DE2722346A1 - WATER-SOLUBLE HALOGEN COMPLEXES, PROCESS FOR THEIR PRODUCTION AND THEIR USE IN HYGIENE AND DERMATOLOGY AND FOR MAKING FLUIDS ASEPTIC - Google Patents

Description

The invention relates to new, neutral and insoluble complexes! which by complexing metalloid halogens in an insoluble, non-toxic, physical or chemical Affinities for these halogens having matrix can be obtained.

Furthermore, the invention relates to a process for the preparation of these new complexes and their application for all technical Applications in which an oxidizing effect of metalloid ^ halogen and especially metalloid iodine is desired, especially for cleaning and in particular bacteriological cleaning of different liquids and gases, or for the treatment of different parts or organs of objects or living beings in order to achieve bactericidal, antiseptic and fungicidal effects, in particular when used in the field of plant health, in veterinary medicine or as a medicine,

In the following description, reference will always be made to iodine, this being as a non-limiting example of one Halogen was chosen; of course, those skilled in the art can understand the properties achieved with iodine also transferred to the other halogens. It should be noted, however, that iodine is the halogen, its effect occurs fastest in bacteria.

It is known per se that iodine, for example in the form of an aqueous solution in potassium iodide, can be replaced by polymeric substances chemical structure can be absorbed.

The test known as "iodine absorption" and proposed by V. LACKO and M. GALANSKI (CA ^, 4085f) is in fact often used to visualize and characterize structural modifications of a polymeric material _for physical, chemical or physico-chemical treatment such as heating has been subjected to irradiation or oxidation,

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and it has been carried out on numerous polymers.

In addition, it is known that polymers or macromolecules Have physical properties, which are often influenced by factors such as the degree of polymerization, the two-dimensional or three-dimensional character of the linkage and of course the chemical nature of the monomer are dependent.

However, it is known that their very low solubility in water and often also in organic solvents is practical is a general rule.

On the other hand, there is no lack of technical or purely chemical means to make a polymer material insoluble, e.g. the incorporation of halogenated monomers, the removal of all free, hydrophilic groups, the crosslinking by incorporating bifunctional coreaction participants such as divinylbenzene or the aut © condensation of polymer chains belonging reactive groups to obtain a three-dimensional network.

Therefore, it is easy to make various, insoluble, polymeric materials that have groups in their chains, which complexes of suitable stability with halogens can give.

Because of the per se known advantage of halogens and certain Derivatives thereof in all areas that address the problems of disinfection, sterilization, bacteriological Cleaning, fungistatic stabilization, etc., the considerable benefit can be seen a complexation of halogens and their derivatives and in particular of iodine, the effect of which is the fastest, inside such an insoluble matrix could bring with it side effects, for example on the mucous membranes (Eyes of bathers in swimming pools), odor or unpleasant smell in liquids (with beverages or in particular also in swimming pools) can be safely reduced to a minimum. 7Q9848 / 1060

Most of the known compositions containing iodine concerns in mass 1% borrowed complexes, therefore are unable to carry out operations such as the purification of water for industrial use, beverages, swimming pools, the treatment of any liquids intended for beverages, etc.

In addition, the iodine absorption tests did not examine the bactericidal activity of the iodine absorbed containing, polymeric fiber carried out in order to ensure the availability of the absorbed in this way and the previously mentioned, industrial applications enabling iodine to be detected, whereby the complexation of iodine by the fiber was in each case incomplete because of the procedure used in these tests.

However, reference should be made to the formation of complexes of iodine with copolymers between cellulose and benzyl methacrylate or styrene (CA 21 »51161b) and a polyether wax (CA 51 « 15395h), but in both of these cases the complexation of iodine seems to be incomplete play in liquid phase.

Furthermore, US Pat. No. 3,084,132 and GB Pat. No. 1,101,344 disclose iodine-treated polymers described, but the products obtained can be solubilized by water or by conventional organic solvents.

Finally, US Pat. No. 3,625,025 is known where a polyethylene-vinyl-2-pyrrolidone copolymer is used, also FR patent specification 1 354 II5, where the matrix due to the insoluble, crosslinked polymer of vinyl-2-pyrrolidone is formed.

However, it emerges from the latter patent if one considers the fate of the in the tight reaction vessel with the insoluble, crosslinked vinyl-2-pyrrolidone polymer imported, metalloid iodine that one

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only about 2/3 in the course of a determination of iodine with sodium thiosulphate under conditions which can be addressed as normal finds again, i.e. one can be sure that it is the determination of the whole, actually in oxidizing Form existing, metalloid iodine enable.

It should be noted that the same amount of loss, i.e. about 1/3 ", in this patent for complexation of iodine is found by other crosslinked, insoluble polymers of N-vinyl-heterocycles, and that this is constant Value of the extent of the loss regardless of that Heterocycle, which leads to the well-known ratio (iodine) / (iodic acid) = 2, can be interpreted as follows.

The presence of water in a substantial amount in these insoluble polymers is certain, even if no precise determination is given and in spite of the mention of “drying at 50 ^° C. under vacuum”. Such insoluble macromolecular compounds, which have been thoroughly washed with water to remove the basic catalyst present, are well suited for absorbing water in large quantities.

Since it is known that iodine has a tendency to break into moist medium a disproportionation reaction in iodine water to give off acid and hypoiodic acid, one arrives therefrom to hydriodic acid because of the loss of oxygen.

This conversion reaction of iodine into hydriodic acid by the action of water can be made much easier take place in the presence of organic compounds, where the presence of the substitution activating groups of the radical type brings with it the possibility of iodination reactions, the derivative formed can rapidly undergo later hydrolysis to give the aforementioned hydriodic acid without substantial modification of the polymeric material to form.

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The presence of this residual water in the polymers used can therefore be one of the causes of the loss of the third of the iodine introduced in treating the mixture.

This interpretation is also confirmed when one considers the work described in US Pat. No. 2,826,532, where the addition of about 5 # water to water soluble polyvinylpyrrolidone is considered essential for that appropriate stability of aqueous solutions is considered to be formed by the iodine carrier produced in the solid phase, always with the same ratio (iodine) / (acid) = 2.

In fact, the strong acidity of such aqueous solutions is also compatible with the presence of iodic acids, and one finds here also the loss of about a third of the imported iodine.

The conditions of the reaction on the one hand and the chemical reactivity of the crosslinked and non-crosslinked polymers on the other hand, they are sufficiently analog that the previously formulated hypothesis can be confirmed.

As a result, the description of the aforementioned crosslinked polymers and their complexes with iodine makes it possible predicted that such complexes would probably have about a third of the iodine used in their manufacture in the state of water-soluble iodic acids and can therefore be removed by washing with water.

From this arises one of the main disadvantages with respect to the industrial Use of such complexes, be it for the purification of all waters or drinks or for the application on objects or organs and mucous membranes, which can be changed by a strong acidity, so that these Complexes have not been developed. It was therefore completely surprising to find a variety of new, iodine-containing

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To find complexes whose properties were like theirs Application for industrial purposes, as they were previously mentioned, was possible.

