SE189727C1

SE189727C1 -

Info

Publication number: SE189727C1
Authority: SE
Publication date: 1964-01-01

Description

Uppfinnare: R L Markus Uppfinningen avser framstallning av sampoly'merer innehallande tvarbryggor och hanfor sig speciellt till ett forfarande for framstallning av svallbara sampolymerer innehallande endast en liten mangd av en bryggbildare, vilket forfarande har den fordelen, att reproducerbar likformighet hetraffande tvarbryggor och polymerisation samt repro ducerbara svallningsegenskaper kunna astadkommas, att utbytena uppga till nara 100 % av de teoretiska och att Rad hastighet vid sampolymerisationen kan astadkommas. Inventor: RL Markus The invention relates to the preparation of copolymers containing cross bridges, and more particularly to a process for the preparation of swellable copolymers containing only a small amount of a crosslinker, which process has the advantage of reproducible uniformity in cross bridges and polymerization. swelling properties can be achieved, that the yields amount to almost 100% of the theoretical ones and that Rad speed during the copolymerization can be achieved.

Standarclforfarandena for polymerisation ha resulterat i en dalig kontroll av kedjelangden och "sarskilt i en dalig kontroll av fordelningen av bryggbildaren i identiska satser av de uppkommande hartsen. Ett forsOk har tidigare gjorts att undanrodj a denna nackdel genom anvandning av polymerisation i suspension eller emulsion. Dessa forfaranden gave emellertid endast mattliga forbattringar betraffande kontrollen av kedjelangden, fordelningen av bryggbildaren, etc. Det har varit nodvandigt att anvanda mycket effektiva fraktioneringsforfaranden, som krava omstandliga atgarder och aro behaftade med vasentligt 'spill, i andamal att astadkomma en i huvudsak likformig polymer. Vid framstallning av sampolymerer, som Rimpa sig att anvanda sasom svallbara hartser och innehalla en mycket liten mangd bryggbildande material, maste graden av bryggbildning med nodvandighet vara lag. Det har emellertid varit svart, fiir att joke saga omjligt, att reproducera resultaten sats fOr sats och darigenom framstalla ett likformigt harts eller ett harts med i huvudsak likformig grad av bryggbildning och Rkformiga svallningsegenskaper. Bestamningen av svallningen i kombination med bestamningen av halten av kedjepolymerer fir kand sasom ett lampligt satt att karakterisera graden av bryggbildning i hartser. Med svaLlbara hartser ar det sarskilt betydelsefullt, att bryggbildningen Or likformig, eftersom en minskningi graden av bryggbildning med en brakdel av en procent av "sevart okar bildningen av kedjepolymerer, vilka i sin tur Oro losliga i stallet for svallbara. En ringa okning i graden av bryggbildning a andra "sidan resulterar i bildning av ett tatt, tredimensionellt natverk och en allvarlig forlust i materialets svallbarhet, vilket joke ar onskvart. The standard polymerization procedures have resulted in poor control of the chain length and, in particular, poor control of the distribution of the crosslinker in identical batches of the resulting resins. Attempts have been made in the past to obviate this disadvantage by using polymerization in suspension or emulsion. procedures, however, gave only moderate improvements in the control of the chain length, the distribution of the bridge former, etc. It has been necessary to use very efficient fractionation procedures, which require cumbersome procedures and are fraught with substantial waste, in order to produce a substantially uniform polymer. The production of copolymers, such as ripples used as swellable resins and containing a very small amount of crosslinking material, must necessarily be lawful, but it has been black, to make it impossible to joke, to reproduce the results batch by batch and thereby from form a uniform resin or a resin having a substantially uniform degree of crosslinking and smoke-like swelling properties. The determination of the swelling in combination with the determination of the content of chain polymers is known as a suitable way to characterize the degree of crosslinking in resins. With swellable resins, it is particularly important that the bridging formation be uniform, since a reduction in the degree of crosslinking by a fraction of one percent of the weight increases the formation of chain polymers, which in turn are soluble instead of the swellable ones. bridging on the other hand results in the formation of a dense, three-dimensional network and a serious loss of swellability of the material, which joke is unfortunate.

Genom foreliggande uppfinning blir det mojligt att framstalla de svallbara hartserna enligt "ett forfarande vid vilket resultaten kunna nog-'grant reproduceras. Dessutom har sattet enligt uppfinningen Oven den fordelen, att det ger utbyten, vilka narma sig 100 % av det teoretiskt mojliga. The present invention makes it possible to produce the swellable resins according to a process in which the results can be accurately reproduced. In addition, the method according to the invention also has the advantage that it gives yields which approach 100% of the theoretically possible.

" Det har namligen visat sig, att ern en speciell grupp sampolymerer framstallas i narvaro av en vattenl5sning av en lamplig tvavard jon, sh kan en likformig grad av bryggbildning och satsvis reproducerbarhet av resultaten erhallas. Vid sat-tat enligt uppfinningen sampolymeriserar man a) ett monomert material, som innehaller en dubbelbindning och Or i stand att underga bade homopolymerisation och sampolymerisation med b) ca 0,01-2,0 % av en monomer, raknat pa komponenternas a) och b) sammanlagda vikt, vilken monomer b) är en med komponenten a) sampolymeriserbar bryggbildare cob innehaller minst tva dubbelbindningar Det for sattet enligt uppfinningen utmarkande bestar i framsta rummet dari, att sampolymerisationen genomfOres i narvaro av ett vattenhaltigt reaktionsmedium, som Or atminstone 1/2 molart med avseende pa ett losligt salt, innehallande en tvavard, joke redoxsystem bildande jon, som utgores av en jordalkalimetalljon eller av en sulfat- eller sek.fosfatjon. Namely, it has been found that if a particular group of copolymers is prepared in the presence of an aqueous solution of an appropriate crosslinking ion, a uniform degree of crosslinking and batch reproducibility of the results can be obtained. In the composition according to the invention a) a monomeric material containing a double bond and capable of undergoing both homopolymerization and copolymerization with b) about 0.01-2.0% of a monomer, based on the total weight of components a) and b), which monomer b) is a with the component a) copolymerizable crosslinker cob containing at least two double bonds The distinguishing feature of the method according to the invention consists primarily in that the copolymerization is carried out in the presence of an aqueous reaction medium which is at least 1/2 molar with respect to a soluble salt containing one , joke redox system-forming ion, which consists of an alkaline earth metal ion or of a sulphate or sec.phosphate ion.

Eventuellt kan man Oven tillsatta suspensions-medal for erhallande av parlbildning och undvikande av sammanbakning. Optionally, you can also add a suspension medal for obtaining pearl formation and avoiding baking together.

