DE1917374A1 - Polymerization process - Google Patents

Description

Patent attorneys' DIpI. Ing.F.Weickmann, 1911374 Dlpl.lng. H.Welckmann, Dipl.Phys.Dr.K.FIncke

Dipl. Ing, F. A. Weickmann, Dipl. Chem. B. Huber B Munich 27, MShlstr. 22nd

SMIIH - 719 23t

AMBHIOAlT MCHIWB Am EOTJKDRY COMPANY Hew York / USA

Polymerisation process

The present invention relates to a method of polymerizing of a monomer in an aqueous emulsion system of the monomer on a carrier polymer in which the carrier polymer under suitable polymerization conditions is contacted with a system »that the monomer, Water and an emulsifying agent contains »around the formed To stabilize the emulsion and the wetting of the surface

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surface of the Irägerpolymerisats by the emulsion and the Promote formation of a composite polymer.

The present invention thus relates to polymerizations. In particular, it relates to a process for polymerizing a honeycomb onto a carrier polymerizate, i.e. a Grafting process in an aqueous emulsion polymerization system.

The one used in describing the present invention The term "infiltration" denotes the penetration of the Honor on and in the inert base or the carrier polymer and the accompanying polymerization therein.

The term "polymerization" used in describing the present invention means polymerization of polymerizable in a conomer that the solid Carrier polymer surrounds »

Many processes are already known for the production of polymers. However, the development of processes that result in high yields products with high quality ₅ to kowtow field of! Technology-.toner still problems. This applies in particular with regard to polymerization processes, in which a polymerizable lionoioer is grafted onto a carrier polymer. In addition, many of the already known graft polymerization processes often require high-energy radiation in order to obtain quality products in satisfactory yields. The numerous end uses of the polymer products produced by such processes include ion exchange substances and the like, in particular permselective membranes. Accordingly, the "present invention, though generally applicable to aqueous emulsion polymerization, becomes

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is applicable, hereinafter for the purposes of illustration especially in their application to permaelective membranes described, but the invention is not intended to be limited thereto.

A common difficulty in converting resinous film materials to permselective membranes occurs in the first reaction stage, in which a polymerizable monomeric material is grafted onto the PiIm, especially when relatively large graft dimensions are desired and even more so if a crosslinking agent is used to create a more stable structure with the film. The problem is compounded by the difficulty of penetration difficult, which occurs with some films when they are contacted with the monomeric material · These Disadvantages are particularly prevalent in normal bulk grafting processes, where there is little grafting due to gelation of the bath and also uncontrolled polymerization or a polymerization that goes through, when high concentrations of crosslinking agent are used. Accordingly, there is a manufacturing process such products the need to eliminate the serious disadvantages of the already known processes.

This is achieved according to the invention by a process in which an organic, Ethylenically unsaturated monomer polymerized on a carrier polymer, with the irägerpolymerisat under Contacting polymerization conditions with a system containing the monomer, water and an emulsifying agent, which stabilizes the emulsion formed and the

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The emulsion promotes wetting of the surface of the carrier polymer and forms a composite polymer.

Exemplary carrier polymers that are used in the implementation The present invention can be used are generally vinyl polymers or copolymers, terpolymers and the like such as polyvinyl halides, e.g. polyvinyl chloride, polyvinyl dichloride, polyvinyl trichloride, polyvinyl bromide, polyvinyl fluoride »polyvinyl difluoride, Polyvinyl trifluoride and the like, polyvinylidene halides, such as polyvinylidene chloride, polyvinylidene bromide, PolyvinylidβηΓΙυοride and the like, perhalofluorocarbon polymers, like poly (trifluorochloroethylene), Tetrafluoroethylene and the like, polymers of acrylonitrile, amorphous and isotactic polyolefins, such as Polyethylene, polypropylene and poly-4-methylpentene-i, Polybutadiene, amorphous and isotactic vinyl ethers and thermosetting resins and the like such as urea resins and phenolic resins, alkyl acrylates and alkyl ethyl aorylates, such as ethyl or ethyl acrylates and methacrylates, and natural and synthetic rubbers and the like, the be produced by known methods. Also these substances can be used alone or in various combinations. In the field of permselective Membranes are polychlorotrifluoroethylene and polyethylene with film-forming densities, 4.h. from about 1.9 to 2.2 or from 0.90 to 0.95 »particularly useful, although the described polymers, the Dalten in one area from about 0.80 to about 2.5 are generally useful.