It has now been shown for the first time that a large number of insoluble complexes containing iodine can be formed, every time metalloid iodine and a substance of the insoluble, polymeric type are brought together.

The process according to the invention consists either in heating the mixture of iodine and polymer in solid form Phase with stirring the mixture or in heating a solution of the halogen in a suitable solvent, e.g. halogenated solvents, ethers, alkanes and cycloalkanes, whereby the polymeric material is in suspension is in this solution.

Incidentally, this heating may not be necessary if the polymeric material has remarkable physical properties or has chemical affinities for the substances to be absorbed and in particular the halogens.

The required heating temperature is generally between approximately 90 ^° C. and 100 ^° C. in the solid phase and between the usual temperature and the boiling point of the solvent in the case of complexation in the liquid phase.

For example, was passed through 1OO ° C, because of a - in the case of a matrix with intermediate affinity, however, heating to 90 may - 100 ⁰ C be advantageous if the latter at a temperature below 90 for a few hours after the treatment in liquid phase The boiling point of the solvent used is not sufficiently high, as in the case of carbon tetrachloride or a light petroleum ether.

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The selection of the method depends, among other things, on the chemical stability of the polymer in the presence of iodine.

So working in the liquid phase can also be done in the Recommended cases where the polymer used contains traces of a fraction that can be dissolved in this method is soluble in organic solvents which can be used by iodine.

In contrast, polyamides can because of their thermal stability in the presence of iodine without disadvantage after one or the other treatment method, but the solid phase treatment for economic reasons can be preferred.

The duration of heating and the amount of iodine fixed also depend on the chemical nature of the monomer or monomers used to make the polymeric material from, wherein the polymeric material can have a very different affinity for iodine, further from that physical state of this material, this state being dependent on the treatments carried out before complexation and influences, among other things, the porosity, the grain size distribution, etc.

All of the unique complexes obtained had very advantageous properties if the following conditions were met were complied with:

- The polymer material used must have a very low moisture content (below 0 _t 3 #), and it must be absolutely insoluble in water (solubility _value below 10-5) so that soluble fractions (water or organic solvents) preferably through a previous treatment must be removed, especially for applications where the intended liquid has to be filtered, including beverages;

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the proportion introduced into the mixer must be at least 20 % below the saturation value of the polymeric material;

the heating must be continued for a sufficient period of time for optimal introduction of the iodine to bring about, whereby this heating period can be followed by an under-vacuuming of the mass, so that the last Traces of iodine which have not yet penetrated the absorbent mass can be removed.

Under these conditions are the advantageous and unique properties that the novel, industrial Applications of the new complexes according to the invention allow mainly the following:

- All polymeric materials used hold all of the iodine that was added to them during the mixing process, except for a few minimal losses (maximum 1 to 3 #) die are essentially of mechanical origin, returned exclusively in the oxidizing, metalloid iodine state;

- All complexes obtained in this way give on transferring into suspension with stirring in neutral water at all no acidity, the possibly released traces of iodine in the case of prolonged stirring by more than a few minutes, which were determined by microtitration, in most cases only of the order of magnitude of ppm (ppm = parts per million) without any disadvantage in terms of smell, taste or quality of the treated Water can be removed, either by adding a few ppm of sodium thiosulphate or by simple Carry out over some grains of e.g. animal charcoal or vegetable charcoal.

As already described above, the working conditions enable the complexation according to a variant of the method it is in any case to produce complexes in which the halogen is more or less bound, so that the requirements for the application of these various complexes are fulfilled.

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In addition, it should be pointed out that one - fsu.ls this what is desired - animal charcoal or biochar (activated charcoal) can be added directly to the iodine-containing powder, and -that this Mixture can then be used to purify any liquid.

Under these conditions microtitration of iodine yields only traces which can be below 0.1 ppm for the most highly complexing polymeric materials which have received the most effective treatment and in which the incorporation of iodine is on the order of at most 50 % of their maximum absorption has been performed. The complexation of iodine by the polymer matrix can be restricted by a degree of saturation of iodine below the degree of saturation normally obtained.

The observation of the absorption of traces of iodine by a material like coal in all its forms is already ancient: Activated carbons have been widely used in nuclear plants, to contain the traces of volatile radioactive iodine in the exhaust gas streams, and it is well known that these Fixation is remarkably powerful.

However, it does not seem to be the case between iodine and the complexes obtained in any form from the various carbons had previously been considered and investigated as such and that it would therefore have been found that it could be a source of iodine, i.e. the properties these complexes have only been identified from the point of view of their ability to retain iodine (or other halogens) investigated under the influence of fluid means (liquids, gases) or thermal means, but at all not from the point of view of the activity of the halogens included in these complexes towards their reactive ones Antagonists such as thiosulphate and chemical reducing agents or against bacteria and biological Reducing agents.

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The types of carbon in all forms, which Kotilenstoffpolymerisate are insoluble in water and organic solvents, and if necessary, take the necessary precautions are taken, they are non-toxic, for their remarkable decolorization properties Absorption of chemical substances (liquids, dissolved substances, fine solids) particularly well-known matrix materials represent.

According to a feature of the present invention would be exact showed that suitable types of carbon polymeric materials of the type described above (organic polymers) with regard to their properties and in particular their ability to absorb and for their applications after the Represent fixation of halogens.

According to the invention, the complexes according to the invention originate from polymers which are insoluble in water and aqueous liquids, and they are based on organic, polymeric matrix materials,

which suitable functions to ensure complexation of halogen molecules by charge transfer or bonds of the van der Waals type, obtained, such Polymers belong to the class, which by polyvinylpyrrolidone, the polyamides of copolymers or polycondensates and the types of coal in all their forms, as well as their origin, their grain size distribution and their previous ones Treatments are to be formed.

All of these new complexes are remarkable because that complexed Halogen is only retained in molecular and therefore active form, and because the presence of the halogen is always present by the bactericidal properties attributable to the halogen in question.

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The main uses of halogen are disinfection, antiseptic treatment, sterilization, fractional sterilization, and rapid pasteurization of all liquids that are to come into contact with mucous membranes or other living tissues. In such a case, it is advantageous to limit the amount of iodine included in such complexes to 10 %, and preferably to 6 to 9 #.

Asepticization of gases can be done with complexes with higher iodine content (10 to 15 #) on condition of selection an insoluble starting polymer which is not hygroscopic should be and has good absorption.

All treatments in the field of plant health can be carried out with complexes with a comparable iodine content as well as fungicidal treatments, the treated material, however, being to a given limitation of what is desired Iodine content can lead.

It is also possible, as previously described, to use complexes in which the iodine is less strongly complexed to Generators for weakly coded water (1 to 5 ppm) simply passing water over such special complexes: such coded waters represent remarkable Liquids for disinfection and washing in industrial applications as well as applications in the household.

Finally, in the medical field, such complexes can be used in powder form for rendering skin surfaces aseptic or use mucosal surfaces, with a suitable fine division (micronization) through Synthesis obtained powder if necessary to the desired

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the highest degree of fineness, one can continue to do the complexes in the form of capsules, coated tablets, suppositories or tablets for making aseptic in situ and in the form of soaps, Use dry shampoos, ointments or pomades, toothpastes, chewing pastes for hygienic and dermatological applications.