Sasom exempel pa lampliga monomera material ma namnas: akrolein, allylidendiacetat, akrylnitril, akrylsyra, salter och estrar av akrylsyra, innefattande metylakrylat och etylakrylat, metakrylsyra, salter och estrar av metakrylsyra, inne- 2— — fattande metylmetakrylat orb etylmetakrylat, fumarsyra, monometylfumarat, dimetylfumarat, monoetylfumarat, dietylfumarat, maleinsyraanhydrid, maleinsyra, monometylmaleat, dimetylmaleat, monoetylmaleat, dietylmaleat, dimetylmetylenmalonat, dietylmetylenmalonat, itakonsyra, monometylitakonat, dimetylitakonat, monoetylitakonat, dietylitakonat, atropinsyra, metylatropat, etylatropat, klorakrylsyra och estrar darav, bromakrylsyra och estrar darav, jodakrylsyra och estrar darav, o-. m- och p-metylstyren, o-, m- och p-fluorstyren, o-, m- och p-klorstyren, a-sulfoakrylsyra samt salter och estrar darav, aaminoakrylsyra och syrasalter samt estrar darav, akrylamid, N-monometyl- och N, N-dimetylakrylamid, akrylsyraanhydrid, metakrylsyraanhydrid, metylvinylketon, hydrcadmetylvinylketon, o- och p-metoxistyren, etylenglykolmonomaleat, etylenglykolmonofumarat, N-vinyl-metylacetamid, vinylacetat, vinylbutyrat, vinylbensoat, vinylkinolin, vinylpyridiner, t. ex. 2-vinylpyridin, 2-mety1- 5-vinylpyridin, 4-vinylpyridin, 2-viny1-5-etylpyridin, N-vinyIpyrrolidon, cyklopentadien, N-vinylftalimid, N-vinylsuccinimid, N-vinylacetamid, Nvinyl-diacetimid, dvs. en forening innehallande en dubbelbindning, som kan underga polymerisation i narvaro av lampliga katalysatorer eller initieringsmedel och vid lampliga 'reaktionsbetingelser. Lampliga polyomattade material (innehallande minst tva dubbelbindningar) aro exempelvis butadien, N,N-diallylakrylamid, diallylamin, diallylmetakrylamid, 2,5-dimety1-3,4-dihydroxi-1,5-hexadien, 2,5-dimety1-2,4-hexadien, divinylbensen, divinyleter av dietylenglykol, isopren, trivinylbensen, 2,7-dimety1-1,7-oktadien, 1,7-oktadien, p-diisopropenylbensen, 1,3,5-triisopropenylbensen,p, p'-diiso-propenyldifenyl, 1,1,3, 5-tetraally1-1,3-propandiol, 1,1,3,3-tetrametally1- 1,3-propandiol, 4,6-dimety1-4, 6-dihydroxi-1,8- nonadien, 2,4,6,8-tetramety1-4,6-dihydroxi-1,8- nonadien, nonadien-1,8 och 2,8-dimetyl-nonadien-1,8, dvs. ett material, som innehaller tva eller flera dubbelbindningar on kan underga bryggbildning med de oven definierade mono-mere materialen och vilket kan vara antingen aromatiskt eller alifatiskt. Ett kritiskt element vid foreliggande uppfinning ar att det dub-belt omattade materialet skall anvandas i en sadan mangd, att det uppkommande svallbara hartset innehaller mellan 0,01 och 2,0 viktprocent av det bryggliknande materialet. Anvandes mindre mangder an detta, är den uppkommande polymeren vanligen loslig, under det att endast begransad svallbarhet uppkommer, d mangder overstigande de ovannamnda anvandas. Lampliga sampolymerisationen initierande medel Mom ramen fir uppfinningen aro exempelvis bensoylperoxid, 2,2-azo-bis-isobutyrnitril, kaliumpersulf at, acetylperoxid, natriumalkenderivat, di-tert.- butylperoxid, kumenhydroperoxid, tetrafenylsuccindinitril, tetra-p-metoxifenylsuccindinitril, dvs. polymerisationen initierande (eller fria radikaler bildande») material, som astadkomma polymerisering av de vaIda monomera amnena under sam- tidig sampolymerisering av det dubbelt omattade materialet. Katalysatorn anvandes vanligen i en mangd av 0,01-1,0 viktprocent, raknat pa den sammanlagda viktmfingden av ovannamnda komponenter a) och b). Examples of suitable monomeric materials are: acrolein, allylidene diacetate, acrylonitrile, acrylic acid, salts and esters of acrylic acid, including methyl acrylate and ethyl acrylate, methacrylic acid, salts and esters of methacrylic acid, including methyl methacrylate acrylate, monomethyl methacrylate, dimethyl fumarate, monoethyl fumarate, diethyl fumarate, maleic anhydride, maleic acid, monomethyl maleate, dimethyl maleate, monoethyl maleate, diethyl maleate, dimethyl methylenemalonate, dietylmetylenmalonat, itaconic acid, monomethyl itaconate, dimethyl itaconate, monoetylitakonat, diethyl itaconate, atropic, metylatropat, etylatropat, chloro acrylic acid and esters thereof, bromo acrylic acid and esters thereof, jodakrylsyra and estrar darav, o-. m- and p-methylstyrene, o-, m- and p-fluorostyrene, o-, m- and p-chlorostyrene, α-sulfoacrylic acid and its salts and esters, aminoacrylic acid and acid salts and esters thereof, acrylamide, N-monomethyl- and N, N-dimethylacrylamide, acrylic anhydride, methacrylic anhydride, methyl vinyl ketone, hydroxymethyl vinyl ketone, o- and p-methoxystyrene, ethylene glycol monomaleate, ethylene glycol monofumarate, N-vinyl-methylacetamide, vinyl benoacetyl, vinyl acetate vinyl. 2-vinylpyridine, 2-methyl-5-vinylpyridine, 4-vinylpyridine, 2-vinyl-5-ethylpyridine, N-vinylpyrrolidone, cyclopentadiene, N-vinylphthalimide, N-vinylsuccinimide, N-vinylacetamide, Nvinyl-diacetimide a compound containing a double bond which can undergo polymerization in the presence of suitable catalysts or initiators and under suitable reaction conditions. Suitable polyunsaturated materials (containing at least two double bonds) are, for example, butadiene, N, N-diallylacrylamide, diallylamine, diallylmethacrylamide, 2,5-dimethyl-3,4-dihydroxy-1,5-hexadiene, 2,5-dimethyl-2,4,4 -hexadiene, divinylbenzene, divinyl ether of diethylene glycol, isoprene, trivinylbenzene, 2,7-dimethyl-1,7-octadiene, 1,7-octadiene, p-diisopropenylbenzene, 1,3,5-triisopropenylbenzene, p, p'-diisopropylene propenyldiphenyl, 1,1,3,5-tetraallyl-1,3,3-propanediol, 1,1,3,3-tetrametallyl-1,3-propanediol, 4,6-dimethyl-4,6-dihydroxy-1,8- nonadiene, 2,4,6,8-tetramethyl-4,6-dihydroxy-1,8-nonadiene, nonadiene-1,8 and 2,8-dimethyl-nonadiene-1,8, i.e. a material which contains two or more double bonds may be bridged with the monomeric materials defined above and which may be either aromatic or aliphatic. A critical element of the present invention is that the double unsaturated material should be used in such an amount that the resulting swellable resin contains between 0.01 and 2.0% by weight of the bridge-like material. If smaller amounts are used than this, the resulting polymer is usually loose, while only limited swellability occurs, when amounts in excess of those mentioned above are used. Suitable copolymerization initiators The scope of the invention are, for example, benzoyl peroxide, 2,2-azo-bis-isobutyronitrile, potassium persulphate, acetyl peroxide, sodium alkene derivative, di-tert-butyl peroxide, cumene hydroperoxide, tetraphenylsuccindinitrilitrile, the polymerization initiating (or free radical generating) materials which effect polymerization of the selected monomeric substances while simultaneously copolymerizing the double unsaturated material. The catalyst is usually used in an amount of 0.01-1.0% by weight, based on the total weight ratio of the above-mentioned components a) and b).

