the polymer after the Sul fohalogenation remains in solution and therefore subsequently by precipitation and redissolving in the solvent of all adhering impurities can be exempted. In this way, polymers can be produced that  defined content of sulfonyl halide and other organic residues exhibit.

The advantages of the production process according to the invention for polymers which contain sulfonyl halide groups can be summarized as follows:
Any polymer that forms soluble organometallic salts can be subjected to this manufacturing process.

The reaction proceeds quickly and with a high yield.

In contrast to sulfochlorinated polymers, which are obtained by chlorinating the sulfonic acid group using chlorinating agents such as PCl ₅ , POCl ₃ , SOCl ₂ etc., there are no caustic and toxic wastes that have to be neutralized and laboriously disposed of.

The sulfohalogenated polymer can be isolated because surprisingly Festge was that there is only a slight tendency to Hy drolysis with humidity or water shows. The sulfohalogenated polymer can therefore be subjected to further, defined reaction steps become.

If an aromatic deprotonated by organometallic compounds If the polymer is sulfohalogenated by this process, the sulfonyl halogens nid group usually in the part of the part which is more stable against elimination and hydrolysis Aromatic system introduced.

The sulfonyl halide group is obtained using the process according to the invention introduced very gently and safely, because the reaction at low temperatures (-20 to -100 ° C) and under protective gas. Polymer degradation and / or side reactions are therefore practically insignificant.

The polymeric sulfonic acid halides can now be subjected to all reactions which are also known from low molecular weight sulfonic acid halides:
Hydrolysis to the corresponding sulfonic acid or to the corresponding sulfonic acid salt by treatment with acid, base or water at elevated temperature. Very hydrolysis-stable poly (sulfonic acid) s or poly (sulfonates) are formed here by partial or complete reaction with amines to give sulfonamides. If diamines are used, the poly (sulfonic acid halide) can be crosslinked. Crosslinked polymers with graded hydrolysis stabilities can be produced by appropriate choice of the diamine (for the crosslinking of PEEK sulfochloride with diamines, see also EP 0 574 791 A2).

If polyamines are used, homogeneous, crosslinked interpolymers can be used re are produced, the crosslinking density by choice of sulfonyl halide content of the sulfohalogenated polymer and by choosing the Amino group content of the amino polymer varies within wide limits that can.

On the polymeric sulfonyl halide groups unsaturated compounds such. Styrenes, acrylates, methacrylates etc. are polymerized in a "living radi cal" polymerization reaction, with catalysis by CuCl / bipyridine, RuCl ₂ (PPh ₃ ) ₃ Tns (tnphenylphosphine) ruthenium (II) -di chloride) / aluminum triisopropylate or similar redox catalysts, as in M. Matsuyama, M. Kamigaito, M. Sawamoto, J. Polym. Sci. 34, 3585 (1996) for low molecular weight sulfonic acid chlorides, the polymeric sulfonyl halide having to be dissolved in a suitable solvent which does not react with the catalysts or the radicals formed. Suitable solvents are, for example, sulfolane, dialkylsulfones, aromatics such as benzene, toluene or xylene, or ethers such as THF, dioxane, glyme, diglyme etc. Graft copolymers can thus be produced from the sulfohalogenated polymers, the properties of which can be varied within wide limits by choosing the monomer to be grafted on and by varying the chain length of the side chains formed. All olefins which are capable of radical polymerization with sulfohalides can be used. Preferred are olefins from the group of acrylic compounds, styrene compounds and vinylpyridine compounds. If the olefins are acrylic acids, weakly acidic cation exchange polymers are formed, if the olefins are phosphonic acids, if cationic exchange polymers are of medium acid strength, if the olefins are 2-vinylpyridine or 4-vinylpyridine, weakly basic anion exchange polymers are formed. If the nitrogen of the vinyl pyridine units is alkylated, strongly basic anions are formed as an exchange polymer.