Of course, the selection of polymeric material for such applications in the medical field is for Humans or animals depending on the tolerance and toxicity of this material that is in direct contact with Mucous membranes and living organs should come more restricted.

In particular, the new substances or drugs used as medicaments, which contain the complexes, contain approximately 80 % carrier or diluent and 20 % complexes, these being in the form of powders with a fine particle size distribution and their complexed iodine content in weight practically 5 % .

The new complexes with iodine are for various industrial and technical applications in the following areas certainly:

Hygiene products, treatments with germicides, pesticides, fungicides, bactericides, antiseptic treatments therapeutic areas in humans or animals, as well as in the treatment of plants, for disinfection of all liquids that come into contact or are intended to come into contact with living tissues, especially with Mucous membranes such as water, especially for drinks, water in swimming pools, for industrial work processes certain water and in particular in the field of cosmetics, food, agriculture etc., for beverages of any vegetable origin (fruit juices) or animal origin (milk).

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Likewise, the new complexes according to the invention for The aseptic treatment of gases and especially of air can be used for cleaning everything in the household and in industry and devices or objects used in public or private areas (walls, floors etc.) for the fungistatic treatment of tissues, of Layer or press plates, of ropes, nets or sails, which are used in shipping, and more generally Way in all cases where there is a germicidal effect of iodine in preventive or curative form or for both purposes at the same time is desired, the essential advantages of these new complexes according to the invention come into play, namely their complete insolubility, their retention of Iodine and the complete absence of acidity and harmfulness.

Returning to the extraordinary properties of the ^{novel 1} ,, iodine-bearing complexes produced according to the invention and thus to the remarkable process for their production by combining the agents used for the first time, the following features should be pointed out in particular:

If a slow release of iodine through the action of water is desired, in this case cleaning water is used With a low iodine content, the complexes suspended in the neutral water result in the latter no acidity at all and no discoloration and no reaction with starch, which is the complete character the complexation of iodine and the remarkable retention of iodine inside the complex.

The titration of iodine with alkali thiosulphate is difficult, when using the normal method, which consists in using a pre-adjusted sodium thiosulphate solution until it disappears the yellow to red color of the complex.

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This practice is with an iodine-bearing, water-soluble complex such as the water-soluble polymer described of vinyl-2-pyrrolidone, its iodine, although it is is partially "masked", immediately under the action of an antagonistic reactant such as Releases thiosulfate.

In the case of the new complexes prepared according to the invention the discoloration observed is extremely slow, even if the equivalence point is exceeded, which is an additional one The argument is that the extraordinarily strong complexation of iodine and the difference compared to the state the results achieved by the technique.

A determination of the active iodine is made using the bactericidal effect of the complexed halogen a known amount of germs such as coli bacteria, staphylococci, Enterobakte'r cloacae are preferred.

Taking into account the percentage of iodine introduced and the absence of iodic acids and thus based on the foreseeable percentage of iodine that the compound to be determined will release, the bactericidal effect of a solution with a known iodine content and of three samples of the complexes to be determined is compared in certain quantities for the same number of germs as follows: m _Q (foreseeable mass taking into account the previously estimated percentage),
m _o / 2 and J> n _Q / 2.

In general, the effects (defined below) of the sample iodine solution and the calculated mass of the complex to be determined (m _Q ) are completely comparable, the results obtained by the amounts m / 2 and 3 ^ / 2 of the same complex being substantially different from the are given by the mass m _Q.

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It should be noted that in the case of the coded complexes * which were obtained from the different types of carbon used, a suitable determination or titration of iodine can be achieved using a "determination technique", the implementation of which (see the following remarks) shows the particularly slow release of iodine from these complexes. This determination or titration gives indeed results fully comparable to those obtained by the biological method.

This determination, which is used especially for complexes using carbons as starting material, is relatively gentle, since under the same conditions most of the other complexes provided according to the invention "which were produced from organocarbon polymers, lead to results that are always below 5 % of the content resulting from the first technique, this obviously being much more conclusive and representative of the bactericidal properties of the novel complexes prepared according to the invention, taking into account the desired application purposes.

In the same way, such complexes, which were prepared from polymers other than carbon, with a Solvents are treated like acetone, which extracts a small part of the molecular iodine; however, leads itself after longer extraction with larger volumes of solvents, the titration that can be carried out with thiosulphate in this case even to very minimal values.

It should be noted that solvents typical for iodine, such as polyhalomethanes, have no extracting effect on the For example, complexes derived from polyamides proved.

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Especially in the case of complexes obtained from polyamides, the iodine extracted during the extraction is below 1% of the expected, if

the mass fraction of iodine introduced into the polyamide is taken into account. It can therefore be seen that there is an absolute complete complexation has been achieved and that total masking has an optimal retention effect of the iodine with all resulting consequences can be expected.

The characterization of the new complexes is as follows: they are in the form of powders with a yellow to reddish brown color corresponding to the content of complexed iodine, if an organocarbon polymer is used as the matrix; if a carbon of any origin is used, the complex formed will of course be black. The complexes have neither a taste nor a smell. Like the matrix materials from which they are derived, they are completely insoluble in water and organic solvents. .

It is noteworthy that the spectroscopic properties (especially the IR spectra) differ very little from those of the starting matrix materials, in contrast to that which, taking into account the well-known, the aforementioned investigations would have been expected.

The bacteriological study, which allows the activity of the new iodine-bearing complexes to be assessed, was carried out according to a technique, the general principle of which is well known: it consists in inoculating bacteria on the surface of a layer which, by incorporating the produced powder in a culture medium, is inoculated homogeneously, this incorporation preferably taking place at approximately 45 ^° C. (supercooled nutrient medium).

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For about twenty bacterial strains the antiseptic effect was obtained in this way for different concentrations investigated on active iodine from complexes with polyamide 11, this substance being chosen here as an example to to compensate for the requirements of achieving suitable homogeneity and easy installation.

A comparative test had previously shown that the polyamide 11, like the other materials investigated has no antiseptic effect of its own, which therefore allows the concentration of this polyamide 11 in the nutrient medium can be varied without prejudice to strict adherence to the procedure.

Inoculation was carried out by means of cultures in liquid medium containing 10 to 10 germs / ml and were so diluted that colonies were obtained which were enumerated and well individualized? could be (50 up to 100 colonies per Petri dish with a diameter of 6 cm).

There were three types of reaction when the new, iodine-containing complexes to be expected: no activity, a bacteriostatic effect or a bactericidal effect.

Therefore, in order to demonstrate the performance of the invention, a rigorous bacteriological examination was carried out, which It made it possible to determine the limit concentrations of iodine for each of the germs examined, which were named for each of these three Reactions correspond to determine.

As a bacteriostatic effect, the fact of the observation either of a lack of colonies or of clustered, hypotropic bacterial colonies compared to the comparative sample, with a new addition of nutrient broth gave a positive culture in 24 hours at 37 ° C.

