DE2237214A1 - Reactive polymeric gel - based on acrylamide and methylene - bisacrylamide - Google Patents

Abstract

Prods. are of type A.B (where A is a water-sol. or water-miscible monomer having a C=C (ethylenic) bond, e.g. acrylamide, and B is a water-sol. and water-miscible monomeric crosslinking agent having >=2 cross-linkable end gps., e.g. methylenebisacrylamide). A.B are copolymd. and/or a graft copolymer is added onto A.B so that there are reactive sites present at the gel. Prods. are used in mfr. of ion exchange resins, drying agents, in substn., fractionation reactions, immunological processes, as redox and fluorescent polymers, in isolating, purifying and detecting of metal ions.

Description

"Polymeric Gel" The invention relates to a polymeric gel which by Reaction of a water-soluble monomer, such as acrylamide, with a water-soluble 1 calibration crosslinking agent, such as N, N'-methylenebisacryl ämid-, is produced, wherein the crosslinking agent undergoes free radical polymerization with the monomer enters into a gel in an aqueous medium. If necessary, can later a third reactant, such as triethylenetetraamine, are added.

In particular, the invention relates to a polymeric gel of type A. Bx, where A is a water-soluble or water-miscible monomer with a Carbon double bond (Ethyler bond) is the one below education can be split by free valencies, and B is a polyfunctional monomer Crosslinking agent that provides the desired crosslinked polymeric gel during the free radical Polymerization forms. B should also be soluble in water or miscible with water and contains at least two to participate in a crosslinking reaction capable end groups. x is the amount of B present in the crosslinked gel, which is preferably 2.0 to 12 mole percent based on 100 mole percent A.

The gel of the invention is made by putting A and B together in an aqueous medium in the presence of a free radical initiator at room temperature and atmospheric pressure are implemented.

Typical examples of A are acrylic acid, methacrylamide, diethyl vinylamine and the same. The preferred crosslinking agent is N, N'-methylenebisacrylamide used. It was already a gel made of acrylamide and N, N'-methylenebisacrylamide manufactured.

However, the new gels according to the invention have different properties and are suitable for other purposes than the gel made of acrylamide and N, N'-methylene bisacrylamide.

In addition to a gel of the general formula A Bx, the invention includes also gels of the general formula A-Bx-C, in which A and B have the meanings given above and C is a material capable of participating in the polymerization reaction. C must therefore have a group that can react with a double bond in the Monomers or in the crosslinking agent B is capable in the polymerization, and must also have another end group that easily substitutes with additional groups i.e., a functional end group that can be further substituted. The gel A Bx cannot work with other groups through a substitution or addition reaction, as there are no reactive groups for substitution reactions are available. The other respondents C containing gels contain a reactive group, which then follows can be substituted, as will be explained in more detail below. Typical examples for C are triethylenetetramine, diethylenetriamine, polyindiamines, such as ethylenediamine, 1, 3-propanediamine and other types of amines explained in more detail below. As well as on the gels of type AB as well as type A Bx. C can be A alone or CtA grafted on after the gels have been formed. For example, the gel A 'B converted into a gel that is accessible for replacement and addition substitutions is by bringing the gel formed with additional material C + A together. One can also use the monomer A alone, which contains some useful groups, groups suitable for ion exchange, for example. You can also use material graft onto A through reactions with terminal groups.

The polymeric gels according to the invention can be in the form of particles, for example from powdery to pill-shaped granules, in the form of foils, Ribbons and in the form of molded bodies.

The gels according to the invention are of the aqueous type and therefore for use suitable in aqueous media. The gel easily adsorbs water in dry form and can therefore be used for volume concentration. The gel is stable in boiling water, in most organic solvents and in dilute ones Solutions of acids and bases. The polymeric gels according to the invention can be their application can be handled easily, for example, easily and in a short time of solutions with the help of a paper filter be separated. she can be regenerated, oven dried and stored. The gels come with a few Exceptions clear to translucent after manufacture and when dry colorless to slightly colored. Most of the gels according to the invention are drier than that Heat stable up to temperatures of over 1000C. Furthermore, gels are according to the invention accessible for substitution reactions in which groups are completely replaced or additional groups are added to groups. The polymeric gels according to the invention Finally, they can quickly and directly in an aqueous medium in the open air getting produced. The heat generation can therefore be easily controlled.