Exemplary polymerizable monomers for the

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Grafting onto which! Embossing polymers are suitable »belong the styrenes and styrene derivatives such as α-alkyl styrenes, for example α-methylstyrene, α-halogenated styrenes, for example α-chlorostyrene and α-bromostyrene, haloalkyletyrenes, for example chloromethylstyrene and bromoethylstyrene, and esters of styrene sulfonic acid. Also useful are vinylpyridine, vinylpiperidine, vinyllutidine, vinylcarbazole, Yinylsulfone, vinylnaphthalene, vinylaniline, Acrylic acid, methacrylic acid, allylarain and Ιί, Ν-dialkylaminoethyl methacrylate, like Ν, Ιί-dimethylaminoethyl acrylate and methacrylate, ϊΙ, Ιί-diethylamine ethyl acrylate and methaerylate and the like made by known methods. These substances can be used alone or in different Combinations are used. Particularly useful polymerizable monomers in the manufacture of pennselective Membranes are styrenes and derivatives thereof, aorylates and methacrylates.

As mentioned above, cause crosslinking reactions with a view to producing a well grafted product an even bigger problem. However, such crosslinking reactions are useful in changing the Polymer structure. The stability, i.e. physical properties, for example with regard to the dimension, and chemical properties, such as inertness and longevity, of membranes made in accordance with the invention is also increased by high networking. A wide variety can be used in practicing the present invention used by crosslinking agents.

Examples of useful crosslinking agents include divinyl or trivinyl monomers, such as divinylbenzene, Butadiene, ethylene glycol dimethacrylate, diallyl carbonate,

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Diallyl phthalate and siallyl cyanureate. The amount used of crosslinking agent is generally sufficient to improve stability, and the crosslinking agent can be used in Amounts up to about 20 wt .- ^ are used based on the weight of the polymerizable monomer used. The crosslinking reactions brought about by the use of such gowns regulate the extent of the Swelling that takes place in the carrier polymer film. At the same time, however, the rate of polymerization remains of the polymerizable monomer, i.e. the grafting on the carrier polymer, practically unaffected or is advantageously accelerated.

In carrying out the present invention will be Emulsifiers used, which stabilize the emulsion formed and the wetting of the carrier polymer surface promote through the emulsion. Suitable emulsifying agents can be either anionic, cationic or nonionic Be emulsifier. The emulsifiers are generally used in amounts that are at least sufficient to to maintain a stable emulsion of the monomer to be grafted onto the carrier polymer · The special Quantities can therefore, within a wide range, be in Vary depending on the monomeric material used. In general, however, the emulsifier is in in an amount ranging from about 0.05 to about 4.0 weight percent based on the weight of the monomeric material used, is present, the emulsifying agent preferably being present in an amount of from about 0.1 to about 1.0 weight percent. Exemplary Emulsifiers which can be used in carrying out the process of the invention are Soaps, alkyl sulfates, alkyl aromatic sulfonates and the Alkali and alkaline earth metal salts thereof and the like. Loading

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Particularly useful emulsifiers are ITa triumauryl sulfate and alkylnaphthalene sulfonates, especially those in which the alkyl groups contain from about 1 to 18 carbon atoms, as well as the alkali and alkaline earth metal salts thereof and especially propylated naphthalene sulfonate. The emulsifiers , like the monomeric substances, can be used alone or in mixtures with one another.

The present process, as mentioned above, is an aqueous emulsion process and becomes a maximum amount of water that is sufficient to produce a stable, uniform emulsion in the presence of an emulsifying agent of the monomer, and in the carrier polymer to provide a uniform and sufficient degree of grafting. In the spring case is because when performing the present invention a stable aqueous emulsion is formed which eliminates gelation of the polymerization bath. In addition, if the grafting takes place on the carrier polymer and the emulsion is exhausted is or is beginning to be depleted, additional components of the erulsification system including a minimum amount of water, i.e. only enough to allow convenient handling $ be added to the polymerization bath, so that θβ is kept constant in a state in which it is substantially uniform, continuous Grafting onto the carrier polymer and essentially uniform continuous polymerization of the polymerizable Monomers are present.