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The bactericidal effect was considered to be the fact that a complete absence of colonies on the surface of the nutrient medium was observed, with a new addition of nutrient broth at 37 ° C in 24 hours in a test tube no bacterial growth resulted.

On the basis of the examples described in detail below, it has been found that concentrations of iodine in the order of magnitude of 0.05 % generally produce a suitable bacteriostatic effect, while a bactericidal effect is achieved for levels in the order of magnitude of 0 _f 07. #, where the specified percentages of iodine in the description relate to percentages by weight.

Taking into account the quantitatively completely comparable reaction of the different investigated Bacterial strains are here only the effects on enterobacteria (Colibacteria), which the applications for the Cleaning of liquids with different intended purposes, described, e.g. the types of water, which are to be brought to "consumption quality", the Water for swimming pools or the sterilization of liquids at ambient temperature that enter the interior to be introduced by living organisms.

Inoculation of physiological water by a known amount of coli bacilli was therefore carried out.

This artificially contaminated water (100 ml) was treated with stirring with 0.1 g of a 4% encoded powder in such a way that a suitable suspension was obtained.

Samples were taken every 15 minutes and for inoculation of dishes with nutrient medium according to the technique given above.

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The bacteriostatic effect was considered to be ' that no growth was observed (the comparative examination of the matrix without iodine showed the presence of numerous colonies and thus a lack of any effect), and the bactericidal effect was considered to be the fact that that again no germ was observed at all if the dishes were flooded with culture broth after 24 hours became.

With regard to the cleaning of more complex liquids in the food sector such as milk, fruit juices, Alcoholic or non-alcoholic beverages, the studies were carried out on cow's milk as it is well known is that this is one of the fluids for drinking, the most rapidly defining, major changes among the effects of all chemical and bacterial agents.

Here the attempt was made to have milk from the farm in attendance of the new complexes, namely the complexes derived from nylon 11 and an activated carbon, used for this study were chosen to stir.

A microscopic examination of the flora before and after staining was carried out on fluids exposed to exposure of the new complexes for 1 minute (0.1 g per 100 ml of raw milk supplied by a contracted farm) the comparison was made with a comparative sample that had received no treatment at all

In an analogous manner as in the treated water locations vaccination trials were carried out on culture media for 24 hours in an oven at 37 ⁰ O.

First, the milk was observed after decanting (stopping the stirring) in order to avoid any loss of fat.

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acids to be determined by absorption on the complex. Thereafter a microscopic examination was carried out before and after staining to detect any changes as well as the presence of a flora, the density of which was examined in comparison with the untreated control sample.

Finally, at the end of the oven treatment, filtration on paper made it possible to identify any Presence of coagulates.

A chemical study of the behavior of the iodine included in the new complexes which was brought into contact with reactants for iodine was carried out. Besides sodium thiosulphate, which has already been mentioned, the effect of ethylene-like compounds (alkenes and unsaturated Fatty acids as found in the form of triglycerides in milk) to determine whether any, even a low risk of iodine being entrained in any form in the purified liquids via a Intermediate effect of any fixation on the double bond is given.

The alkene or the fatty acid (in free form or as the sodium salt or methyl ester) was converted into solution and treated with its weight of iodine (i.e. 10 times its weight of complex with 10 % iodine or 25 times its weight of complex with 4 - % iodine) treated.

At the end of a stirring period of 24 hours at ambient temperature the solution was filtered, the solid mass of the iodine-bearing complex was washed with solvent, the obtained Solution evaporated and the residue according to the usual analytical procedure in inorganic compounds transferred to determine the iodine, which might have been in any form (molecular or organic) can be carried away.

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The transfer of the iodine-containing, produced according to the invention, new complexes in their form depends essentially on their insolubility, this being an original Characteristic for the non-acidity is.

It should be pointed out, however, that the fine comminution (micronization) of the iodine-containing powders of normal particle size distribution "taking into account the polymer used converted into powder, which ultimately into any Liquids can be transferred into suspension.

You can go directly to the "powder" form, as well as the complex directly is obtained for disinfecting large surfaces (floors, carpets, tiles) or small surfaces (biological Damage, plant damage or animal injuries) Use e.g. by spraying on or dispersing with the aid of a propellant gas (spray powder, dividing devices, etc.).

The complexes in solid form can also be used in filter cartridges for cleaning all types of liquids like the different beverages (non-alcoholic or alcoholic beverages, milk, fruit juices, mineral waters); the waters used in industry (in closed circuits, in the paper industry, for cosmetic Purposes) and for drinking water for animals and humans and especially for all natural waters.

In these cases, the filtration can possibly entrain a few ppm of iodine, which (especially in the case of pure water) give a weak taste, so it may be advantageous to have a small section at the lower end of the cartridge provide containing an absorbent charcoal or any analogous insoluble substance known to that it retains iodine at very low concentrations, whereby of course the matrix of the complex already can be coal or not coal.

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As already described above, one can also use the iodine-bearing Mix complexes to a carbon powder in any form.

In such a case, after oxidation and conversion to the inorganic state, no more than 0.05 ppm Find iodine in a liquid. The taste cannot be determined either.

Of course, the same applies in the case of an iodine-bearing complex only on the basis of charcoal in any. Shape.

For the other applications, the iodine-containing, synthetic powder is used in the form of a cream, pomade, ointment, etc. transferred, which by dispersing the coded, optionally micronized or finely comminuted complex in a suitable substrate, i.e. from a physical point of view preferably water-miscible substrate and from the chemical point of view a substrate unreactive with oxidizing iodine.

The invention is illustrated in more detail by means of the following examples.

The following examples relate to the preparation of the new complexes according to the invention.

example 1

100 kg of polycondensate are poured into a mixer with corrosion-resistant walls (preferably made of enamelled steel) 11-Amino-undecanoic acid methylate (under the name Nylon known) introduced.

The temperature is brought to 100 ^° C. and the reaction vessel is placed under vacuum, the powder being stirred in such a way that the removal of moisture is supported. If the opti-

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male vacuum is reached depending on the apparatus! the normal pressure adjusted again and quickly introduced 10 kg of crystallized iodine.

The reaction vessel is immediately closed tightly and the stirring and heating to 100 ^° C. are maintained for 10 hours.

It is found that this in large quantity affects the cold Wall of the lid of the reaction vessel in the first period of mixing, iodine progressively sublimated into the powdery Builds in mass, and that at the end of the reaction practically nothing remains of this on the lid.

As a precaution, however, the reaction vessel is at 110 ° 0 placed under vacuum for about an hour, then the iodine-containing or iodine-bearing, in this way obtained complex. '

Complete complexation of the iodine is confirmed by filtering 10 ml of water on 1 g of the powder: at all no discoloration nor a taste can be determined; the addition of starch gives no color at all and the pH a neutral water does not change.

The titration of iodine is carried out in the following way: an equal volume of physiological inoculated with coli bacilli Water, as previously described, is introduced into:

- 100 ml of water containing 1 mg of iodine in solution,

- 100 ml of water with 11 mg (m _Q ) of the complex in suspension,

- 100 ml of the water with 5.5 mg of the complex in suspension,

- 100 ml of water with 16.5 mg of the complex in suspension.