When trying to mix sulfohalogenated polysulfone (PSU) with unmo differentiated polysulfone and with silylated polysulfone in a common solution  It was surprisingly found that sulfohalogenated PSU with unmodified / silylated PSU forms homogeneous polymer solutions. This is surprising in that unmodified / silylated PSU with sulfonated PSU is immiscible, which is due to the phase separation of the solution of both poly mere shows. Are made from the homogeneous solutions of sulfohalogenated and native / silylated PSU thin polymer films by evaporating the Lö produced solvent, they have proven to be mechanically very stable sen, which is believed to be due to the strong interpenetration of the polymer tangle of sulfohalogenated and native / silylated PSU. The unmodified / silylated polymer acts as a stable support phase in which the sulfohalogenated polymer is embedded. The polymer films can now in a second step of acidic, basic or aqueous hydrolysis in he subjected to high temperatures, so that all sulfonyl halide groups pen can be converted into sulfonate groups. It will be this way Obtain polymer films with morphologies such as those obtained by mixing sulfo nated and native polymer could not be obtained. Because of the strong Penetration of polymer balls of native and sulfohalogenated poly The morphology of the polymer film is fixed, so it can also be determined by the hy Drolysis of the sulfonyl halide groups no longer changed macroscopically become.

In this way, it is possible to obtain blend membranes made of sulfonated and unmodified polymers, which have a considerably higher mechanical stability compared to other ion exchange membranes and whose micro-phase structure is wide by varying the ratio and type of sulfo-halogenated and unmodified blend components and, if appropriate, other blend components Limits can be varied. Further degrees of freedom of variation of the glare membranes are:
Addition of a third component to the blend of sulfohalogenated and unmodified polymer, for example addition of a polymer containing a basic nitrogen group, which can crosslink with the sulfohalide groups to form sulfonamide bridges. Crosslinking of the poly (sulfohalide) with itself and / or with the unmodified polymer if the poly (sulfohalide) and / or the unmodified polymer is an aromatic polymer and a Friedel-Crafts catalyst such as AlCl ₃ , AlBr ₃ , BF ₃ , FeCl ₃ etc. is added and / or the temperature is increased and the sulfo halide group reacts with an aromatic H as follows:

The -SO ₂ crosslink bridges are chemically very stable. With the sulfochlorinated polymers according to the invention are also bipolar membranes (bipolar membranes are membranes which consist of an anion exchange polymer and a cation exchange polymer layer and which are used in electrodialysis for water splitting [KN Mani, J. Memb. Sci. 58, 117-138 (1991), R. Simons, J. Memb. Sci. 78, 13-23 (1993)]) easily accessible: You only have to apply a solution of the sulfohalogenated polymer to an anion exchange polymer membrane, evaporate the solvent and by means of the sulfohalogenated polymer convert acidic, neutral or alkaline hydrolysis to the corresponding sulfonated polymer. The solution of the sulfohalogenated polymer can be yet another polymer, e.g. B. an aminated or an unmodified polymer, as described above. If the aminated polymer easily reacts with the sulfohalogenated polymer, the primary, secondary or tertiary amino group can first be provided with a protective group, which is then cleaved off again at the same time as the acidic or alkaline hydrolysis of the sulfohalide groups of the polymeric sulfonic acid halide layer on the anion exchange membrane. A slightly alkaline or acidic protective group for primary amino groups is the acetyl group, which is generated by reaction of the amino group with, for example, acetic acid chloride:

Polymer-NH ₂ + H ₃ C-COCl → polymer-NH-CO-CH ₃ .

Amino groups can also be masked by reaction with benzenesulfochloride:

Polymer-NH ₂ + C ₆ H ₅ -SO ₂ Cl → polymer-NH-SO ₂ -C ₆ H ₅ .

The sulfonamide formed can be acidic while retaining the amino group will split.

Many examples of are from the literature, in particular from protein chemistry Protecting groups for amino groups are known.

The particular advantage of the above bipolar manufacturing process Membranes is that the sulfohalogenated polymer in a solution can be dissolved (for example tetrahydrofuran), which the anions exchanger polymer layer does not attack. In the common production bipola  rer membranes via lamination of anion exchange polymer membranes with cation exchange polymer solutions there is the problem that the Dissolution of the cation-exchange polymer necessary dipolar aprotic Solvent (N-methylpyrrolidone, N, N-dimethylacetamide, N, N-dimethyl formamide, dimethyl sulfoxide etc.) the anion exchange layer or even dissolves and thus the sharp boundary necessary for bipolar water splitting layer between the anion and cation exchange polymer membrane in the Bipolar membrane cannot be formed.