While not necessary, it can also be beneficial be to use an inert solvent in the emulsion polymerization systems of the invention. to

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such solvents include benzene, cyclohexane, Nitrobenzene and toluene and the like, alcohols with lower Molecular weight, such as methanol, ethanol »propanol and the like, triohlorethylene, chloroform, dioxane, Acetone »Athylendiohloridι Tetrahydrofuran and other suitable ones Solvent. The use of such solvents Generally speaking, it is particularly advantageous if they swell the carrier polymer and thereby the penetration of the polymerizing monomer into the Support carrier polymer and subsequent process steps, for example, the conversion to ion exchange ermat er ial, improve. Accordingly, it is preferred that any solvents present in the syotem mainly consist of substances that swell the carrier polymer instead of the polymerizable monomer or the adversely affecting polymer formed therefrom. However, it should be noted that in the description As used in the present invention, the term "solvent" is to be understood to include materials are that dissolve the carrier polymer or that dissolve the carrier polymer only swell. Typically, such solvents will be used in a range from about 10 to about 75 weight percent. and preferably in a range of from about 30 to about 60 weight percent based on the weight of the emulsion only Water, used.

In addition to the solvents, the polymerization system according to the invention can also contain mild polymerization inhibitors which do not enter the pores of the carrier polymer. Such inhibitors are generally added to the polymerization system after the polymerization of the monomer and the grafting are in progress. Useful inhibitors include copper powder, brass rods, copper

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.naphthenate, sulfur »high molecular weight phenols, for example polyaromatic phenols and other effective inhibitors that do not get into the pores of the Xragerpolynerieat occur, but at the same time regulate the polymerization of the monomer in the emulsion. You !! close to the Polymerization inhibiting material varies widely Scope. In general, however, about 0.01 to about StO wt .- ^, based on the weight of the polymerizable Ilonomers, used and preferably can be about 1.0 to 3.0 $ to the polymerization inhibitor for the implementation of the present invention can be used.

Although the present proceedings in the absence of one Catalyst and can be carried out without activation by photoohenisoht gowns and / or warnings is in generally preferred that a catalyst is present · Eb can all known, relatively water-insoluble, free radical-generating polymerization catalysts are used, for example peroxides, hydroperoxides, diazonium compounds, such as aliphatic © azobianitrile, and like that. However, it is preferred that the catalyst used be a water-insoluble polymerization catalyst. Besides er d βα can be activated by photochemical means as well as warnings., Such catalysts are generally in small quantities in a range of about 0.05 wt .- $ S and less up to about 3 »0 wt .-% or more used, based on the weight of the polymerizable honey in the system. In any case, nut At least sufficient catalyst can be used to polymerize the polymerizable honey as well initiate the grafting on the Srügerpolymeriaat.

The method according to the invention comprises the contacting of

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solid polymer! Carrier material with monomeric) material in an aqueous emulsion phase with or without the presence of catalysts, with polymerization if desired Sinhibitor and a solvent for the carrier polymer can be pre-banded in the system, and wherein the system is subjected to polymerisation conditions in order to effect the polymerisation of the monomeric material, while at the same time the polymerisingθ monomers is grafted into and onto the carrier polymer. The process can also be continuous, semi-continuous and carried out in batches. Albeit the present one Invention is generally applicable to polymerization, then, as already mentioned above, this is the case The carrier polymer is usually in the form of a pilme. However, it should be noted that the present invention also the use of carriers in particle fore or in any other suitable physical state includes. On the other hand, vcm pera » selective membranes of the carrier polymeriBatfilm and the Aqueous emulsion of the polymerizable monomer are generally brought into contact with one another by means of the fiIs is introduced into a bath of the emulsion »

The Borühningsäaiser between the Erage ^ polyaierisat vm aqueous emulsion of the polymerizable monomer - depending on the desired grafting measure vary * contact sides from about 3 hours to about are generally sufficient for the production of vöb iimaterial for the conversion into active membranes suitable is.

Wipe the touch of the aqueous emulsion away

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and the carrier film by immersing the carrier film in the aqueous emulsion bath can be carried out at widely varying temperatures. For example, the temperature of the aqueous emulsion may be in a Bereioh from about 5O ° G and less up to about 100 ⁰ O vary »while the decomposition and / or softening temperatures of the film or of the emulsion should not exceed. Generally the process is carried out at atmospheric pressure. However, in cases where pressure is applied, the temperature may exceed the numerical limits given above. Ausserdera is noted that can be achieved when using the erfindungegemäßen aqueous emulsions, in practice Pfropfgeschwindigkeiten of 5 or more per hour. On the other hand, according to the invention, it is also possible to introduce the film into an emulsion bath which contains a specific amount of polymerizable monomer which is sufficient to achieve a desired degree of grafting and to allow the reaction to proceed to the end point. When the grafting is complete, the film is then removed from the bath and excess monomer, if any, is washed off with a volatile solvent. Thereafter, if the grafted product is to be used in the field of permselective membranes, it is treated with suitable chemical methods in order to introduce ion exchange groups onto the active polymeric branches.