The polymeric gels according to the invention can be used for the most varied Purposes are applied. You can, for example, fractionate, adsorb and exchanges in immunological processes, in ion exchange and molecule exchange processes can be used. Furthermore, some polymers of the invention can be used as metal peel additive can be used for the isolation, cleaning and detection of metal ions. They can also be used as redox polymers and fluorescent polymers for the detection of Radiation and the like can be used. Furthermore, some polymers can be used after of the invention due to their hydrophilic character especially for drying wet polar and polar solvents are not used. Furthermore, they can can be used for combined tasks, for example for drying and neutralizing or for drying and desalting. The aforementioned properties depend of course on the type of polymer gel.

The basic A Bx gels are explained in more detail below. To make these basic gels, an in Water soluble or water-miscible monomeric compound A required for free radicals Polymerization is suitable.

Compound A can therefore have the following general formula: in which R1 is hydrogen, R2 is hydrogen, methyl, halogen or substituted amine groups, R3 is hydrogen, methyl or halogen and R4 is a reactive group consisting of carboxy derivatives including acids, amides and substituted amides, esters including alkyl, allyl and vinyl esters, Carbonyl derivatives including aldehydes and alkyl ketones, ether derivatives including vinyl ethers and N, N-dialkylamino ethers, aliphatic ethers, amine derivatives including primary amines, N-alkyl-substituted secondary amines, N, N-dialkylamines and trialkylammonium salts, primary, secondary and tertiary alkyl-substituted amines and various N-ring substituted compounds, class comprising benzene, nitrile, halide, nitro, sulfonic acid or amide and ethylenic groups is selected. Furthermore, a bond can be present between R2 and R. so that a .4 anhydride is present, for example maleic anhydride. Typical preferred examples of A are acrylic acid, methacrylic acid, diethyl vinyl amine, N -vinyl pyrolidone, methacryl amide, vinyl sulfonic acid and mixtures of these compounds, for example mixtures of acrylic acid and diethyl vinyl amine or of acrylic acid and vinyl sulfonic acid.

In order to form the gel according to the invention, the monomer A must be crosslinked with a suitable polyfunctional monomer which is suitable for free radical polymerization. B must also be soluble or miscible with water and has the following formula: in the in which R5 is hydrogen or methyl and R6 is hydrogen, methyl or halogen. y is two or three, depending on whether a divinyl or trivinyl crosslinking monomer is desired. Each Z group can be different from the other Z groups bonded to L or can also be the same as the other Z groups. L is a molecule or a group which forms a center connecting two or three Z groups to one another. When y is 2, L can include a methylenebis type group including a group of the sulfone bis type Ether like an amine derivative like and phenylene, when the monomer is of the trivinyl type, L may contain groups of the following formulas: Triacylamine Trisulfonylamine The most preferred crosslinking agent B is N, N'-methylenebisacrylamide. The amount of crosslinking agent B used to form the polymers of the invention is at least 2.5 mole percent, based on the amount of A. In general, B is used in an amount of 2 to 12 mole percent.

To achieve a polymerization, a free radical initiator, for example ammonium persulfate, potassium persulfate, or another similar known one Initiator can be used. The initiator is used in an amount of 0.5 to 3.0 mole percent used, at least 1.0 mole percent to 100 mole percent A are used. The medium for the polymerization is water and is used in an amount from 1000 to 1700 mole percent based on 100 mole percent A.

The polymerization reaction will be at neutral to alkaline pH carried out. A and B are added to the polymerization medium in an open beaker Water added. The starting temperature can be, for example, 1700 or the starting temperature corresponds to the room temperature. The temperature initially drops because of one at the Dissolution of occurring endothermic effect from something.

After the solids dissolve, the required amount of free radical will be added Added initiator and mixed with the aqueous medium so that it is in the dissolves aqueous medium. Observed after about half an hour to an hour one the first sign of gelation. The temperature gradually rises to about 30 to 35 ° C up to at this point. This is followed by an accelerated radical polymerization, the temperature rising rapidly to 50 to 650C and approximately 5 to 7 minutes after the initial gel formation, complete polymerization is reached. The temperature then drops very quickly. The resulting product is a solid mass of clear and usually colorless gel. The gel is on Surface dry, has little flexibility and can be used with the fingers be crushed.