Darest ett suspensionsmedel for erhallande av parlbildning och undvikande av sammanbakning anvandes, bar detta tillsattas i en mangd Overstigande c:a 0,01 viktprocent och hogst upp till c:a 0,1 viktprocent, lamphgen 0,02 viktprocent, raknat pa komponenternas a) och b) sammanlagda vikt. Representative material, som lampa sig sasom suspensionsmedel, aro exempelvis kasein, vatmedel, gelatin, vaxtgummin, kaolin, metylcellulosa, polyvinylalkohol, partiellt hydrolyserat polyvinylacetat, talk, dragantgummi och skyddskolloider, som aro valkanda i tekniken. Ett losningsmedel kan anvandas, som Er kemiskt indifferent i forhallande till reaktionskomponenterna och reaktionsprodukterna. Representative losningsmedel aro exempelvis aceton, attiksyra, petroleumeter, bensen, toluen, xylen, alifatiska, aromatiska och alicykliska kolvaten. If a suspending agent for obtaining pearl formation and avoiding caking is used, it should be added in an amount exceeding about 0.01% by weight and up to about 0.1% by weight, or less than 0.02% by weight, based on the components a) and b) total weight. Representative materials which act as suspending agents are, for example, casein, wetting agent, gelatin, plant gums, kaolin, methylcellulose, polyvinyl alcohol, partially hydrolyzed polyvinyl acetate, talc, tragacanth rubber and protective colloids, which are valued in the art. A solvent can be used which is chemically inert in relation to the reactants and the reaction products. Representative solvents are, for example, acetone, acetic acid, petroleum ether, benzene, toluene, xylene, aliphatic, aromatic and alicyclic hydrocarbons.

Reaktionen genomfores genom att de mono-mere materialen och det dubbelt- eller polyomattade materialet sammanforas i narvaro av en vattenlosning av den tvavarda, redox-system icke bildande oorganiska jonen. Dessa material sammanforas vid en temparatur fran c:a rumstemperatur och upp till Aterflodestemperatur for reaktionsblandningen vid det anvanda trycket. Tryck kan palaggas medelst en indifferent gas, t. ez. koldioxid, kvave eller flagon adelgas, i andamfil att reglera systemets Aterflodestemperatur (flyktighet). Efter en lamplig tidsrymd, som i allmanhet icke overstiger c:a tva timmar, liar sampolymerisationen fullbordats och parlor bildats. I vissa speciella fall (om styren anvandes sasom en huvudmonomer) kan tjugo timmar erfordras I Or fullstendig omsattning. Darpe avskiljes materialen genom filtrering eller andra lampliga isoleringsforfaranden, och man erhaller sa ett material med likformig bryggbildning, som kan reproduceras i den andra, tredje och hundrade satsen genom anvandning av i huvudsak samma meto d. The reaction is carried out by combining the monomeric materials and the double- or polyunsaturated material in the presence of an aqueous solution of the two-part inorganic redox-forming inorganic ion. These materials are combined at a temperature from about room temperature and up to the backflow temperature of the reaction mixture at the pressure used. Pressure can be palaggas by means of an inert gas, e.g. carbon dioxide, nitrogen or flake noble gas, in andamphile to regulate the system's Atmospheric temperature (volatility). After a suitable period of time, which generally does not exceed about two hours, the copolymerization is completed and beads are formed. In some special cases (if styrene was used as a main monomer), twenty hours of complete conversion may be required. Darpe is separated from the materials by filtration or other suitable insulating procedures, and a material with uniform crosslinking is obtained which can be reproduced in the second, third and hundredth batches using essentially the same method.

Det ma framhallas, att mangden di- eller polyomattat material, som infores i reaktionen, kommer att reglera graden av sampolymerisation och samtidigt graden av svallbarhet, och att noggrann kontroll av mangden av denna bryggbildare, som omsattes, dr av storsta betydelse. It should be noted that the amount of di- or polyunsaturated material introduced into the reaction will control the degree of copolymerization and at the same time the degree of swellability, and that careful control of the amount of this crosslinker formed is of paramount importance.

Utbytena he.nfora sig till torrvikten av fraktionen av svallbart harts (polymer med tverbryggor)• efter fullstandig extraktion av de losliga fraktionerna (kedjepolymerer) i ett lampligt losningsmedel (svallningsmedel). The yields refer to the dry weight of the fraction of swellable resin (polymer with transverse bridges) • after complete extraction of the soluble fractions (chain polymers) in a suitable solvent (swelling agent).

Foljande exempel avse att illustrera uppfinningen utan att darfor begransa densamma. The following examples are intended to illustrate the invention without, therefore, limiting it.