Embodiments example 1 Production of sulfochlorinated polysulfone with a SO ₂ Cl group approach

11.05 g of commercially available PSU Udel® P 1800 (0.025 mol) dried
400 ml THF anhydrous
2.5 ml n-BuLi 10 N (0.025 mol)
2.4 ml SO ₂ Cl ₂ (0.03 mol)
Molecular mass of sulfochlorinated PSU: 540.5 g / mol
Molecular mass of sulfochlorinated-hydrolyzed PSU: 522.0 g / mol
Target capacity:
1.85 meq / g SO ₂ Cl
1.92 meq / g SO ₃ H.

execution

Anhydrous THF was introduced into a 1 L reaction vessel under protective gas. The dried polymer was then introduced into the reaction vessel with stirring and vigorous purging with argon. After the polymer was dissolved, it was cooled down to -70 ° C under a vigorous flow of argon. The polymer solution was then titrated with n-BuLi until a slight yellow / orange color indicated that the reaction mixture was now anhydrous. Then 10 N n-BuLi was injected within 15 minutes. The reaction mixture was allowed to react for 1½ hours. Then SO ₂ Cl ₂ was quickly injected. 25 ml of water were then injected into the reaction mixture in order to hydrolyze excess SO ₂ Cl ₂ . The reaction mixture was then allowed to warm up to room temperature.

100 ml of the solution were then removed from the reaction vessel and this was precipitated in 500 ml of isopropanol, preferably by spray precipitation. After filtration, the polymer granules were slurried in 100 ml of methanol and stirred for 1 hour. Then it was filtered off again. The polymer was dried at 50 ° C in a vacuum. Then it was ground. After grinding, it was slurried in diethyl ether (100 ml) and stirred for 1 hour. The ether was then rotated off. Drying was carried out at 50 ° C. first in a membrane pump vacuum, then in an oil pump vacuum. Drying should be very careful since the samples were then examined using ¹ H-NMR and IR spectroscopy. An elemental analysis, a ¹ H-NMR spectrum and an IR spectrum were recorded from the dried polymer (KBr pellet).

The remaining polymer solution was precipitated in 1 liter of water with spray precipitation. The polymer was filtered off and dried at 80 ° C. in a drying cabinet. Then it was slurried in 100 ml of water and left in the drying cabinet at 80 ° C. until it was hydrolyzed (2 days). It was then filtered off and predried at 80 ° C. in a drying cabinet. Then it was ground. The polymer was slurried in 100 ml of diethyl ether, left to stir for 1 day, and then the ether was stripped off in a rotary evaporator at atmospheric pressure, the adhering water being taken along azeotropically. The polymer was dried to constant weight in an oil pump vacuum at 80 ° C. A ¹ H-NMR spectrum, an elemental analysis and an IR spectrum (KBr pellet) are produced from the polymer.

characterization

Yield: 97%
Ion exchange capacity (IEC): 1.89 meq SO ₂

Cl / g ( ^1st

H-NMR)
IEC: 1.78 meq SO ₂

Cl / g (elementary analysis)
IEC (hydrolyzed): 1.75 meq SO ₃

H / g ( ^1st

H-NMR)
IEC (hydrolyzed): 1.45 meq SO ₃

H / g (titration).

Example 2 Production of sulfochlorinated polysulfone with 3 SO ₂ Cl groups approach

11.05 g PSU Udel® P 1800 (0.025 mol) dried
400 ml THF anhydrous
10 ml n-BuLi 10 N (0.1 mol)
12 ml SO ₂

Cl ₂

(0.15 mol)
Molecular mass of sulfochlorinated PSU: 737.5 g / mol
Molecular mass of sulfochlorinated-hydrolyzed PSU: 682.0 g / mol
Target capacity: 4.07 meq / g SO ₂

Cl
4.44 meq / g SO ₃

H (after hydrolysis).

execution

The THF was introduced into a 1 L reaction vessel under protective gas. The dried polymer was then introduced into the reaction vessel with stirring and vigorous purging with argon. After the polymer was dissolved, it was cooled down to -60 ° C under a vigorous flow of argon. The polymer solution was then titrated with n-BuLi until a slight yellow / orange color indicated that the reaction mixture was anhydrous. Then 10 N n-BuLi was injected. After the BuLi injection, the thermostat of the cooling unit was set to -30 ° C. The rising temperature was observed and the reaction mixture was allowed to react for 2 hours after reaching -30 ° C. It was then cooled back down to -70 ° C. Then the SO ₂ Cl ₂ was quickly injected.