According to the basic embodiment of the invention 5 g of acrylamide and 0.3 g of methylenebisacrylamide (i.e. based on the used Amount of acrylamide 2.7 mole percent methylene-8 bisacrylamide) together in 15 milliliters Water dissolved in a 40 cm beaker. The initial temperature was 17 ° C and fell due to an endothermic effect at 180C. After dissolving the starting materials 0.5 g of potassium persulfate was added all at once and mixed with the aqueous medium mixed. After an hour and eight minutes it was the first sign observed gel formation. Then the radical polymerization took place its progress, with the temperature rising very rapidly to near 650C and within three to four minutes the polymerization was complete. The resulting end product was a solid, clear and colorless gel mass. The gel was dry on the surface, exhibited little flexibility but could be crushed and with fingers crumbled with a metal spatula. The gel was then passed through a sieve, which had a mesh count of 16 meshes / cm, although of course a different one Mesh number can be chosen. The fine particles were then made from the sieved gel Washed out, whereupon the gel several times in water to remove impurities was suspended. The gel was finally filtered, with distilled Rinsed with water, alcohol and acetone and then dried in an oven. there has been a Almost 100% yield of dry white grains obtained per gram of gel showed a water absorbency of 4.6 g.

Example 1 In the basic exemplary embodiment explained above of the invention, the resulting polymer product was neutral; i.e. it did not show any Ionization. The following explains the production of a gel that acts as an ion exchanger can be used.

Using the explained in the basic embodiment Procedure were 5 g of acrylic acid and Q, 3 g of methylenebisacrylamide together in 15 milliliters Water dissolved in a 100 cc beaker. The resulting acidic solution was with 5 nNaOH neutralized and brought to a pH between 10 and 11. after the Solution had cooled to near room temperature, 0.1 g of potassium persulfate was in 2.5 milliliters of water were added and mixed with the solution. The reaction proceeded slow. The time required for gel formation was approximately 34 minutes and that Temperature rise was 2600. The resulting end product was clear, somewhat pink gel of firm but rubbery texture.

The gel was then granulated and washed thoroughly. It was then brought into the sodium form by an alkaline wash, which swelled strongly. The swollen Gel was then combined with dilute hydrochloric acid and thereby in the water form converted that has been isolated. A yield of 100% light beige colored Grains was scored. -The water absorbency per gram of gel was in the hydrogen form 2.0 g - and in the sodium form 8.6 g. The hydrogen form of the gel acted as a cation exchanger the Cupriions to form a deep water-blue gel that bound with an acidic Solution with a pH of 2 or below regenerated to the colorless form could be. One gram of gel in the hydrogen form showed neutralization capacity of almost 1.5 meq. Base.

Embodiment 1 thus explains a polymeric Gei according to the Invention of type A Bx, which can be used as a cation exchanger. Used in Example 1, instead of acrylic acid, diethyl vinylamine is obtained Gel that can be used as an anion exchanger.

On gels of the above type, using a graft monomer, which is identical to the compound A, for example, reaction components with terminal amines are grafted on.

For example, one based on the basic exemplary embodiment Gel made according to the invention using acrylamide as the punching monomer Diethylenetriamine grafted on. If the graft polymerization is carried out using a Compound carried out with terminal amines, the resulting can be graft polymerized Gel can be further substituted.

From the starting materials A and B according to the basic method of Gel A Bx produced in accordance with the invention has no reactive centers, so that reactive centers by dropping Au4 or by introducing substitution groups must be created.