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It is found that the bactericidal effect is achieved in tests 1 and 2 in a practically comparable manner, this is a good confirmation of the value of 9 % iodine, which results from the amounts by weight of the matrix material and the iodine introduced into the mixer.

Example 2

The drying of the organic polymer (nylon 11) is in a reaction vessel by the action of twice Weight of heptane, which is brought to reflux, achieved the azeotropic distillation of the in the polymer contained water.

The remaining heptane is then removed by evaporation under partial vacuum, and the treatment is then concluded as in Example 1 by adding 10 kg of crystallized iodine and heating to 100 ^° C. for 10 hours.

The final vacuum transfer is also carried out as this removes the last traces of unwanted material Solvent allows.

The titration or determination as in Example 1 also results in an iodine content of approximately 9 #

Example 3

As in Example 2, after the water has been completely removed by azeotropic distillation, the solvent is in the Maintain the excess and add the iodine in the form of a dilute solution, e.g. in heptane or another solvent, added.

After heating for 10 hours at 100 ⁰ C, the treatment is as previously completed by distillation of the solvent and the vacuumizing of the reaction vessel.

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The content of fixed iodine, determined as in Example 1, is also about 9 #.

The complexes obtained according to Examples 1, 2 and 3 show no difference whatsoever with regard to this appearance or further behavior.

Example 4

25 kg of activated carbon in granular form (average diameter of ₁ O 5 mm) are slowly poured into a solution of 4 kg of iodine in 100 light petroleum ether.

The solution is completely decolorized. The excess solvent is then filtered and recovered, and then bringing the Peststoff obtained under vacuum (about 5 millimeters of mercury) to a temperature of 60 to 70 ⁰ C. In this way one obtains 29 kg complex was in which the iodine is determined by the following method :

Approximately 1 g of the powder is mixed with 20 ml n / 10 sodium thiosulfate solution treated in a sealed Erlenmeyer flask.

The mixture is stirred for 4 hours (magnetic stirrer), then after the addition of starch solution, the excess of thiosulphate is removed by adding a n / 10 solution of iodine until the characteristic starch coloration titrated.

In this way the percentage of iodine is obtained from the values in the usual way. It will be a salary of 13 * 6 # found, while the theoretical, calculated value 13 »8 # amounts to.

Example 5

25 kg of activated carbon in powder form of medium size (grain size distribution on the order of 50 to 100 microns) are stirred with 2.5 kg of very finely powdered iodine.

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272234g

After stirring for 4 hours at a temperature of 50 to 60 ^° C., approximately 27 kg of a solid complex are obtained which, in the back titration method with thiosulfate, has a content of 8.9 # iodine.

Example 6

From 100 kg of a polycondensate between adipic acid and hexamethylenediamine (nylon 6,6), which as in Example 1 for Dehydration were treated, and 5 kg of iodine are obtained by the same procedure 104.5 kg of complex, which at the determination by bacteriological means show a content of about 4.5 # iodine.

Example 7

Treated from 100 kg of caprolactam polycondensate (nylon 6) as in Example 2, as well as 7 kg of iodine, 106 kg of coded complex containing more than 6 # iodine, determined on bacteriological basis, are obtained Way, contains. '

Example 8

In this example the procedure for the production of encoded polyvinylpolypyrrolidone is described, in particular is advantageous for its applications in the hygienic and pharmaceutical fields.

There are three working methods for cleaning:

A. Commercial polyvinyl polypyrrolidone (PVPP) is purified using the following procedure (Removal of the larger proportion of the water present and the soluble polymer present):

100 g of the commercial product are successively mixed with 6 fractions of 100 ml of boiling water treated, each addition followed by filtration and vigorous suction.

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This is followed by two washing processes with two fractions carried out by 200 ml of boiling ethanol to absorb the greater part of the absorbed on the polymer Remove water.

Finally, the suctioned off (sucked off) is dried Powder, which is arranged in layers in an oven gradually brought to 100 C, and under a vacuum of the order of 1 mm of mercury for at least 2 hours.

A determination of the water according to the KARL-FISCHER method gives a result below 0.5 #, while the linear, soluble PVP is estimated to be approximately 10 ppm.

B. The commercial PVPP is purified using the following technique which, since it uses ethanol, has the advantage of not temporarily increasing the water content of the commercial product.

The commercial product is brought under vacuum in the order of 1 mm of mercury to a temperature brought from 100 ° C for 2 hours, this already results in a weight loss of about 2 to 3 # » i.e. more than half of the water to be removed.

Then allowed to cool to 8O ⁰ C and covered with boiling ethanol.

The mixture is stirred slowly for half an hour, allowed to decant, the supernatant liquid is removed, filtered on a suction bottle, centrifuged and treated the mixture on the filter press in such a way that that the soluble components are removed.

This treatment is repeated twice in addition.

The treatment is completed as in Example 1 after suction removal by drying under vacuum in the heat.

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Under these conditions, the determination of the water yields a result below ₁ O 5 #, where the content of linear, soluble PVP is at about 10 ppm.

C. Commercial PVPP is purified by treatment with N-methylpyrrolidone as in Example 2 using ethanol was, the advantage of a better solubility of the water-soluble polymer, a less volatility of the solvent and thus a reduction in losses.

The treatment is followed by washing with boiling ethanol and drying, as described in Example 2, closed.

Under these conditions, the determination of the water gives a result below 0.3 % and a content of water-soluble polymer below 5 ppm.

The complex is made in the following way:

In a mixer with corrosion-resistant walls (preferably enamelled steel) 100 kg are crosslinked, according to one of the Procedures A, B, C introduced purified polymers and 6.5 kg of finely crystallized iodine.

The mixture is stirred for one hour at ambient temperature in order to disperse the iodine well, then the temperature is gradually increased to 80 ^° C. in half an hour and then to 100 ^° C. over a further hour.

The mixture is left at this temperature for 8 hours, then the temperature is brought rapidly to 120 ⁰ C.

After one hour the mixer is placed under vacuum and the vacuum is maintained until it is optimal The value depends on the apparatus, i.e. in the order of 1 mm of mercury.

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The powder thus obtained is cooled. The end of the reaction is determined by filtering 10 ml of water over 1 g of the powder.

The addition of soluble, powdered starch must not be visible Cause discoloration.

The determination of iodine is carried out by back titration in the following way:

Approximately 1 g of the powder is mixed with 10 ml n / 10 sodium thiosulfate solution treated in a sealed Erlenmeyer flask.

With the aid of a magnetic stirrer, the mixture is stirred for 2 hours, then filtered rapidly, the precipitate being carefully removed is rinsed and the wash waters are added to the filtrate.

Then it is titrated by back titration with an adjusted iodine solution.

If V ml is the volume of the solution that is then consumed ^: and V ml is the volume of the iodine solution corresponding to 10 ml of sodium thiosulphate, and if m (g) is the mass used for the experiment, the iodine content is given by the following equation:

JODGO = (V - V)

The complex prepared gave a result for iodine in (#) of 5.85 to 5.95.