Exempel 1. En blandning av 100 g akrylsyra, 1,2 g divinylbensen och 1 g bensoylperoxid sattes. till en matted magnesiumsulfatlosning i vatten och upphettades till 95° C. Efter 16 minuter erhells 100,5 g av ett harts med hog svallningsfor- - -3 maga, och samma harts kunde lätt erhallas genom upprepande av forfarandet Exempel 2. En blandning av 100 g akrylsyra, 0,92 g divinylbensen och 0,4 g azo-bis-isobutyrnitril sates till en mattad vattenlosning av berylliumklorid och blandningen upphettades till 95° C. Eller upphetining 13 minuter erholls 78,2 g av ett harts med hog svallningsfOrmaga. Dessa resultat kunna ldtt reproduceras genom upprepande av fOrfarandet. Example 1. A mixture of 100 g of acrylic acid, 1.2 g of divinylbenzene and 1 g of benzoyl peroxide was added. to a matted magnesium sulfate solution in water and heated to 95 ° C. After 16 minutes, 100.5 g of a high swelling resin was obtained, and the same resin could be easily obtained by repeating the procedure of Example 2. A mixture of 100 g of acrylic acid, 0.92 g of divinylbenzene and 0.4 g of azo-bis-isobutyronitrile were added to a matt aqueous solution of beryllium chloride and the mixture was heated to 95 ° C. Or heating for 13 minutes 78.2 g of a resin with high swelling capacity was obtained. These results can be easily reproduced by repeating the procedure.

Exempel 3. En blandning av 100 g metakrylsyra och 0,92 g divinylbensen blandades med 1,0 g bensoylperoxid, och blandningen sattes till en mattad losning av magnesiumsulfat i vatten. Efter upphettning i 30 minuter erholls 64,5 g av ett harts med hog svallningsformaga. Detta forfarande upprepades och en i huvudsak likformig parlstorlek liksom samma grad av svallbarhet hos produkten erholls. Example 3. A mixture of 100 g of methacrylic acid and 0.92 g of divinylbenzene was mixed with 1.0 g of benzoyl peroxide, and the mixture was added to a matt solution of magnesium sulfate in water. After heating for 30 minutes, 64.5 g of a high swelling resin were obtained. This procedure was repeated and a substantially uniform bead size as well as the same degree of swellability of the product was obtained.

Exempel 4. En blandning av 100 g akrylsyra, 0,59 g 3,4-dihydroxi-2,5-dimety1-1,5-hexadien och 0,30 g azo-bis-isobutyrnitril sattes till en mattad vattenlosning av magnesiumsulfat och upphettades under 20 minuter till 95° C. Pa detta satt erWills 134 g harts, som kunde reproduceras genom upprepande av forfarandet, Liven efter utbyte av magnesiumsulfatet mot natriumsulfat. Example 4. A mixture of 100 g of acrylic acid, 0.59 g of 3,4-dihydroxy-2,5-dimethyl-1,5-hexadiene and 0.30 g of azo-bis-isobutyronitrile was added to a matt aqueous solution of magnesium sulfate and heated. for 20 minutes at 95 ° C. On this was added WillS 134 g of resin, which could be reproduced by repeating the procedure, Life after exchanging the magnesium sulphate for sodium sulphate.

Exempel 5. En blandning av 100 g akrylsyra och 2,2 g divinylbensen och 10 g kaliumsulfat sattes till en magnesiumsulfatlosning i vatten. Efter upphettning 1 timme till 60° C erholls 114,5 g hydrofilt harts, som kunde reproduceras genom upprepning av forfarandet. Example 5. A mixture of 100 g of acrylic acid and 2.2 g of divinylbenzene and 10 g of potassium sulfate was added to a magnesium sulfate solution in water. After heating for 1 hour at 60 ° C, 114.5 g of hydrophilic resin were obtained, which could be reproduced by repeating the procedure.

Exempel 6. En blandning av 277 g etylakrylat, 1,84 g divinylbensen och 0,6 g azo-bis-isobutyrnitril sattes till en mattad losning av magnesiumsulfat I vatten och upphettades 40 minuter till 95° C. Hdrvid erholls ett utbyte av 169 g harts med ringa grad av bryggbildning, vilket harts Mit kunde reproduceras genom upprepning av forfarandet. Example 6. A mixture of 277 g of ethyl acrylate, 1.84 g of divinylbenzene and 0.6 g of azo-bis-isobutyronitrile was added to a matt solution of magnesium sulphate in water and heated to 95 ° C for 40 minutes to give a yield of 169 g. resin with little degree of crosslinking, which resin Mit could be reproduced by repeating the procedure.

Exempel 7. En blandning av 100 g akrylamid och 0,92 g divinylbensen jamte 0,3 g azo-bis-isobutyrnitril sasom katalysator sates till en mattad losning av magnesiumsulfat i vatten och upphettades till 95° C. Utbytet var 103 g harts med hog svallningsformaga, vilket harts kunde reproduceras genom anvandning av samma material och forfaringssteg. Example 7. A mixture of 100 g of acrylamide and 0.92 g of divinylbenzene together with 0.3 g of azo-bis-isobutyronitrile as catalyst was added to a matt solution of magnesium sulfate in water and heated to 95 ° C. The yield was 103 g of resin with high swelling, which resin could be reproduced using the same material and process steps.

Exempel 8. 50 g monoetylfumarat, 50 g styren och 0,92 g divinylbensen jamte 0,30 g azo-bisisobutyrnitril sasom katalysator sattes till en mattad losning av magnesiumsulfat i vatten. Vid upphettning av blandningen till 95° C erholls 83 g av ett harts med ringa grad av bryggbildning, vilket harts erhiills anyo genom upprepning av forfarandet. Example 8. 50 g of monoethyl fumarate, 50 g of styrene and 0.92 g of divinylbenzene together with 0.30 g of azo-bisisobutyronitrile as catalyst were added to a matt solution of magnesium sulphate in water. When the mixture was heated to 95 ° C, 83 g of a resin having a low degree of crosslinking were obtained, which resin was obtained by repeating the procedure.

Exempel 9. 50 g dietylfumarat, 50 g styren, 0,92 g divinylbensen och 0,30 g azo-bis-isobutyrnitril sattes till en mattad losning av magnesiumsulfat i vatten och upphettades till 95° G. 48,5 g harts med ringa grad av bryggbildning erholls, vilket harts var svallbart till c:a 100 ganger sin volym i vattenhaltiga, sura material och latt kunde reproduceras genom upprepning av ovanna.mnda steg. Example 9. 50 g of diethyl fumarate, 50 g of styrene, 0.92 g of divinylbenzene and 0.30 g of azo-bis-isobutyronitrile were added to a matt solution of magnesium sulfate in water and heated to 95 ° G. 48.5 g of low grade resin of bridging is obtained, which resin was swellable to about 100 times its volume in aqueous, acidic materials and could be easily reproduced by repeating the above steps.