To form gels of the A.Bx.C type, reaction component C is also added to the starting components used to form the gel, which provides sites which can easily be substituted with functional compounds either by displacement or addition reactions. The C introduced into the polymerized gel should be soluble in water or miscible with water, should not have a reaction-inhibiting effect and should have a functional end group which is still present after the polymerization reaction which takes place to form the gel. A soluble preformed polymer such as polyvinylamine can also be used as reactant C. C has the following general formula: T bM- T ab in which T comprises an end group from the a -NH2, -NH-NH2, -OH, -NH-OH, -SH, and -NH- (CH2CH2) 2 "NH" group Class is to form a saturated heterocyclic ring structure. Tb is selected from a group which includes the class for T and amines and mono-, di-, bi-alkyl-substituted amines having 1 to 20 carbon atoms, as in the following: Monoalkyl amine: 2-ethyl aminoethanol dialkylamine: N, N-diethylethylenediamine trialkylamine: -CH2-CH12-OH 2-hydroxyethyl trimethylammonium chloride carboxyl groups as in Aminoacetic acid sulfate groups as in NH2-C2H4-OSO3H 2-aminoethyl sulfate phosphate groups as in NH2 -02H4 -OPO3H2 2-aminoethylphosphate Phl oroglucinol, heterocyclic derivatives such as 2-ethanolpyridine and piperazine and aromatic groups such as ring amino groups which are not substituted by dietary inhibitors and a carboxylic acid group as in The M appearing in the middle of the formula for reactant C is derived from comprehensive group selected, where w, x and z are each 1 - 12, y is 0 - 8, P and Q are the same or different and are hydrogen, aliphatic chains with 1 - 12 carbon atoms, aromatic, heterocyclic, alicyclic groups, Acid groups, nitrile, halogen, nitro groups and T iC} T are, where K is 0, NH, N-NH2, N-NHOH and Tc is NH2, NHNH2 or NHOH.

Gels are of particular interest when they are produced as a reaction part taker C triethyl entetramine, diethyl entriamin, 1,6-hexanediamine, 1,3-propanediamine, Ethylenediamine, phlorogl ucinol, various substituted amines including Hydroxylamine, diethylamine, N, N-diethyl hydroxylamine, diethylamino-ethylamine, (2-hydroxyethyl) trimethyl ammonium halide, aminoacetic acid, aminoproprionic acid, Triethanolamine and 2,2 '2', 2 '' 'ethylenedinitrilotetraethanol, hereinafter referred to as EDTE designated, can be used. Using the compounds listed above C as well as acrylamide or acrylic acid and methylenebisacrylamide as reaction components A and B gels were made.

Example 2 5 g of acrylamide, 0.3 g of methylenebisacrylamide and 2 g of triethylenetetramine were dissolved together in 15 milliliters of water in a 50 cc beaker. To the A solution having a pH between 11 and 11.5 became a solution of 0.1 g of potassium persulfate and 2 5 milliliters of water were added and mixed vigorously with the starting solution. The polymerization began within a few seconds, the temperature being within Rose to nearly 85 ° C for 1.75 minutes. The temperature then decreased very quickly. That resulting polymer was a clear, colorless solid gel of rubbery texture and firm consistency. The gel could be crushed with your fingers and easily granulated will. The gel formed was crushed and by a stainless steel Sieve mesh made of steel with 16 meshes / cm. From the accruing Granules were leached out by washing with frequent changes of water and removed. The grains were then finally washed with distilled water and then rinsed with methanol and acetone to dehydrate the gel grains. After drying at between 70 and 80 ° 9, a yield of almost 100 was obtained % of crusty white-colored grains. The resulting polymeric gel was in all polar and non-polar solvents as well as in acids, alkalis and hot concentrated formic acid not soluble. The gel was made from alcohols and acetones dehydrated. The wet polymer gel could be used in solvents such as dioxane, dimethylformamide, Pyridine and tetrahydrofuran. The gel charred in concentrated Sulfuric acid. When the gel was heated in 1 nNaOH, an ammonia odor was felt.

The resulting polymer did not have a discrete melting point, but rather had a melting temperature between 190 and 212 C.

This melting temperature is the temperature at which the polymer loses its rigidity and collapses when squeezed with a spatula will. By analysis it was found that the molecular weight of the repeating Unit is approximately r.

When the dry grains are brought together with water it easily turns an equilibrium is established and the grains swell more in an alkaline solution on than in an acidic solution. The water uptake per gram of dry gel was 6.3 g. To determine the water absorption, the gel was used for at least 10 hours brought together with water and then filtered on paper. from to the Gel on the paper was blotted off the water until the gel was dry was. The dry gel was then weighed to determine water uptake. In the infrared spectrum of the gels prepared according to Example 2 were based on primary and secondary amino groups absorption bands to be traced back at 35004450 cm or at 8 - 9 »; for amide, amino and C-O stretching -1, while a carboxylate effect was found at 1400 cm or 7.1zu was observed. There were more bands of weaker intensity between 1100 and 1200 cm or 8.3-9.05r noted based on methine and C-N stretching Clues.