For example, cation exchange material can be converted by sulfonation of the aromatic group in the side chains will. This procedure can be carried out by treatment with chlorosulfonic acid «oleum, concentrated sulfuric acid or Sulfur trioxide can be carried out. Amination by a tertiary amine after chloromethylation of the aromatic groups

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pen provides very satisfactory quaternary amine anion retainer material, In the cases where the active polymer branch material naturally contains ions, is not further treatment required · For example, no further treatment is required »to remove ion exchangers» membranes made of vinylpyridine, vinylpiperidine, vinyllutidine, Vinylaniline, allylamine and Ιί ,, Ιί-dietliyleminoethyl acrylate or to produce methacrylate.

The following detailed examples are intended to further illustrate but not limit the invention In the examples, all ropes and percentages are by weight related, unless otherwise stated ο

Be i s ρ ie I

An aqueous emulsion concentrate containing 1760 g styrene, 240 g desinhibiertes Divitiylbenzol (50 fSig active approximately) containing 3.52 g Benzoylpeiioxyd, 164 g Hatriumlaurylsulfat and 3000 g of distilled water, is prepared by mixing the ingredients at room temperature (about 25 ⁰ G) until a stable _p uniform Emuleionskoneentrat (about 40 fi styrene and Divinylbeiiaol) is obtained are mixed in a hand "pumped homogenizer. 1,100 g de.s Eonsentrats are diluted with 8800 g of distilled water, to provide a uniform, stable Emulsionspfropfmischung containing about 376 g of styrene and 51 "3 g of divinylbenzene contains (approximately £ 50 ig active). '

A sample of 0.19 mm (7.5 mil) thick fluorocarbon oil Mixed polymer carrier film 53.3 cm wide (21 inches) and 4.57 m (15 feet) in length, the Poly

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BATH

. (ohlortrifluorethylen) in an excess of 90 i 'and the remainder poly (vinylidene fluoride), is immersed in a Glaereaktionsbehälter containing the diluted emulsion => The grafting is started at 6O ⁰ O, and it is 30 minutes to 70 ⁰ C increased. After 2 hours of grafting, examination of the film in the infrared spectrum shows an average degree of grafting of 2.5 ^, while after 3 hours there is an average degree of grafting of only 35%, which shows that the emulsion does not indicate a sufficient amount on the carrier film for grafting polymerizing styrene is available until a total grafting time of 6 hours has passed. ViSLQh 4 hours has been "lifted up and after 6 hours it reaches a final value of about 8 #, after which the test is terminated, the average degree of grafting to 4.2 i; the crosslinking comprises an average of about 6% divinylbenzene based on styrene.

Venn the grafted sample into a conventional method Cation exchange material is converted, so results an excellent ρenaselective membrane with the the following desirable properties

ion exchange capacity (Xrockenbaais) average 0.72 mXqu./g,.

electrical Weohaelstrom resistance (0.6n KOl) an average of 2.1 Ohm cm ² ,

Gel water content (! Crochet base) average 25.3 ^.

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example

Aqueous emulsion graft bath containing 680 g of styrene, 170 g of bivinylbene sol (about 50% active), 1.4 g of benzoyl peroxide, 360 g of propylated maphthalene sulfonate and 10 080 g of distilled water is prepared by purchasing the ingredients from KauiatexBperat ^ r (about 20 ⁰ O) susaBHaengeiniseht until a stable, even emulsion is formed.

A sample of 0.254 mm (10 mil) thick poly (eblortrifluoräthylen) film having a size of 6 _S 1 m χ 53 "3 cm (20 feet inoh χ 21) and having a density of about 2.0 is from a Rilckspuivorriehtimg lowered into AEA's bath which is maintained at about 70 ⁰ G. The film is continuously rolled up for about 5 hours and then rolled back into the bath. After this period of time, the average degree of grafting in the film is about 11 to 12.5% by weight, based on a content of about 10 5 »bivinylbenzene solvent on styrene, present »beatismit on an infrared spectrophotometer which has been calibrated beforehand in order to show the polystyrene content of the mime in comparison with an ungrafted film and with film proofs which are grafted to various degrees.