Example 9

The procedure of Example 8 is repeated, but using 11 kg of iodine; a complex is obtained which contains between 9.70 and 9.80 % iodine according to the analytical method described above.

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Example 10

Complexes heavily loaded with iodine can also tinter Following the procedure of Example 8 but using up to 16 kg of iodine can be produced.

The iodine content is always a little different from the theoretical content.

The action of water on such complexes, however, releases iodine up to 10 ppm, which is due to the coloring, the soluble Strength results can be determined.

By simple filtration over 100 mg of animal charcoal, 20 ml of filtration water, which over 2 g of such a complex with approximately 14% iodine, completely decolorized.

In the same way, complexes less heavily loaded with iodine can be obtained, either by using lower amounts of iodine or by diluting complexes with medium concentration of Example 8 or higher concentration as before with purified polyvinyl polypyrrolidone.

The study of the bacteriolytic effect of the new complexes was carried out in the following way:

The powder used had a concentration of 4 % active iodine.

It was added to the nutrient medium according to the usual procedure in such a way that a final value between 0.005 % and 0.10% (expressed in relation to the nutrient medium) was obtained.

The results obtained were as follows:

Study 1 : For two strains of Staphylococcus aureus with a complex based on nylon 6,6, the bacteriostatic effect was shown for iodine concentrations as low as 0.01%, the bactericidal effect requiring a value of 0.07%.

Similar results were obtained with a complex based on activated carbon.

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Study 2: For Colibacilli, the corresponding threshold values were 0.06 % and 0.08 % with a complex based on FVPP.

Examination: 3; For Klebsiella Pneumoniae, the respective threshold values were 0.02 and 0.06% when using complexes based on nylon 6,6.

Investigation 4; For Providencia, the threshold values are 0.06 and 0.08% for complexes based on PVPP or activated carbon.

Study 5: For Enterobacter Cloacae, the threshold values are 0.04 and 0.08% if complexes based on methyl polyaminoundecanoate (nylon 11) or PVPP are used,

Investigation 6; For Citrobacter, the threshold values are 0.05 and 0.09 % with complexes based on activated carbon.

Study 7: For Proteus Mirabilis, the threshold values are 0.06 and 0.08% if complexes based on PVPP or activated carbon are used.

Investigation 8; For Salmonella Typhi, the threshold values are 0.05 to 0.09 % with complexes based on PVPP or nylon 11.

Investigation 9; For Pyocyanique, the threshold values are 0.06 and 0.08% if complexes based on nylon 6,6 or PVPP are used.

Study 10: For staphylococcus epidermitis, the threshold values are 0.04 and 0.09% with complexes of nylon 11 or of activated carbon.

Investigation 11; For enterococcus, the threshold values are 0.04 and 0.07%> if the complexes originate from activated carbon or PVPP.

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Study 12: For Candida Alcibans the threshold values are 0.03 and 0.08% with complexes of activated carbon.

Investigation; 13: 0.1 g of iodine-containing powder with 4% active iodine was poured into 100 ml of water, which was artificially contaminated by 10 colibacilli, the matrix used being either nylon 6, nylon 11, nylon 6,6, PVPP or an activated carbon was.

The powder was converted into suspension with stirring. In all cases, i.e. regardless of the manufacturing process of the investigated, iodine-containing complex polymer used had bactericidal properties 5 minutes ago and bacteriostatic properties observed in less than 10 minutes.

Study 14: At the end of one hour of stirring as in study 13, the iodine-containing powder, which had already purified 100 ml of water diluted in study 13, was separated off and used again with 100 ml of the same water.

It was found that a bactericidal effect and a bacteriostatic effect of 10 minutes and 20 minutes, respectively Minutes can be reached, which shows that the treatment still contains a large amount of oxidizing agent in the powder has left behind, i.e. that the quantities and times given in investigation 13 are not far away either are a limit value for the optimal effectiveness of the novel complexes according to the invention.

Study 15: 100 ml of cow's milk (three identical samples, labeled L1, L2 and L3) are used in this study. The sample L1 is kept under the same conditions as the samples L2 and L3.

The last-mentioned are alone with 100 mg of the complex prepared in Example 1 and with 100 mg of the treated according to Example 5 complex prepared. To the

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- 58 -

Samples L2 and L3 no change at all is observed in the microscope.

After the staining, the presence of a relatively large microbial flora in comparison to the L1 sample the test sample, which is composed essentially of coliforms and streptococci. Both Milk samples L2 and L3, the latter cannot be found.

After inoculation on a nutrient medium and storage for 24 hours at 37 ° C, sample L1 becomes a strong flora, consisting of coliforms, was found, while samples L2 and L3 did not have any microbial flora in significant Show crowd.

In addition, it was found that the comparative sample IA shows the characteristic odor as a result of the formation of lactic acid, while the samples L2 and L3 have unchanged organo-Ieptic qualities.

Filtration on paper enables numerous coagulates to be separated in the comparative sample, in contrast to the samples L2 and L3, which filter without any residue.

Finally, it is found that a composed of fatty cream settles on the samples L2 and L3, and _i While in an identical volume and of identical type as that obtained at the beginning of the experiment on a control sample, which the non-absorption of fatty substances by the inventive , shows new complexes and thus the preservation of the nutritional properties of the milk (of beverages) after cleaning by the new, iodine-containing complexes.

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Study 16: In order to assess the possible dangers of an accidental overdose of the new complexes according to the invention, the same experiments are carried out using not 100 mg, but 1 g of the iodine-containing complex obtained with the help of any polyamide or any activated carbon in 100 ml of milk, carried out under the same conditions.

The results were similar to those reported in Study 15 • completely identical. The absolute harmlessness of the new, iodine-containing complexes is therefore readily apparent.

The design and applications of the new complexes are explained in more detail using the following examples:

Example A: Powder for a dry powder treatment (use in humans or in veterinary medicine)

To produce 100 parts of this product, 50 parts of microcrystalline cellulose (trade name Avicel) are intimately mixed with 50 parts of the iodine-containing powder obtained according to Example 1 or Example 4-, this powder depending on the intensity of the desired effect between 0.5 and 20 % Iodine.

Example B:

Powders for the same application as described in test 14 are made by mixing microcrystalline Cellulose and the iodine-containing obtained according to Examples 2 or 5 Complex in a ratio of 5/95 to 95/5 by weight obtain.

Example C: Treatment powder (for use on plants or in technology)

To 13 parts of the iodine-containing complex obtained according to Examples 4 or 6, which is preferably between 0.1 and 5 % iodine

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contains, while 5 parts wind-sighted, finest talc powder and 2 parts of a suitable wetting agent or film-forming agent are added.

Example D: Powder for a pressure bottle (use on humans, plants or in veterinary medicine)

From 25 parts of the obtained according to Examples 5-7 or 8, iodine-containing complex and 5 parts of isopropyl myristate with 70 parts of a propellant which is a mixture of, for example Contains 2/3 FREON (R) 11 and 1/3 FREON (R) 12 - the powder is made.