In the preparation of the polymeric gels of type A-Bx-C, the amount of B and C based on 100 mol percent A. B can be in an amount from 2.27 to 11.86 Mol percent are used. C can be used in an amount of 9 to 29 mole percent will. The initiator can be used in an amount of 0.3 to 0.7 mol percent will.

That used as an aqueous medium for carrying out the reaction Water can be used in an order of magnitude, for example 1000 up to 2000 mole percent.

The gel produced according to Example 2 can be used as a matrix for immunological Exchange and adsorbents, ion exchangers, molecular exchangers and for manufacture can be used by redox polymer. It can also cause the formation of a gelling agent can be used for divalent ions. The gel is a fluorescent polymer and can be used at low temperatures down to 1000.

According to the exemplary embodiment explained with reference to Example 2, the most diverse gels of the As Bx type. C are produced, the are suitable for a wide variety of purposes. In Table I are the starting materials and the main purpose for further specific examples juxtaposed.

TABLE I A- Bx C-Gel Main Use 1-1 Acrylic Acid - Methylenebis- Desiccant or kaacrylamide-ethylenediamine ion exchanger (H-form) -2 acrylamide: methylenebis- Matrix for immunological acrylic amide: diethyl entriamine absorber (exchanger) -3 acrylamide: methylenebisacrylamide: 1,3-propanediamine -4 acrylamide: methylenebisacryl - Immunological exchanger amide: Phloroglucinol -5 Acrylamide: Methylenbisacryl- Polyamide capable of gelation: hydroxylamine mer -6 acrylamide: methylenebisacrylamide: Diethyl amine anion exchanger (chloride form) -7 Acrylamide: methylenebisacryl drying agent amide: ethylenedinitrilotetraethanol Of those listed in Table I. Starting materials A and B are always the same, namely acrylamide and N, N'-methylenebisacrylamide, whereas C is different. There can be other examples of the production of different 'gels can be performed in which different combinations of A and C are used, while methylenebisacrylamide is used as B constant will. Thus, as A acrylic acid with C in the form of aminoacetic acid, aminoproprionic acid, Ethyl endinitrile tetraethanol or diethylamine can be combined. It was too vinyl sulfonic acid already combined with aminoproprionic acid or EDTE. It can also A can be varied, for example diethylvinylamine can be used as A, while either diethylamine or EDTE is used as C. According to the invention can two monomers can also be used as A, for example both diethylvinylamine and acrylic acid as well as acrylic acid and vinyl sulfonic acid combined with EDTE. at the above-mentioned combinations of reactants result in cation exchangers, Anion exchangers or mixed ion exchangers.

If N-vinylpyrrolidine is used as A and triethylenetetramine as C the resulting gel can be used as a molecule exchanger.

The following are substituted and grafted polymeric gels of the Type A. B and A. B. C explained so that the gels according to the invention for any Purpose that can be used must have reactive centers on the surface be provided, due to which the gel to chemical typical for the application Reactions can participate. As already explained above, for this reason the A.B.C type gel preferred. Component C provides functional ones in the finished gel reactive centers capable of participating in further reactions. In A B.C. type gel but only a limited number of such reactive centers of C present, as evidenced by experimental studies has turned out. To increase the number of reactive centers present can the gel formed with a mixture of C and A in the presence of a radical Catalyst are implemented in an aqueous medium. The monomer A binds additional C on the surface of the gel, creating additional functional reaction centers be created on the surface. It is believed to be a graft polymerization takes place, in which the monomer A is bound to double bonds present in the gel which are split up to form free valences. If A itself is a monomer that has some useful groups, it can affect that alone Gel can be grafted on and thus provides more functional groups on the gel surface. A monomer used for grafting without C present must be functional Have end group which is suitable for ion exchange, molecular exchange, etc. If a monomer of the desired functional group is not available, a mixture of 0 + A must be used, where C is the desired reactive Terminal group or functional group supplies and to the gel via the neutral monomer A is tied.