50 ml of water were then injected into the reaction mixture in order to hydrolyze over excess SO ₂ Cl ₂ and to transfer the salts into the aqueous phase. The reaction mixture was then allowed to warm up to room temperature. The reaction mixture was poured into a separatory funnel and the phases were allowed to separate. The organic phase containing the sulfochlorinated polymer was precipitated in isopropanol and filtered off. Then it was stirred again in 300 ml of isopropanol and filtered off again. After filtering, the polymer granules were dried at 50 ° C. in vacuo. It was then slurried in diethyl ether (100 ml) and stirred for 1 day. The ether was then filtered off. Drying was carried out at 50 ° C. first in a membrane pump vacuum, then in an oil pump vacuum. Drying should be very careful since the samples were then examined using ¹ H-NMR and IR spectroscopy. An elemental analysis, a ¹ H-NMR spectrum and an IR spectrum were recorded from the dried polymer (KBr pellet).

A sample of the polymer (4 g) was then slurried in 100 ml of water and left in the drying cabinet at 80 ° C. until it had dissolved under hydrolysis. After dissolution, the aqueous polymer solution was dialyzed until neutral. The dialysate was evaporated in a drying cabinet at 80 ° C. to give the solid polymer and then comminuted. The polymer was slurried in 100 ml of diethyl ether, allowed to stir for 3 days, and then the ether was filtered off. The polymer was dried in an oil pump vacuum at 80 ° C. to constant weight. A ¹ H-NMR spectrum, an elemental analysis and an IR spectrum (KBr pellet) were prepared from the hydrolyzed polymer. In addition, the ion exchange capacity of the hydrolyzed polymer was determined by titration. For this purpose, 0.5-1 g of the polymer were dissolved in 50 ml of water (possibly by heating in a drying cabinet) and then titrated with 0.1 N NaOH.

characterization

Yield: 98%
Ion exchange capacity (IEC): 3.33 meq SO ₂

Cl / g ( ^1st

H-NMR)
IEC (hydrolyzed): 3.64 meq SO ₃

H / g ( ^1st

H-NMR)
IEC (hydrolyzed): 3.33 meq SO ₃

H / g (titration).

Example 3 Production of a blend membrane from sulfochlorinated polysulfone with 1.5 SO ₂ Cl groups and unmodified polysulfone

1.5 g of a sulfochlorinated polysulfone with 1.5 SO ₂ Cl groups per repeating unit were dissolved together with 0.5 g of unmodified polysulfone P 1800 in 10 ml of tetrahydrofuran. A thin film was drawn from the polymer solution on a glass plate and the solvent was allowed to evaporate at room temperature. The film was detached from the glass plate and hydrolyzed in water at 80 ° C for 48 hours. The result was an ion-conductive, transparent polymer film with the following characteristics:
Swelling H⁺ form in water: 45%
Ion exchange capacity: 1.65 meq SO ₃ H / g polymer
Surface resistance H⁺ (Na⁺) form (determined by impedance spectroscopy in 0.5 NH ₂ SO ₄ 10.5 N NaCl): 0.032 (0.317) Ωcm
Specific resistance H⁺ (Na⁺) form (determined by means of impedance spectroscopy in 0.5 NH ₂ SO ₄ / 0.5 N NaCl): 5.9 (58.8) Ωcm.