Example E; Clear gel for internal or external treatment (use in humans, plants or veterinary medicine)

From 8.8 parts of the iodine-containing complex obtained according to Example 1, 0.5 part of carboxyl resin (trade name CARBOPOL 40 (R), for example), 90.2 parts of purified water and 0.5 part of diisopropanolamine and optionally a suitable amount of perfume the gel is made. (This gel can be applied directly for external use, or inserted into natural cavities, for example with the help of a pressure bottle.)

Example F: Cream for external or internal treatment (use in humans or in veterinary medicine)

Mixing 20 parts of polyoxyethylene glycol (molecular weight of 400) and 55 parts of polyethylene glycol (molecular weight 6000) purified with 5 parts of water, followed by dispersing 20 parts of the obtained according to Example 5, iodine-containing complex in the resulting cream.

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Example G; Clear gel for sterile applications (human and veterinary use)

15 parts of the iodine-containing obtained according to Example 1 or 5 are added Preparation to a gel made from 70 parts of vaseline oil and 15 parts of magnesium stearate had previously been prepared, the gel carrier itself being made by dispersing the magnesium stearate in the oil and by heating for about 15 at 150 ° C to form a transparent and sterile gel.

Example H; Clear gel for internal or external treatment (use in humans or in veterinary medicine)

10 parts of the obtained according to Examples 4 or 6, iodine-containing complex to form a gel composed of 10 parts of carboxymethyl cellulose and 1.5 parts of water-soluble polyvinylpyrrolidone and 78.5 parts of purified water was obtained.

Example I; Dry bandage (human or veterinary use)

On a suitable textile backing of suitable width and strength with regard to the intended application a suspension of the iodine-containing complex (10 to 40 parts) according to the examples is brought according to the usual technique 1, 5 or 7 of the appropriate concentration of iodine along with 60 parts of a carrier.

Example J: suppositories

For example, one rubs into 95 parts one made of semi-synthetic Glycerides or cocoa butter existing diluent 5 parts of the iodine-containing preparation prepared according to Example 5 with a suitable iodine content until a homogeneous mixture is produced, which is to a satisfactory consistency is brought for casting according to the known working methods.

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Example K; Medicated soaps for hygienic purposes

The term soaps denotes products of saponification of fatty substances of the general formula R-CCX) B, where R-CCX) represents the totality of the fatty acids of the starting material and B represents that which is supplied to the saponification through the alkali compound Cation is

The soaps can be hard or soft, depending on whether the by-product of saponification, the glycerine, is extracted or is left in the mixture.

For example, you can 5 parts of the according to Examples 1, 5 or 7 produced, finely comminuted (micronized) iodine-containing preparation to 95 parts of previously produced Add soap at a suitable temperature following the procedures known per se to make a homogeneous paste before molding to obtain. ,

Example L: Medical dentifrices for hygiene purposes

For example, the following formulation was prepared, which is arbitrary depending on the taste, appearance and the desired conditioning can be modified:

Sodium Lauryl Sulphate 11.25 %

Calcium carbonate, finely crushed 24.75 # colloidal silicon dioxide 2.75 %

Sodium saccharinate 0.50 %

Sodium para-oxymethylbenzoate 0.25%

iodine-containing preparation 5.50 %

purified water 55 »00; pounds, by weight,

A homogeneous mixture of the powders is made and the water is added until a paste of half-thick consistency is obtained will.

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The iodine-containing obtained according to Examples 1 or 5 is added Add the preparation in a suitable manner and fill the paste obtained in accordance with the usual procedures in tubes.

Example M; chewing gum

As an example, the following combination was made:

Basis (DREYFUS, description of goods) 26.00 %

Glycerine _ 4.00%

finely powdered sucrose. 44.50 %

Aroma (eugenol) 0.50 %

iodine-containing preparation 5 - 00 %

purified water 20.00%, in

weight

In a suitable manner is added to the brought to a temperature of about 60 ⁰ C based (trade name DHEYFUS) gradually sucrose in the form of a fine powder, flavor, purified water, the glycerin and the iodine-containing preparation is added until the consistency of a homogeneous Paste is achieved.

This mass is subdivided into strips or any other commercially available shapes to their desired th shape with the desired dimensions according to the usual procedures.

The harmlessness of the preparations based on the new complexes was demonstrated on the preparations made with nylon 11 and granular activated carbon.

This harmlessness was determined according to the following test program .

1) Oral application in Wistar rats

a) Comparative series: 100 mg nylon 11 per 24 hours

are administered via a nasogastric tube in the form of a 2% suspension in gum arabic. 709848/1060

b) Treated series: 100 mg of the complex are used at 4 % per 24 h (same route of administration).

10 animals are treated per series, namely 5 males lind 5 females with a mean weight of 250 g.

During the eight-day treatment described above the diet consists of drinking water ad libitum as well as granular, standard food.

There was no toxic sign at all during the treatment and during the end of the application observed the following fifteen days.

2) Skin tolerance test in Swiss white mice

After shaving a spot and disinfecting the shaved surface with 60% alcohol, the pure powder at 4 % (50 mg) was applied under a final dressing that was renewed every 48 hours.

At the end of the application for eight days, no particular signs of irritation were observed at all.

From this it can be concluded that under these test conditions there was no sign of intolerance.

The new iodine-containing preparations therefore seem to be harmless.

For clinical trials carried out with the aid of the iodine complexes with nylon 11 / with a content of approximately 5 % complexed iodine, the following two exemplary observations should be made to underline the antiseptic, medicinal forms of application of the complexes according to the invention.

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Observation; I :

A man aged 4-0 was 8% on the right from steam

Poor up to the second degree .. burned - It. v became that in Bei-, THe rs division painted jöei game ΈΆ)

game A / powder described by powdering in dry Condition applied and a sterile, non-final dry dressing applied, with a renewal every 48 hours took place. The job was painless and the person treated did not report any additional sensations Burning or extra pain.

There were no purulent secretions during the course of treatment. The wound scars looked normal from the 6th day after the first application.

On the other hand, there was no sign of maceration nor any sign of irritation or a local or all-allergy observed.

Observation II:

A woman aged 62 had a varicose vein ulcer in the lower third of the right leg after one chronic reinfection caused by the job (worker in viticulture) j.

After the classic treatments of the ailment (dusting on a DAKIN solution) and drying with a sterile one The powder of Example D was homogeneously dusted on the compress.

The dressing was renewed every 48 hours, and in the course of the renewals it was found that despite a strong Discharge through the ulcer, the bandage did not adhere to the ulcer.

In contrast to the other treatments, deodorization is achieved regularly during the treatment. The local Treatment was carried out over a period of three weeks, at the end of which there was a complete

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disappearance of the earlier secretions, and it was found that bacteriological examination was carried out on these Secretions demonstrated a strong presence of enterococci would have.

Another bacteriological examination, which reveals the discreet serosities left at the end of the treatment could not show the presence of bacterial strains.

At the end of the treatment the scarring of this ulcer, which had been developing for more than a year, was good Path. No negative side effect at all had disturbed the patient's well-being.