The sample thus prepared is then grafted defined chlorsuifo · and at 50 ⁰ C 1
introduce groups,

ned and ^{hydrolyzed at 50 0} C to cation exchange

The resulting ion exchange mesibran has did the inferential Characteristics:

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Ion exchange capacity (dry egg basis) average 1.0 to 1.1 mJtqu./g »

electrical alternating current resistance (0.6n KOl) without average 2.0 to 2.5 Ohm cm ² ,

Gel water content (Sroekenbasia) on average 23 to 27 5 ».

The present example illustrates that essentially uniform degrees of grafting in the film with no continuous Polymerization of the styrene and an elimination of the gelation of the bath can be achieved when using an emulsion system is used, which is in contrast to a polymerization process in Hasse, according to a parallel forecast, there is an average degree of grafting of only 2.5? 6 is obtained before the bath gels

Venn the one produced by the method according to the invention Membrane subjected to an accelerated peroxide stability test the life of the membrane is increased increased than 10 times.

example

The procedure of Example 2 is repeated without a catalyst. The process is carried out in a flask in an 85 ⁰ O water bath. The IiIm is 0.19 mm (7.5 mils) thick and 10.16 15.24-em (4 by 6 inches). For each β-hour grafting, the average degree of grafting is 7.8 # and the divinylbenzene crosslinking is 10 ^, based on styrene. Bas material is not converted into an ion exchange membrane.

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The procedure of Example 2 is #iederholt _s wherein the benzoyl peroxide with 2.0 g Asobisieobutyronitril @ re®tßt is. The same results are obtained *

Example 5

An aqueous Emulsionspfropfungsbad that 15.7 g of styrene "3.94 g of divinyl benzene (about 50 fiig active), Q ₉ 29 g of sodium" lauryl sulfate, 294 g of distilled water and contains 94 * 2 g tetrahydrofuran »is prepared by mixing ingredients at dta Room temperature (approx. 20 ⁰ O) can be brought to a minimum, until a stable, uniform emulsion is formed.

A sample of poly (chlorotrifltsorethylene) film 0.19 mm (7 # 5 rail) thick and 5.1 χ 5 |1 cm (2x2 inches) and having a density of about 2.0 is made Brought into the emulsion bath, which is kept at about 75 ⁰ O, for 10 hours. The degree of grafting is 7 4 and the crosslinking is 10 _t, based on styrene. The sample is not converted into ion exchange material «

Example i e 1

An aqueous emulsion grafting bath containing 340 g of styrene, 85 g of divinylbenzene (about 50% active), 25 g of sodium lauryl sulfate, 2140 g of distilled water, 0.7 g of benaoyl peroxide and 0.68 g of copper powder is prepared by the ingredients are mixed together at room temperature (about 25 ⁰ C) until a stable, uniform emulsion

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is formed.

Six samples of a polyethylene film with _O9 152 mm (5.0 nil) thickness and a size of 10.16 χ 10.16 cn (4x4 inch) and having a density of 0.95 are placed for 7 hours in the Bmulsionsbad that is heated to about 65 ⁰ C, "the degree of grafting is in the different sections after 2 hours 10.4 #» i * after 3 hours 15.4% after 4 hours 20.4 i '% after 5 hours ^22.8! J>, after 6 hours 25 »6 $ S and after 7 hours 32.6 #, while the crosslinking is 6 % , based on styrene. The section with a degree of grafting of 20.4 5 * is converted into cation exchange material with the following properties

Ion exchange capacity (Iroekenbasie) 1.6

electrical alternating current resistance (0.6n KOl) 8.6 Ohm cm,

Gel water content (srooken basis) 19 »8 5«.

The section with a degree of grafting of 25.6 ^ becomes duroh Chloromethylation and then amination with dimethylethanolamine converted into anion exchange material, which has the following properties:

Ion build-up capacity (base syrup) 1.63 mXqu _v / g, electrical breathing resistance (0.6n ECl) 10.1 ohm cm, water content (base base) 20.5 $ *

The present invention offers numerous advantages. For example, the method according to the invention simplifies the Control of the graft polymerization, eliminates the novelty, the baths for the polymerization in (grasp is own, he