Example 4 Production of a blend membrane from sulfochlorinated polysulfone with 1.5 SO ₂ Cl groups and diaminated polysulfone

1.5 g of a sulfochlorinated polysulfone with 1.5 SO ₂ Cl groups per repeating unit were dissolved in 10 ml of tetrahydrofuran together with 0.5 g of diaminated polysulfone (poly (sulfone-di ortho-sulfone-amine) Polymer solution a thin film on a glass plate and allowed the solvent to evaporate at room temperature. The film was detached from the glass plate and hydrolyzed in water for 48 hours at 80 ° C. An ion-conductive, transparent polymer film was formed with the following characteristics:
Swelling H⁺ form in water: 28%
Ion exchange capacity: 1.68 meq SO ₃ H / g polymer
Surface resistance H⁺ (Na⁺) form (determined by means of impedance spectroscopy in 0.5 NH ₂ SO ₄ / 0.5 N NaCl):
0.259 (2.5) Ωcm
Specific resistance H⁺ (Na⁺) form (determined by means of impedance spectroscopy in 0.5 NH ₂ SO ₄ / 0.5 N NaCl): 16.19 (156.09) Ωcm.

Claims (35)

1. A process for the preparation of polymers sulfohalogenierten [polymer (SO ₂ Hal) _x], characterized in that a solution of the metallated polymer [polymer (Me) _x], with sulfuryl halide [SO ₂ Hal _2] at temperatures of man - 20 ° C to -100 ° C implemented. 2. The method according to claim 1, characterized in that the polymer residues [polymers] are selected from poly (ether sulfones), Po ly (phenyl sulfone) s, polyether (ether sulfone) s and / or poly (phenylene sulfide) s. 3. The method according to claim 1, characterized in that one uses a solution of the metallated polymer [polymer (Me) _x ], whose main aryl chain polymer has the repeating units R ₁ and / or R ₂ , wherein
R ₃ for hydrogen, trifluoromethyl or C _n H _{2n + 1} , with n = 1 to 10, in particular special methyl
R ₄ for hydrogen, C _n H _{2n + 1} with n = 1 to 10, in particular methyl or phenyl and
x represents 1, 2 or 3,
which are linked via bridge groups R ₅ or R ₆ ,
in which
R ₅ for -O- and
R _{6 stands} for -SO ₂ -. 4. The method according to claim 1, characterized in that the metalated polymer [polymer (Me) _x ], metalized polysulfone (PSU), wherein [R ₁ -R ₅ - R ₂ -R ₆ -R ₂ -R ₅ ] _n and R ₂ : x = 1 and R ₄ = H, the sulfohalogenated PSU having 0.1 to 3.5 SO ₂ Cl groups per repeating unit. 5. The method according to claim 1, characterized in that the metallized polymer [polymer (Me) _x ] is produced by:
Deprotonation of the unmodified polymer with alkali metals or alkyl / aryl alkali metal compounds, in particular alkali metal lithium and sodium, and in the case of alkyl / aryl alkali metal compounds, in particular Li organic compounds, for example butyl lithium or
Halogen-metal exchange of a halogenated polymer with lithium metal or Li-organic compounds. 6. The method according to claim 1, characterized in that the Lö solvents ether compounds, especially tetrahydrofuran, dioxane, glyme, Diglyme and / or triglyme. 7. The method according to claim 1, characterized in that the sulfuryl halide is selected from SO ₂ FCl and SO ₂ Cl ₂ . 8. The method according to claim 1, characterized in that the reak tion temperature is in the range of -30 ° C to -80 ° C. 9. The method according to claim 1, characterized in that the polymer concentration is 1-3 wt .-% is preferred. 10. A process for the preparation of sulfohalogenated polymer [polymer (SO ₂ Hal) _x (EL) _y ], characterized in that the metalated polymer with further electrophiles (EL), which can be gaseous or liquid or solid, in addition to SO ₂ Hal _{2 is brought} to reaction. 11. The method according to claim 10, characterized in that with the metallized polymer, the SO ₂ Hal ₂ and the electrophiles are reacted in any order, in particular all the electrophiles are reacted simultaneously. 12. A method for reacting the sulfohalogenated polymers according to claims 1 to 11, characterized in that the sulfohalides are subjected to basic, acidic or neutral hydrolysis to give the corresponding sulfonate, where X is H, Me, in particular Na, K, Rb, Cs , Li, Ag, divalent and trivalent metal cations, ammonium NR ₄₊ , pyridinium, imidazolium and / or benzimidazolium with R = H or R = 1 to 8 carbon atoms or aryl. 13. A method for implementing the sulfoha according to claims 1 to 11 logenated polymers, characterized in that the sulfohalides with Di- or oligoamines to form crosslinked polymers or crosslinked polymer membranes industries are implemented. 