Exempel 10. En blandning av 200 g metylendietylmalonat, 1,84 g divinylbensen och 0,6 g azobis-isobutyrnitril sattes till en losning av magnesiumjon i vatten och upphettades till 95° C. Efter filtering, tvattning och torkning erholls 124 g av ett mjukt gummiartat harts, som var svallbart i tetrahydrofuran. Example 10. A mixture of 200 g of methylene diethyl malonate, 1.84 g of divinylbenzene and 0.6 g of azobis-isobutyronitrile was added to a solution of magnesium ion in water and heated to 95 ° C. After filtering, washing and drying, 124 g of a soft rubbery resin which was swellable in tetrahydrofuran.

Exempel 11. 100 g styren, 0,092 g divinylbensen och 0,250 g bensoylperoxid sattes till en magnesiumsulfatlosning och upphettades 16 timmar. Efter filtering, tvattning och torkning erbolls 97,5 g av ett i bensen svallbart harts, som kunde reproduceras genom upprepning av forfarandet Sulfonering av sampolymeren pa kant satt ger ett i vatten svallbart material. Example 11. 100 g of styrene, 0.092 g of divinylbenzene and 0.250 g of benzoyl peroxide were added to a magnesium sulfate solution and heated for 16 hours. After filtration, washing and drying, 97.5 g of a benzene swellable resin are obtained, which could be reproduced by repeating the process. Sulfonation of the copolymer by edge gives a water-swellable material.

Exempel 12. En blandning av 165 g 2-mety1-5- vinylpyridin, 0,46 g divinylbenseh och 0,3 g azo-bis-isobutyrnitril sattes till en mdttad lOsning av magnesiumsulfat i vatten, varvid erhdlls 155 g harts med ringa grad av bryggbildning, vilket harts i hog grad av svallbarhet i utspadd vattenhaltig klorvatesyra. Hartset kan latt reproduceras genom upprepning av ovannamnda fOrfarande. Example 12. A mixture of 165 g of 2-methyl-5-vinylpyridine, 0.46 g of divinylbenzene and 0.3 g of azo-bis-isobutyronitrile was added to a saturated solution of magnesium sulfate in water to give 155 g of resin having a low degree of bridging, which is a resin with a high degree of swellability in dilute aqueous hydrochloric acid. The resin can be easily reproduced by repeating the above procedure.

Exempel 13. En blandning av 100 g N-vinylpyrrolidon, 1,0 g divinylbensen och 0,3 g azo-bisisobutyrnitril sattes till en losning av magnesiumsulfat i vatten och upphettades, varvid erholls 81 g i vatten svallbart harts med ringa grad ay bryggbildning, vilket harts latt ken reproduceras genom upprepning av ovannamnda forfarande. Example 13. A mixture of 100 g of N-vinylpyrrolidone, 1.0 g of divinylbenzene and 0.3 g of azo-bisisobutyronitrile was added to a solution of magnesium sulphate in water and heated to give 81 g of water, with a slight degree of crosslinkable resin. resin has been reproduced by repeating the above procedure.

Exempel 14_ En hlandning av 30,0 g N-vinylfta- 0,27 g divinylbensen och 0,3 g bensoylperoxid sasom katalysator i mattad lOsning av magnesiumsulfat i vatten upphettades 38 minuter till 92° C. Pa detta Ott erhdlls 29,5 g harts, som är svallbart i en blandning av fenol och N,N-di.metylformamid (4: 1) i en utstrackning av 8 ml per g. Example 14 A mixture of 30.0 g of N-vinylphtha- 0.27 g of divinylbenzene and 0.3 g of benzoyl peroxide as a catalyst in a molten solution of magnesium sulfate in water was heated for 38 minutes to 92 ° C. , which is swellable in a mixture of phenol and N, N-dimethylformamide (4: 1) to the extent of 8 ml per g.

Exempel 15. En blandning av 100 g N,N-dimetylakrylamid och 0,92 g divinylbensen jamte 1,0 g bensoylperoxid sasom katalysator i mattad vattenlosning av magnesiumsulf at upphettades 28 minuter till 90° C. PA detta sat erholls 96,6 g harts, som är svallbart i destillerat vatten i en utstrackning av 32 ml per g. Example 15. A mixture of 100 g of N, N-dimethylacrylamide and 0.92 g of divinylbenzene and 1.0 g of benzoyl peroxide as a catalyst in saturated aqueous solution of magnesium sulfate was heated for 28 minutes at 90 ° C. 96.6 g of resin were obtained. , which is swellable in distilled water to the extent of 32 ml per g.

Exempel 16. En blandning av 20 g akrylamid, 5 g akrylsyra och 0,170 g divinylbensen samt 0,250 g bensoylperoxid sasom katalysator i vattenhaltig md.ttad magnesiumsulfatlosning upphettades 6 minuter till 93° C. PA detta salt erholls 17,85 g harts med ringa grad av bryggbildning, vilket harts är svallbart i destillerat vatten i en utstrackning ay- 310 ml per g. Example 16. A mixture of 20 g of acrylamide, 5 g of acrylic acid and 0.170 g of divinylbenzene and 0.250 g of benzoyl peroxide as a catalyst in aqueous magnesium sulfate solution was heated for 6 minutes to 93 ° C. On this salt 17.85 g of low grade resin were obtained. bridging, which resin is swellable in distilled water to an extent ay- 310 ml per g.

Exempel 17. En blandning av 100 g metakrylsyra, 9,0 g styren och 0,92 g divinylbensen samt 0,3 g azo-bis-isobutyrnitril sasom katalysator i en mattad lOsning av magnesiumsulf at i vatten upphettades 16 minuter till 93,5° C. Pa detta satt erh011s 90,9 g av ett harts med ringa grad av bryggbildning, vilket harts är svallbart i destillerat vatten i en utstrackning av 44,0 ml per g. 4— — - Exempel 18. En blandning av 50 g akrylsyra, 50 g styren, 0,92 g divinylbensen och 0,3 g ambis-isobutyrnitril sasom katalysator i en losning av magnesiumsulfat i vatten upphettades 40 mimiter till 94° C. Pa detta satt erholls 89 g harts med ringa grad av bryggbildning, vilket harts i destillerat vatten uppvisade en svallningsvolym av 60 ml per g. Example 17. A mixture of 100 g of methacrylic acid, 9.0 g of styrene and 0.92 g of divinylbenzene and 0.3 g of azo-bis-isobutyronitrile as catalyst in a matt solution of magnesium sulfate in water was heated to 93.5 ° for 16 minutes. C. 90.9 g of a resin having a low degree of crosslinking are obtained, which resin is swellable in distilled water to the extent of 44.0 ml per g. Example 18 - A mixture of 50 g of acrylic acid , 50 g of styrene, 0.92 g of divinylbenzene and 0.3 g of ambis-isobutyronitrile as catalyst in a solution of magnesium sulphate in water were heated 40 mm to 94 ° C. This gave 89 g of resin with little degree of crosslinking, which resin in distilled water showed a swelling volume of 60 ml per g.