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Allows you to use elevated consistencies aa highly active disinfection agents _f eliminates! Runaway polymerization during the exothermic dissolution which takes place and provides a practical, continuous process for graft polymerization processes The bath is completely up to a separate solid phase, which can easily be dispensed, can be allowed to polymerize »If, on the other hand, polymerisation processes in bulk and / or in solvents are used» the waste product is only partially polysate and has to be reacted before use. iä further he ο Pol ^ s @ rii & ti @ n stabilized because di @ @ 33th @ sia © E @ action b © l ή ei 'further poly » can lead to Wqu & t and / oSer SxplogioiiöQ.

if products with high quality in high ®M with hMte®Z'®n MQl®irßlB2? are received, the imwenüimg of Waasar as thinner is raittol ®iß g? © ß © i? WirtBdhaftl-iöh @ r Advantage «Numerous

are spawning for the ^ ohssann

Based on the above Bsschreibimg are zahlraiuhe for Taehmann Ausführungsforuien u @ t invention obvious without doing the AEAS l hman the invention is leaving sen.

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Claims (1)

PA! TEHgAKS P R f 0 EE; 1/. Gekennselohnet process for polymerizing elaes organieohen _t äthyle '' nisoh unsaturated monomers on a! EragerpolymarAaftt in an aqueous Smulsionesyetem "in the fact that it contacts the Trägerpolymerisat under Polymexlsationsbedlngungen with a system containing the monomers, water and an emulsifier, the emulsion formed aas stabilized and the wetting of the surface of the carrier polymer e by the emulsion and the formation of a composite polymer promotes. 2. The method according to claim 1, characterized in that that the organic athyleniseh unsaturated monomers Styrene is. 3. Method according to Claim 1 , characterized by ₉ that the system contains a pole polarization sensor. 4 · Yerfah / ien according to claim 1, üB & uveh characterized in that a crosslinking agent is present · 5 »Yerfahren according to claim 1, characterized in that additional components of the system ₅ which contain a minimum of water, are added proportionally 6. The method according to claim 1, characterized in that that the carrier polymer is a vinyl polymer * - 19 - 909 8-U / 1690 BAD 7. The method according to claim 6, characterized in that that the carrier polymer is polyvinylidene fluoride » 8. The method according to claim 1, characterized in that that the carrier polymer is a perhalogenated PUiorkohlen material polymer is. 9. The method neoh claim 8, characterized in that the carrier polymer is a copolymer ₉ which contains polychlorotrifluoroethylene in an excess of $ 90 and the remainder consists of polyvinylidene fluoride. 10. The method according to claim 8, characterized in that that the carrier polymer is polychlorotrifluoroethylene. 11 β method according to claim 1, characterized in that that the carrier polymer is a polyolefin. 12, method according to claim 11, characterized in, that the polyolefin is polyethylene. 13 »Method according to claim 1, characterized in that that the emulsifier is an alkylnaphthalene sulfonate * 14. The method according to claim 1 _r characterized? that the emulsifier is sodium lauryl sulfate. 15. The method according to claim 1, characterized in that} that a polymerization catalyst was present 16 «Method according to claim 15, characterized» that the polymerization catalyst is insoluble in water and ~ 20 0 9 8 4 4/1690 BAD 1 91737Λ that the monomer is allowed to penetrate into the (carrier polymer will. 17> Method according to claim 16 »characterized in that that the carrier polymer is in the form of a film 13. The method according to claim 16, characterized in that that the system partially added a crosslinking agent will. 19 «Method according to claim 17 * characterized» that the PiIm is a vinyl polymer. 20. The method of claim 17 'characterized in that the organic _t "ethylenically unsaturated monomers
Styrene is. 21. The method according to claim 17 »characterized» that the system contains a polymerization inhibitor. 22. The method according to claim 17, characterized in that » that the system contains tetrahydrofuran. exchange membranes »characterized ^ 4a ^ man in
an aqueous emulsion system ^ _eJLB ^ festos, organic Iräerpolymerisat under Eo-lyiSerisationsbedingungen with a KontakJUteriT that is a polymerizable, organic » Ethylene, 6htine-saturated 8 humors, water and a mn ^ ahlldate ühnulaion fltabili- - 21 - 9098 44/169 Claims 23. Use of the product according to one of claims 1 to 22 for the production of permselective ion exchange membranes by generating ion exchange groups in the graft polymer. 24. Use according to claim 23 »wherein the ion exchange groups are generated by sulfonation. 25. Use according to claim 23 »wherein the ion exchange groups can be generated by chloromethylation and subsequent amination. 909844/1690