With regard to the applications in the filtration of liquids of any kind and in particular of beverage water tests were carried out according to one of the procedures described below.

It became a filter cartridge that was used to treat household drinking water or is particularly applicable to water for swimming pools, manufactured in the following way:

1 kg of the iodine-containing complex described in Example 1 and an additional 200 g of activated charcoal were well homogenized and placed in a filter cartridge, which was filled with water before closing. The cartridge was shaken to put the filter medium in suspension, and the cartridge was placed in the water passage for water filtration appropriate system used.

It has been found that a reasonable throughput of bacteriological pure water, which depends on other parameters of the system, can be obtained in a single pass can. Achieving a higher throughput can be done with the help of

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can be achieved by two identical cartridges arranged in parallel. In the case of the use of heavily polluted water locations can be the contact time using a cartridge having a large ratio of length / diameter increase, or by the requisite number of cartridges to be disposed of suitable dimension in series.

Static sterilization was also carried out

This method is particularly suitable for industrial applications, in which the provision of quantities of sterile water for rinsing after cleaning of any objects or containers, for example for

.or the pharmaceutical industry, the food industry / or also for the packaging of preparations, for example foodstuffs or fhanna- chemicals such as fruit juices, drinkable specialties , etc. is required. ,

For this purpose, it is sufficient to have a large, tight storage container in which one of the previously described, insoluble complexes can be suspended in a large volume of water to be purified , about 40 ares of medium-contaminated water to 1 kg of iodine-containing water produced according to the invention Complex.

After decanting the powder, the purified water can easily be drawn off, either at the bottom of the container or at the top of the liquid, this method allowing the precautions to be taken to avoid entrainment of any part of the iodine-containing complex to be limited.

Of course, further advantages, variants and applications are readily possible within the scope of the invention.

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Claims (12)

Claims Halogen-containing complexes that are insoluble in water and aqueous liquids, obtained from insoluble matrix materials of the type of organic polymers and mixtures thereof, which to ensure the complexation of halogen molecules by charge transfer or by van der Waals Have bonds suitable functions, characterized in that the polymers to the Class belonging to that by polyvinylpolypyrrolidone, the polyamides of copolymers and polycondensates and the substances of the activated charcoal or non-active charcoal type are formed, and that the halogen iodine is whose complexation is carried out only in molecular form. 709848/1060 [> K C. MANITZ ■ DIPL. INC. M. FINSFfIlWALD β MONKS 22. ROBERT-KOC H SiBASSE I TtL. 10891 22 42 II. TtLEX O5-29672 PATMF DIPL-INC. W. Ci RAMKOW 7 STUTTGART SO (BAD CANNSTATT » SEELBERCSTR. 23/25. TEL. <07lllSÖ 72 61 CENTRAL TICKET OFFICE BAYER. VOLKSBANHtN MUNICH. ACCOUNT NUMBER 7370 POST CHECK: MUNICH 77061- (OS ORIGINAL INSPECTED 2. Complexes according to claim 1, characterized in that the iodine is complexed only in molecular form in a proportion by weight of between 0.5 and substantially 20%. 3- Process for the preparation of complexes according to claim 1 or 2, characterized in that: The matrix of the polymers is previously dried and freed from its most soluble fractions by the action of a suitable solvent, so that its degree of moisture is below approximately 0.3% by weight and its content of soluble materials is below essentially 0.01% by weight. % lies, the polymeric matrix, which is insoluble in aqueous liquid, is heated with a solution of iodine in a solvent of the unsubstituted hydrocarbons or halogen-substituted hydrocarbons type, the polymeric materials being in suspension in this solution, and the heating in one of the polymeric ones Materials non-decomposing temperature between ambient temperature and practically 120 ⁰ C takes place depending on the polymeric materials, - the heating is maintained for a period between 6 and 12 hours in such a way that the content of complexed iodine is between 0.5% by weight of the polymeric matrix and a value of substantially 20 % below the threshold value of the saturation of the macromolecular mass, and - Complexing the iodine by bringing the mixture of iodine and polymeric material to a temperature below the decomposition temperature of this polymeric material Material and a maximum of 120 ° C under vacuum and with stirring. 7 09848/1060 4. The method according to claim 5, characterized in that that iodine is used in the form of fine particles in the solid phase. 5. The method according to claim ~ t> or 4, characterized in that insoluble complexes are obtained on which the water and the water-soluble or halogenated organic solvents extract less than 1 ppm of iodine. 6. The method according to claim 3 or 4, characterized in that the complexation of the iodine in one voluntarily limited manner using either a heating time of substantially less than 6 hours or a halogen value above the saturation value of the polymeric material used is carried out. 7. The method according to claim 6, characterized in that that insoluble complexes are prepared on which the water and organic, water-soluble or halogenated Extract solvent 1 to 10 ppm iodine. 8. Use of the complexes according to one of claims 1 or 2 for making aseptic, for disinfection, for sterilization, for partial sterilization, for rapid pasteurization of any liquids which are to come into contact with mucous membranes or other living tissues, characterized in that complexes are used whose iodine content is below 20% and in particular between 6 and 15 % . 9. Use of the complexes according to one of claims 1 or 2 for rendering gases aseptic, characterized in that complexes are used whose iodine content is between 1 and Λ ¹ ) °, Ό , and that the polymeric materials used are not hygroscopic. 7 η π ß u fl / 1 η 6 ο 2722345 10. Application of the according to the method of claims 6 or 7 obtained complexes for the production of aseptic waters, which contain iodine contents between practically 1 and 10 ppm, through simple filtration. 11. Use of the complexes prepared by the method according to claim 8 or 9 for the preparation of a cartridge for Make pluiden aseptic, with this cartridge on the Way of passage of the fluid is arranged thereby characterized in that the fluid passes through at least a first aseptic chamber which contains the iodine-containing complexes, and at least one second chamber passes through which an insoluble substance contains of the type animal charcoal. 12. Use of the complexes prepared by the method according to claim 8 or 9 for the preparation of a cartridge for Rendering fluids aseptic, thereby placing this cartridge on the path of passage of the fluid characterized in that the fluid passes through at least one chamber which is an intimate mixture of the iodine-containing complexes and an insoluble substance of the animal charcoal type. 13 · Use of the complexes according to one of claims 1 or 2 in the medical field, characterized in that one of these complexes is the selects therapeutically acceptable complexes and that they are in the form of a powder with a fine particle size distribution for making skin surfaces and / or mucous membrane surfaces aseptic, in the form of capsules, coated tablets, Suppositories or tablets in conjunction with any suitable diluent or carrier or any other therapeutically acceptable substance applies, whereby the proportion of complexes, based on the substrate, 709848/1080 is about 20%, and wherein the level of complexed Iodine by weight is essentially 5% in the complexes. Use of the complexes according to one of claims 1 or 2 in the hygienic and dermatological field, characterized in that the complexes are in the form of soaps, pomades, toothpastes or chewing gum in the form of powders with a fine particle size distribution in the suitable substrates in an amount from about 5 to 20% by weight and with an iodine content of the complex between 3 and 8 % . 709848/1060