Exempel 19. En blandning av 40 g metylendietylmalonat, 40 g dietylfumarat och 1,84 g divinylbensen jamte 0,6 g azo-bis-isobutyrnitril sasom katalysator i en mattad losning av magnesiumsulfat upphettades 8 minuter till 93° C. Pa detta salt erholls 23,5 g harts med ringa grad av bryggbildning, vilket harts uppvisade en svallning av 11 ml per g i tetrahydrofuran. Example 19. A mixture of 40 g of methylene diethyl malonate, 40 g of diethyl fumarate and 1.84 g of divinylbenzene together with 0.6 g of azo-bis-isobutyronitrile as catalyst in a matt solution of magnesium sulphate was heated for 8 minutes to 93 ° C. .5 g of resin with little degree of crosslinking, which resin showed a swelling of 11 ml per g of tetrahydrofuran.

Exempel 20. En blandning av 40 g metylenxlietylmalonat, 60 g etylakrylat och 1,84 g divinylbensen jamte 0,3 g azo-bis-isobutyrnitril sasom katalysator i mattad losning av magnesiumsulfat vatten upphettades 13 minuter till 93° C. Pa detta satt erh011s 77,0 g harts med ringa grad av bryggbildning, vilket harts är svallbart i en utstrackning av 15 ml per g i tetrahydrofuran. Detta harts kan lätt reproduceras genom upprepning av ovan angivna fOrfarande. Example 20. A mixture of 40 g of methylene ethyl ethyl malonate, 60 g of ethyl acrylate and 1.84 g of divinylbenzene and 0.3 g of azo-bis-isobutyronitrile as catalyst in a matte solution of magnesium sulfate water was heated for 13 minutes to 93 ° C. .0 g of resin with little degree of crosslinking, which resin is swellable to an extent of 15 ml per g of tetrahydrofuran. This resin can be easily reproduced by repeating the above procedure.

Exempel 21. En blandning av 31,5 g 2-vinylpyridin och 0,200 g divinylbensen jamte 0,06 g azo-bis-isobutyrnitril sasom initieringsmedel i en mattad kisning av magnesiumsulfat i vatten upphettades 40 minuter till 92° C. 28 g harts erholls, vilket harts är svallbart i vattenhaltiga syror. Example 21. A mixture of 31.5 g of 2-vinylpyridine and 0.200 g of divinylbenzene together with 0.06 g of azo-bis-isobutyronitrile as initiator in a matt churning of magnesium sulphate in water was heated for 40 minutes to 92 ° C. 28 g of resin were obtained. which resin is swellable in aqueous acids.

Exempel 22. En blandning av 150 g styren och A200 g divinylbensen jamte 0,030 g bensoylperoxid sasom katalysator i matted vattenlosning av kalciumklorid upphettades 20 timmar till 110° C. 149 g harts med ringa grad av bryggbildEing samt svallbart i bensen erholls, varav 83 % war fritt Iran kedjepolymerer. Example 22. A mixture of 150 g of styrene and A200 g of divinylbenzene together with 0.030 g of benzoyl peroxide as catalyst in matt aqueous solution of calcium chloride was heated for 20 hours to 110 ° C. 149 g of resin with little degree of crosslinking and swellable in benzene are obtained, of which 83% was free Iran chain polymers.

Exempel 23. En blandning av 150 g styren, -0,200 g divinylbensen och 0,130 g tetrafenylsuccindinitril sasom katalysator i en mattad vattenlosning av kalciumklorid upphettades 19 timmar ti11115° C. 150 g harts, svallbart i en utstrackning av 50 ml per g i bensen, erholls, varav 74 % var fritt Iran kedjepolymerer. Example 23. A mixture of 150 g of styrene, -0.200 g of divinylbenzene and 0.130 g of tetraphenylsuccin dinitrile as catalyst in a matte aqueous solution of calcium chloride was heated for 19 hours at 111 ° C. 150 g of resin, swellable to an extent of 50 ml per g of benzene, is obtained. of which 74% were free Iran chain polymers.

Exempel 24. En blandning av 150 g styren, 0,300 g triisopropenylbensen och 0,040 g bensoylperoxid sasom katalysator i en mattad vattenlosning av kalciumklorid upphettades 20 timmar till 113° C. 150 g harts erholls, vilket var svallhart i bensen i en utstrackning av 40 ml per g. Example 24. A mixture of 150 g of styrene, 0.300 g of triisopropenylbenzene and 0.040 g of benzoyl peroxide as a catalyst in a matt aqueous solution of calcium chloride was heated for 20 hours at 113 ° C. 150 g of resin were obtained, which was swelling resin in benzene to the extent of 40 ml per g.

Exempel 25. En blandning av 100 g akrylsyra, 1,0 g 4,6-dihydroxi-4,6-dimety1-1,8-nonadien och 0,300 g azo-bis-isobutyrnitril sisom katalysator i en mattad vattenlosning av magnesiumsulfat upphettades 15 minuter till 84° C. 88 g svallbart harts erholls, vilket var fritt Iran kedjepolymerer. Example 25. A mixture of 100 g of acrylic acid, 1.0 g of 4,6-dihydroxy-4,6-dimethyl-1,8-nonadiene and 0.300 g of azo-bis-isobutyronitrile sisom catalyst in a matt aqueous solution of magnesium sulphate was heated for 15 minutes. to 84 ° C. 88 g of swellable resin was obtained, which was free Iran chain polymers.

Exempel 26. En blandning av 100 g akrylsyra och 1,15 g 2,4,6,8-tetramety1-4,6-dihydroxi-1,8- nonadien jamte 0,300 g azo-bis-isobutyrnitril sasom katalysator i mattad magnesiumsulfat-losming i vatten upphettades i 5 minuter till 92° C. 7g svallbart harts erholls. Example 26. A mixture of 100 g of acrylic acid and 1.15 g of 2,4,6,8-tetramethyl-4,6-dihydroxy-1,8-nonadiene together with 0.300 g of azo-bis-isobutyronitrile as catalyst in matt magnesium sulfate solution in water was heated for 5 minutes to 92 ° C. 7g of swellable resin was obtained.