14. A method for implementing the sulfoha according to claims 1 to 11 logenated polymers, characterized in that part of the sulfohalogens nid groups or all sulfohalide groups of the polymer with amines if necessary, partially sulfonamidated polymers are implemented. 15. The method according to claim 14, characterized in that the restli Chen sulfohalide groups of the partially sulfonamidated polymer basic, acidic or neutral to the corresponding sulfonate groups the. 16. A method for implementation according to claims 1 to 11 obtainable sulfohalogenated polymers, characterized in that the sulfohalogens nide with basic nitrogen containing polymers, the primary or sekun där can carry amino groups for the production of cross-linked interpoly mer or cross-linked interpolymer membranes. 17. A process for reacting graft polymers or graft polymer membranes from the sulfo-halogenated polymers obtainable according to claims 1 to 11 with olefins, characterized in that the sulfo halides with initiation by CuCl / bipyridine, RuCl ₂ (PPh ₃ ) ₃ - (Tris ( tri phenylphosphine) ruthenium (II) dichloride / aluminum triisopropylate or similar redox catalysts with olefins for the radical polymerization reaction. 18. A method for implementing the obtainable according to claims 1 to 11 Chen sulfonated polymers with unsaturated groups containing polyme ren, characterized in that a solution of the two polymers in one Solvent is prepared, and then the sulfohalide groups of the egg  NEN polymer with the olefin groups of the other polymer with initiation with the initiators or other initiators mentioned in claim 15 position of AB crosslinked copolymers or AB crosslinked copolymer membranes Branches of polymeric sulfohalides brought to the crosslinking reaction become. 19. Process for the production of membranes from sulfohalogenated Po lymeren according to one of claims 1 to 11, characterized in that the polymeric sulfohalide is dissolved in a solvent, the polymer Solution is pulled out into a thin film, and the solvent ver is steaming. 20. The method according to claim 19, characterized in that in addition to the sulfohalogenated polymers another polymer, especially the unmo dified base polymer of the sulfohalogenated polymer is used. 21. The method according to claim 19 or 20, characterized in that the Polymer solution still aminated polymer is added. 22. The method according to any one of claims 14 to 21, characterized in that polymer with -NHR groups is added to the polymer solution, where R is a protective group for amines, in particular for
stands. 23. The method according to claims 18 to 22, characterized in that that the membrane after evaporation of the solvent of the acidic, alkali is subjected to hydrolysis or neutral. 24. The method according to claims 20 to 23, characterized in that the polymer solution Friedel-Crafts catalysts, in particular AlCl ₃ , AlBr ₃ , BF ₃ , FeCl _{3 are} added. 25. Membranes obtainable by a process according to one of the An Proverbs 1 to 24 for use in membrane fuel cells, in the Mem branch electrolysis, pervaporation, gas separation, perstraction and electrodialysis. 26. Membranes obtainable by a process according to claims 12 to 23 for use in membrane fuel cells, in membrane electrolytes se, in electrodialysis and in electromembrane processes. 27. Membranes obtainable by a process according to one of the claims che 1 to 24 for use in pervaporation, gas separation and perstrak tion. 28. Sulfohalogenated polymers obtainable by a process according to ei nem of claims 1 to 25. 29. Process for the production of laminated membranes, thereby ge indicates that a solution of the sulfohalogenated polymer is available by a method according to any one of claims 1 to 24 to a poly membrane is applied, the solvent is evaporated and the sul fohalogenated layer is hydrolyzed. 30. The method according to claim 29, characterized in that the Polymer membrane is an anion exchange membrane. 31. The method according to claim 29, characterized in that the sulfo halogenated polymer acidic, neutral or alkaline to the corresponding sulfo hydrated polymer is hydrolyzed. 32. Membrane, which is composed of several layers, characterized thereby records that they have at least one layer with sulfohalogenated polymer, he holds according to one of claims 1 to 24. 33. The membrane of claim 32, comprising a layer, the sulfohaloge contains polymer and an anion exchange polymer layer. 34. Membrane according to claim 33, characterized in that the Layer of sulfohalogenated polymer hydrolyzed to sulfonated polymer is.   35. Use of a bipolar membrane according to claim 34 for electro dialytic water splitting.