The following are polymeric gels of type A. B with grafted A and of type A.B.C with grafted A explained in more detail. If only the monomer A alone is grafted onto the formed gel, it must have a functional group have, as has already been explained above. If the monomer A in the gel has a functional exchange group, then should the graft monomer A to Gel monomer A fit so that a high exchange capacity is guaranteed. Gels with grafted polymers are particularly suitable as ion and molecule exchangers. Used preferably vinyl carboxylate is used as the graft monomer A, Vinyl sulfonate, vinyl diethylamine, acrolein and N-vinylpyrrolidone. To carry out of the grafting process, the gel formed with the graft monomer A only becomes in an aqueous medium. in the presence of a radical initiator (catalyst) mixed. As a radical initiator, he can also be used during production initiator used in the gel. In some specific embodiments became the functional group graft monomer A in an amount of 0.008 M per gram of preformed gel used, but also amounts in the range from 0.004 to 0.01M can be used.

The initiator concentration in these examples was 0.0011 M, however, amounts of initiator in the range from 0.001 to 0.002 M per gram can also be used preformed gel can be used. It is one for swelling the gel and for Preparing a slurry requires sufficient water per gram Gel can be approximately from 4 to 25 ml.

The following are polymeric gels of type A-B-C with grafted (C + A) and type A B with grafted (C + A) explained in more detail. It was already stated above that one is a neutral monomer A that is not functional reactive Has places for grafting the reaction component C onto the gel formed can be used if more reactive centers are desired on the gel. One takes indicates that the graft monomer A splits the double bonds present in the gel and in the process, additional C on the polymer due to a likely hydrogen migration due to attachment reaction binds so that on the surface of the gel further functional reactive centers arise. Preferably one uses in the present case as graft monomer A acrylamide, methacrylamide, N-vinyl pyrrole idinone and the like. Most preferred, however, are acrylamide.

As component C to create functional areas on the surface the gel by grafting is preferably used triethylenetetramine, diethylenetriamine, 1 8 -propanediamine, 1,6-hexanediamine and other similar polyamines and alkylenediamines with terminal amino groups. Good results are obtained when the weight ratio for 0: A is approximately 2: 1. The amount used per gram of pre-formed gel an 0 + A can be from 0.005 M to 0.02 M for C and from 0.0025 to 0.01 M for A. The amount of initiator used is in the range from 0.001 M to 0.002 M.

The amount of water used depends on the gel and can range from 4 to 25 ml per gram of gel. A 5-8% crosslinking in the preformed gel is useful , however, gels with a degree of crosslinking of 4-25% can also be used.

Polymeric gels of type A B. C with substituted Groups explained in more detail. It has already been pointed out that a gel of the type A B does not have any functional reactive groups on the gel surface, capable of various reactions by which other substances are bound to the gel can be. Therefore gels were made from components A. B and C, which have functional groups on the surface. Since on the surface one Gels of type A.B.0 functional groups from component C are available, one can add different substances to the Substitute gel. It is also possible to substitute different groups of the gel as well as graft additional material onto the gel A-B.C and even after the Grafting on an additional one again Perform substitution. So you can get the gel AB B after grafting on C + A or A with reactive groups of C and thereby introduce further functional groups. Of special Different types of aminobenzene derivatives, which are produced with the gel A. B. C implemented and can thereby be bound to the gel. These derivatives can then diazotized and both to hapten or other immunological substances as well of ion exchange, redox, fluorescence, metal gelation and molecule exchange compounds be bound.

A first group of respondents created by substitution Can be bound to the gel, includes substances that the gel for further reactions activate those attached to the gel hapten, antigen and other functional substances be bound. This group includes diazotizable arylamines. These connections are aminobenzene formers. An example is p-N-acetylaminobenzene acyl halide, the after substitution can be reduced and deacetylated to a bound to the gel to create p-aminobenzyl group.

Another example is p-N-acetylaminobenzenesulfonyl halide, through which p-aminobenzenesulfonyl group can be bound to the gel. Another one An example is P-nitrobenzene-Malkylhalogen, after reduction of the nitro groups provides a p-aminobenzene group.

P-nitrobenzaldehyde can be reduced to form the p-aminobenzene group will. Another example is -diazonitrobenzene, which after reduction of the nitro group a p-aminobenzene diazog group bound to the gel provides.