Exempel 27. En blandning av 100 g akrylsyra, 0,60 g 1,1,3,3-tetraally1-1,3-dihydroxipropan och 0,300 g azo-bis-isobutyrnitril sasom katalysator i mattad lOsning av magnesiumsulfat i vatten upphettades 5 minuter till 87° C. 82,5 g svallbart harts erholls, vilket var fritt fran kedjepolymerer. Example 27. A mixture of 100 g of acrylic acid, 0.60 g of 1,1,3,3-tetraallyl-1,3-dihydroxypropane and 0.300 g of azo-bis-isobutyronitrile as a catalyst in a matte solution of magnesium sulfate in water was heated for 5 minutes to 87 ° C. 82.5 g of swellable resin were obtained, which was free of chain polymers.

Exempel 28. En blandning av 845 g styren och -1,25 g divinylbensen jamte 0,76 g tetrafenylsuccindinitril sasom katalysator upphettades i en vattenlosning av kalciumklorid under ett tryck av 1 kgIcma kvavegas vid 130° C under 20 timmar. 842 g harts med ringa grad av bryggbildning erh011s, vilket harts var svallbart i bensen i en utstrackning av 45 ml per g. Halten kedjepolymerer i hartset var 26 %. Example 28. A mixture of 845 g of styrene and -1.25 g of divinylbenzene together with 0.76 g of tetraphenylsuccin dinitrile as catalyst was heated in an aqueous solution of calcium chloride under a pressure of 1 kg / l of nitrogen gas at 130 ° C for 20 hours. 842 g of resin with a low degree of crosslinking are obtained, which resin was swellable in benzene to an extent of 45 ml per g. The content of chain polymers in the resin was 26%.

Exempel 29. En blandning av 150 g styren och 0,300 g p-diisopropenylbensen jamte 0,030 g bensoylperoxid sasom katalysator upphettades i en mattad kalciumkloridlosning i vatten 22 timmar till 117° C. 150 g harts erholls, svallbart i en utstrackning av 26 ml per g och innehallande 3 % kedjepolymerer. Example 29. A mixture of 150 g of styrene and 0.300 g of p-diisopropenylbenzene together with 0.030 g of benzoyl peroxide as catalyst was heated in a matte calcium chloride solution in water for 22 hours at 117 ° C. 150 g of resin were recovered, swellable to the extent of 26 ml per g and containing 3% chain polymers.

Exempel 30. En blandning av 150 g styren och 0,150 g p-diisopropenylbensen jamte 0,0g bensoylperoxid sasom katalysator upphettades i en mattad vattenlosning av kalciumklorid i 23 timmar till 119° C. 150 g harts erhalls, vilket harts var svallbart i bensen till 47 ml per g. Detta harts inneholl 11,8 % kedjepolymerer. Example 30. A mixture of 150 g of styrene and 0.150 g of p-diisopropenylbenzene and 0.0 g of benzoyl peroxide as catalyst was heated in a matte aqueous solution of calcium chloride for 23 hours at 119 ° C. 150 g of resin were obtained, which resin was swellable in benzene to 47 ° C. ml per g. This resin contained 11.8% chain polymers.

Exempel 31. En blandning av 150 g styren och 0,150 g p-diisopropenylbensen jamte 0,135 g tetrafenylsuccindinitril sasom katalysator upphettades i en vattenlosning av kalciumklorid i 20 timmar till 117° C. 150 g harts erholls, vilket harts var svallbart i bensen i en utstrackning av 26 ml per g. Halten kedjepolymerer i detta harts var 9,5 %. Example 31. A mixture of 150 g of styrene and 0.150 g of p-diisopropenylbenzene and 0.135 g of tetraphenylsuccindinitrile as catalyst was heated in an aqueous solution of calcium chloride for 20 hours at 117 ° C. 150 g of resin was recovered, which resin was swellable in benzene to an extent of 26 ml per g. The content of chain polymers in this resin was 9.5%.

Exempel 32. En blandning av 150 g styren och 0,150 g p,p'-diisopropenyldifenyl jamte 0,135 g tetrafenylsuccindinitril sasom katalysator upphettades i en kalciumkloridlosning i vatten innehallande 0,220 g partiellt hydrolyserat polyvinylacetat sasom suspensionsmedel i 21 timmar till 117° C. 142 g harts erholls, vilket harts var svallhart i bensen i en utstrackning av 59 ml per g. Halten kedjepolymerer i detta harts var 36,3 %. Example 32. A mixture of 150 g of styrene and 0.150 gp, p'-diisopropenyldiphenyl and 0.135 g of tetraphenylsuccindinitrile as catalyst was heated in a calcium chloride solution in water containing 0.220 g of partially hydrolyzed polyvinyl acetate as a suspension for 14 hours. which resin was volatile resin in benzene to the extent of 59 ml per g. The content of chain polymers in this resin was 36.3%.

Exempel 33. En blandning av 150 g styren och 0,250 g p,p'-diisopropenyldifenyl jamte 0,135 g tetrafenylsuccindinitril sasom katalysator upphettades i en matted vattenlosning av kalciumklorid, innehallande 0,220 g partiellt hydrolyserat polyvinylacetat sasom suspensionsmedel ti11112°C under 18 timmar. 150 g harts erholls, vilket harts var svallbart i en utstrackning av 45 ml per g. Detta harts inneholl 20,5 % kedjepolymerer. Example 33. A mixture of 150 g of styrene and 0.250 g of p, p'-diisopropenyldiphenyl together with 0.135 g of tetraphenylsuccindinitrile as catalyst was heated in a matt aqueous solution of calcium chloride containing 0.220 g of partially hydrolyzed polyvinyl acetate under suspension for 18 hours. 150 g of resin were obtained, which resin was swellable to an extent of 45 ml per g. This resin contained 20.5% of chain polymers.

Exempel 34. En blandning av 100 g akrylsyra och 0,50 g p-diisopropenylbensen jamte 0,30 g azo-bis-isobutyrnitril upphettades i en vattenlOsning av magnesiumsulf at till 92° C under 5 minuter. 72 g kedjepolymerfritt harts erholls. Example 34. A mixture of 100 g of acrylic acid and 0.50 g of p-diisopropenylbenzene and 0.30 g of azo-bis-isobutyronitrile was heated in an aqueous solution of magnesium sulfate to 92 ° C for 5 minutes. 72 g of chain polymer-free resin are obtained.