To other types of substituents that react on the gel matrix can be bound; belong to such groups as acid halides, sulfonide halides, Phosphoryl halides and> A-halo and dih <1oacety1 groups. At one execution Sbeispi el became a Gel made from acrylamide, methylenebisacrylamide and Triethylenetetramine prepared according to Example 2 and then blue with methylene (p-azobenzenesulfonyl) reacted (0.3 g per gram of diazotized gel), with a dark blue (indigo blue) gel was created, which acts as a redox polymer.

Example 3 1 g of a gel prepared according to Example 2 was under Use of between 30 and 40 milliliters of water in a 100 cm beaker. 0.5 g of potassium carbonate and 0.5 g of E-N-acetylsulfanilyl chloride were then added and mixed with the medium in the beaker. The respondents were left React between 75 and 80 ° C for about an hour until all reactants have responded with the exception of the gel.

The part floating on top in the cup was then decanted and that N -acetylaminobenzene sulfonyl-substituted gel was then washed with water until until it was neutral. It was then filtered and then washed well with water and in 0.5N HCI washed. No diazotizable amine had formed at this point.

The e-aminobenzene sulfonyl derivative of the material was recovered after the material in dilute hydrochloric acid with a pH below 1 at 80 C for 1 1/2 hours long deacetylated until an acetic acid odor was detected. The gel was washed by decanting with water until neutral. It was then filtered and rinsed with distilled water and acetone and then dried. That resulting gel, the g-aminobenzenesulfonyl groups introduced by substitution consisted of light cream colored grains with a melting temperature of 198,500. The water absorption capacity of the gel was 6.2 g water per grarr) rr} Gel.

As previously indicated, the substituted gels will be predominant used as an immunological exchanger. For example, when manufacturing of such an immuno-exchanger as the starting material prepared according to Example 3 substituted gel matrix used. The gel is first equilibrated with water, until it has absorbed an amount of water corresponding to its water absorption capacity Has. Subsequently, 0.2 N HCl is then added to form a suspension and the suspension formed is then rapidly cooled to 5 ° C. Then a cooled Solution of 0.135 M NaNO2 added dropwise until a little excess nitrous Acid is detected through starch iodide paper. The reaction mixture is then left React for 1 to 1 1/2 hours, maintaining a pH equivalent to that of Congo Red and sufficient excess nitrous acid must be provided. After this When the diazotization is complete, excess nitrous acid is mixed with sulfamic acid removed before the material is processed further. One to be substituted for the material Hapten is then dissolved in a 0.1 M phosphate buffer with a pH between 8 and 10 and the solution is then cooled to between 5 and 10 ° C. The diazotized matrix is then gradually added to the cooled hapten solution and good with it mixed, maintaining the pH between 8-10 with chilled 1N NaOH. The reaction is allowed to proceed in a refrigerator for several hours, whereupon the gel is filtered and washed thoroughly with repeated changes of water. To the An ultrasonic shaker can facilitate the leaching process during washing can be used. Finally, the gel is washed with dilute acid, then washed with distilled water until neutral, finally with acetone rinsed and then dried.

In Example 4 below, p-chlorophenol is used as a representative of a Hapten molecule used because the chlorine atom is used as a marker atom for analysis can be.

Example 4 0.3 g of the material prepared according to Example 3 were suspended in 10 milliliters of 0.2 N HCl. The suspension was cooled to 500, then diazotized with a 0.135 M sodium nitrate solution added dropwise, until the starch iodide test showed a slight excess. After initially excess nitrous acid had been removed from the cooled solution of the diazonium salt, 0.2 g of e-chlorophenol in 5 milliliters of the diazonium solution were gradually cooled Buffer at pH 10 added. An orange colored azo derivative was formed when the pH of the gel solution increased. The melting temperature of the resulting compound, which is the 4- (2'e-chlorophenol) -azobenzene sulfonyl derivative of acrylamide, Methyl enbisacrylamide and triethylenetetramine are gels formed is 203.5 ° C. Analysis of the resulting compound revealed that about every third aminobenzene group formed an azo derivative. One can use this way not only but immuno-exchangers also produce ion exchange polymers and redox polymers.