Exempel 35. En blandning av 150 g styren och 0,300 g p,p'-diisopropenyldifenyl jamte 0,135 g tetrafenylsuccindinitril sasom initieringsmedel upphettades i en vattenlosning av kalciumklorid — — innehallande 0,220 g partiellt hydrolyserat polyvinylacetat sasom suspensionsmedel i 24 timmar till 115° C. 149 g harts erholls, vilket harts var svallbart i bensen i en utstrackning av 21 ml per g. Halten kedjepolymerer i denna sats var 4,3 %. Bromtitrering visade en kvarvarande omattnad av 2,0 % (omattnad hos monomeren: 100 %). Example 35. A mixture of 150 g of styrene and 0.300 gp, p'-diisopropenyldiphenyl and 0.135 g of tetraphenylsuccindinitrile as initiator was heated in an aqueous solution of calcium chloride containing 0.220 g of partially hydrolysed polyvinyl acetate. which resin was swellable in benzene to the extent of 21 ml per g. The content of chain polymers in this batch was 4.3%. Bromine titration showed a residual unsaturation of 2.0% (monomer unsaturation: 100%).

Exempel 36. En blandning av 100 g akrylamid och 1,00 g p-dlisopropenylbensen med anvandning av 0,300 g azo-bis-isobutyrnitril sasom initieringsmedel upphettades i en vattenlosning av sekundart natriumfosfat under 5 minuter till 91° C. 65 g harts erhdlls, vilket harts var svallbart i vatten i en utstrackning av 130 ml per g. Example 36. A mixture of 100 g of acrylamide and 1.00 g of p-disopropenylbenzene using 0.300 g of azo-bis-isobutyronitrile as initiator was heated in an aqueous solution of secondary sodium phosphate for 5 minutes at 91 ° C. 65 g of resin are obtained, which resin was swellable in water to the extent of 130 ml per g.

Exempel 37. En blandning av 200 g 2-vinylpyridin och 2,0 g p-diisopropenylbensen jamte 0,60 g azo-bis-isobutyrnitril sasom initieringsmedel upphettades i en vattenlosning av sekundart natriumfosfat under 30 minuter till 91° C. 170 g harts erh011s, vilket harts var svallbart i 0,1 N klorvatesyra i en utstrackning av 46 ml per g. Example 37. A mixture of 200 g of 2-vinylpyridine and 2.0 g of p-diisopropenylbenzene and 0.60 g of azo-bis-isobutyronitrile as initiator was heated in an aqueous solution of secondary sodium phosphate for 30 minutes at 91 ° C. 170 g of resin are obtained. , which resin was swellable in 0.1 N chloroacetic acid to the extent of 46 ml per g.

Exempel 38. En blandning av 200 g 2-vinylpyridin och 3,0 g p, p'-diisopropenyldifenyl jamte 0,60 g azo-bis-isobutyrnitril sasom initieringsmedel upphettades i en vattenlosning av sekundart natriumfosfat under 15 minuter till 92° C. 171 g harts erholls, vilket harts var svallbart i 0,1 N klorvatesyra i en utstrackning av 48 ml per g. Example 38. A mixture of 200 g of 2-vinylpyridine and 3.0 gp, p'-diisopropenyldiphenyl and 0.60 g of azo-bis-isobutyronitrile as initiator was heated in an aqueous solution of secondary sodium phosphate for 15 minutes at 92 ° C. 171 g resin was recovered, which resin was swellable in 0.1 N hydrochloric acid to the extent of 48 ml per g.

Exempel 39. En blandning av 100 g N-vinylftalimid, 2,0 g p, p'-diisopropenyldifenyl och 1,0 g bensoylperoxid sasom initieringsmedel upphettades i en vattenlosning av magnesiumsulfat under 65 minuter till 92° C. 75 g harts erh011s, vilket harts var svallbart i en utstrackning av 8 ml per g i en blandning av fenol och dimetylformamid (80 : 20). Example 39. A mixture of 100 g of N-vinylphthalimide, 2.0 gp, p'-diisopropenyldiphenyl and 1.0 g of benzoyl peroxide as initiator was heated in an aqueous solution of magnesium sulfate for 65 minutes at 92 ° C. 75 g of resin are obtained. was swellable to the extent of 8 ml per g a mixture of phenol and dimethylformamide (80:20).

I vart och ett av ovanstaende exempel avskilj des hartset genom filtrering och torkades darefter for beredning av ett i huvudsak likformigt harts betraffande storlek och svallningsegenskaper. Vid upprepande av det forfarande, som an-gives i vart och ett av exemplen, visar det sig att man far ett harts, med i huvudsak samma svallningsegenskaper och samma halt av kedjepolymerer. Dessutom mojliggor forfarandet enligt uppfinningen en bestamd reglering av polymerisationshastigheten liksom liven graden av sampolymerisation. In each of the above examples, the resin was separated by filtration and then dried to prepare a substantially uniform size and swelling properties of a substantially uniform resin. By repeating the procedure given in each of the examples, it is found that a resin is obtained, having substantially the same swelling properties and the same content of chain polymers. In addition, the process of the invention enables a definite control of the polymerization rate as well as the degree of copolymerization.

De angivna svallbara hartsen aro anvandbara sa.som lakemedel eller sasom mellanprodukter vid framstallning av mera komplexa molekyler. The indicated swellable resins are useful as medicaments or as intermediates in the preparation of more complex molecules.

Olika forandringar kunna vidtagas i forfarandet och foreningarna enligt uppfinningen, utan att darfor uppfinningstanken frangas. Various changes can be made in the process and the compounds according to the invention, without the idea of the invention being abandoned.

Claims

Patent claim:

A process for producing a swellable resin which consists of a copolymer with transverse bridges, wherein in the presence of a polymerization catalyst a) a monomeric material which contains a double bond and can undergo both homo- and copolymerization is copolymerized with b) c: a 0.01-2.0% of a monomer, based on the total weight of components a) and b), which monomer b) is a crosslinker with component a) and contains at least two double bonds, characterized in that the copolymerization is carried out in the presence of an aqueous reaction medium which is at least 1/2 molar with respect to a soluble salt, containing a double, lake redox system forming ion, which is formed from an alkaline earth metal ion of a sulphate or sec phosphate ion.

2. A kit according to claim 1, characterized in that the reaction medium in which the copolymerization is carried out contains a magnesium ion.

3. A kit according to claims 1 and 2, characterized in that the copolymerization is carried out in an aqueous magnesium sulphate solution.

4. A set according to any one of claims 1-3, characterized in that acrylic acid is copolymerized with divinylbenzene in the aqueous reaction medium.

5. A kit according to claim 4, characterized in that 100 parts by weight of acrylic acid are copolymerized with 1.2 parts by weight of divinylbenzene. Request publications: Patent papers iron Sweden 145 120; Germany 854851.