The aforementioned types of compounds that are substituted on the polymeric gel can be have different functional groups that are further implemented can be to achieve various properties, due to which the resulting Substance as an immuno-exchanger, ion exchanger, molecular exchanger and the like can be used. There are also different types of substances that can be used substituted for the gel according to the invention can be and in itself already have the same properties without further implementation of the functional groups is required. As a matrix for direct implementation to achieve gels are used for substances with one or more of the aforementioned properties of type A.B.C, of type A.B.C. with grafted 0 + A and type AB B with grafted GFA. These other substances that can be reacted with the gels must be at least difunctional be, with one end of the substances with the functional end group of the compound C can react, while the other functional groups are the ion exchanger-molecule exchanger- or have immunological properties. These substances have the general Formula: -m-E in which d is a halide, alkyl halide, sulfonyl halide, carboxyl halide, Acid salt, anhydride, imide, amine, hydrazine, diazo, alcohol, phenol, sulfhydryl -, isocyanate, isothiocyanate, sulfate-J epoxy or ethylene group, which is a bonding reaction the substituents on the gel matrix allows.

m represents the middle part, which does not even need to be present or which is aliphatic, aromatic, heterocyclic, or metallic Group acts. E represents the functional end group which is a mono-di-tri-alkyl substituted amine with up to 20C-atoms, an acid group including carboxylic acid, sulfonic acid, Phosphoric acid, arsonic acid and phenol groups, a pyridine group and an N-alkylated group May be pyridine salt group.

E can also be a nitro, nitroso, amine halogen, nitrile, sulfate, Ester, amide, alkyl, hydroxyl, or ketone group.

In particular, E can also be a hapten and immunological group be, these groups being substituted and unsubstituted derivatives of substances include, to which all forms of aliphatic compounds such as amino acids, saccharides, Fatty acids and their derivatives, steroids and their derivatives, aromatic derivatives with a single ring or with fused rings such as 2,4-dinitrophenyl- and Tyrosyl derivatives, saturated, unsaturated and fused ring heterocyclic Groups including amino acids, the derivatives of indole, pyrrole and imidazole contain derivatives of pyrimidine, purine, pteridine and pyridine as well as substituents with metallic groups such as porphyrin derivatives. Specific examples of used Substances are alkyl halides and derivatives in the form of ethyl iodide and in the form of a carboxylmethyl chloride, which after reaction with a gel according to the invention form an ion exchanger. A diazonium derivative such as diazobenzenesulfonate provides after reaction with the gel an immuno-exchanger. At DinitrophenyFund Trinitrophenyl -Substitution creates an immuno-exchanger as well as when using ureido- and thioureido derivatives formed from substituted isocyanates and thiocyanates are. Another immuno-exchanger is obtained with a sulfone derivative such as based on of Example 3 has been explained, in which the p-aminobenzenesulfonyl group is attached to the gel is bound.

The polymeric gels discussed above can be considered a new class of substances that are used as starting material or as a matrix can be attached to and / or with which various other substances various other substances can be implemented. With the new substances according to the invention it is not human food or pharmaceuticals, as they are used, for example, to treat illnesses or to relieve pain can be used.

Claims (7)

PATENT CLAIMS: 1. Polymeric gel of the type AB, wherein A is a water-soluble or water-miscible monomeric material with one that can be split into free valencies Carbon double bond and B a water-soluble and water-miscible one monomeric crosslinking agent with at least two to participate in a crosslinking reaction capable end groups, characterized in that AB B copolymerized and / odep A graft monomer is attached to AB B, creating reactive sites on the gel for a certain type of chemical reaction. 2. Polymeric gel according to claim 1, characterized in that the original gel A B is produced in this way (for example in the form of A, A '.B or A, A ', A', B etc.) that it itself contains components that are reactive sites exhibit. 3. Polymeric gel according to claim 1 or 2, characterized in that A B is copolymerized with a compound C which contains a group which with a double bond in the monomer A or in the crosslinking agent B during the polymerization has reacted and still has another functional end group that easily can be substituted with additional groups. 4. Polymeric gel according to any one of the preceding claims, characterized characterized in that a compound is grafted onto the original polymeric gel which has reactive sites. 5. Polymeric gel according to claim 4, characterized in that a material falling under the definition of monomer A either alone or in combination grafted with a falling under the definition of the Ma-material C monomer will. 6. Polymeric gel according to claim 4, characterized in that the Gel is made to have the desired reactive sites. 7. Polymeric gel according to claim 1, characterized in that A is acrylamide and B is methylenebisacrylamide.