DE1745187A1 - Hydrophilic polymers and articles made therefrom and processes for their production - Google Patents

Description

R. POSCHENRIEDER

LING R-J. Muller

äiiiafiWiiila

8 Munich so

Lucile-Grahn-Strasse 38 _Λ .

Telephone 44 37 55 21.

Patent application P 17 45 187.5 Sch / Gl

National Patent Development Corporation, 575 Park Avenue, New Xork, N.Y./ USA

Hydrophilic polymers and objects made therefrom and processes for their production

The present invention relates to novel hydrophilic polymers and processes for making the same, and it stands in particular relation to such hydrophilic polymers, which in the form of semolina syrups, friable solid foams and in powder form, the latter porm being used primarily as a carrier for medically active substances and for natural and synthetic flavors, essences, Fragrances, spices, food colors, sweeteners, dyes is absolutely suitable and the like.

Νθϋθ documents (Art 7 SI Paragraph 2 No. I S.tr Ζ 'Jis Amendment «! *, K. 4,

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It is known per se to produce hydrophilic polymers, in particular crosslinked hydrophilic polymers, and it is also known to produce them in the form of shaped body hydrogels in aqueous solution by copolymerization, a predominant amount of a monoester of acrylic acid o ( 3r methacrylic acid and a bifunctional alcohol which has an esterifiable hydroxyl group and at least one additional hydrophilic functional group is copolymerized in aqueous solution with a small amount of a diester of one of these acids and an alcohol which has at least two esterifiable hydroxyl groups (see US Pat 2 97o 567 and 3 220 960).

It is known that the prior art formed, hydrophilic polymers, which are in an aqueous System have been produced as carriers for medically active substances are technically useful. The professional world it was thus common that medically active substances can be dissolved in the aqueous component of the prior art shaped body hydrogels and thus a gradual release of the medically active substances can be achieved. The emerging solutions, however, are difficult to handle and store and the medicinal active ingredients are the air oxidation, the degradation, the decomposition, exposed to volatilization, etc.

In the previously known methods, it has been necessary to use a solid or shaped body of the hydrophilic Polymerisates to produce and then the medicinal substance, the flavor, the sweetener, the color and the like in the aqueous components of such

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Solve the porous body. In addition, it is with the so far known working methods that. use a copolymerization in an aqueous solution, was not possible, directly to produce a foam by adding one of the usual foaming agents, such as ITodium bicarbonate, because rather a semi-gelatinous hydrogel product as the desired hard, A friable foam was created and it was not possible to turn such a semi-gelatinous product into a friable foam or convert to a compressible powder.

There has also been in the previously known ways of working, which has been known redox Katalyeatoren as IJatriumbicarbonat and ammonium persulfate, potassium sulfate, Hatriumthio- μ sulfate and Ammoniurapersulfat or potassium sulfate, use the Vorvollständigung the polymerization reaction at l'emperaturen above 0 ⁰ C, and thereby Prevents the formation of a prepolymer, preferably in the form of a liquid semolina syrup, because it can be colored, pigmented, thickened and changed in other ways in its Porm and then hardened to solid or shaped objects such as rods, plates, pipes and others To produce posn articles or a hard friable foam, as will be explained later in this description of the invention.

In addition, only arose in the previously known method, incomplete (ie up to about 95 fd) durchpolymerisiertes (polymer and further such a polymer which übermSsp-.tg large amounts of water (more aln 30 wt ^, even to sin 80 weight ^) was able to absorb when eo vmrde equilibrated in solutions.

The new inventive hydrox> hi..len polymers,

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that are made in an anhydrous state are essentially fully polymerized (i.e. to about 99s5 #) and are unable to exceed about 30% Weight- ^ to absorb water when in aqueous Solutions are equilibrated.

It has now been found that hydrophilic polymers can be produced in an anhydrous system in such a way that that the direct production of liquid pouring syrups in prepolymerized form is possible, which can be used for direct polymerization in situ in the form of cast or shaped bodies, films and coatings, which can be combined with the usual foams, such as sodium bicarbonate, are treated to obtain hard friable foams which can be brought directly into the swollen state or can be ground directly into powder.

It has also been found that hydrophilic polymers can be prepared in an anhydrous system such that a as soon as the hydrophilic polymerisation products can be produced in powder form. A purpose of the present invention is to produce said hydrophilic polymers in an anhydrous system in order to convert them directly into to enable a powdered foam, which makes the powdered polymers particularly suitable as a marker for medically active Substances, natural or synthetic flavors, essences, fragrances, spices or the like are suitable, The polymeric powders according to the invention are compact in shape and have the necessary stability and storability, which makes it possible to use them as carriers for medicinal substances and flavorings, welohe chemical reactions, such as air oxidation, deterioration, Are exposed to evaporation and degradation.

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Another advantage, which is also the strength of the above powdered hydrophilic polymers is that when encapsulating said powder, which contains medicinally active substances, fragrances, essences and the like carries, greater stability and a longer shelf life. are present than before.

Polymer powder, which flavors, essences or spices encapsulated, can be added as desired are converted again and thus provide flavor solutions of a superior quality because of the encapsulation the decomposition of the flavor component due to the ingress of air and also prevents losses through volatility. f

The liquid syrups of the present invention are prepared in such a way that a predominant amount of a suitably purified technical polymerizable monoester of an olefinic acid containing at least one substituted hydrophilic functional group is mixed with a minor amount of a free radical-generating catalyst and heated to a temperature heated between room temperature and 8O ⁰ O until the polymer ized 3? part of the monomer no longer has water solubility. This product is then cooled to room temperature and the theoretical amount of catalyst is added. The casting syrup can then be colored in a suitable manner and i pigmented, and the viscosity of the liquid mass can be increased to the desired value by the addition of appropriate thickeners.

The pouring syrup can be hardened to produce products that can be poured, molded, or machined to Rods, plates, etc. can be processed for various purposes. The product can be in rigid or flexible

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in a swollen state or in the form of a foam. That Polymer obtained from the hardened casting fluids has good mechanical strength, reversible fluid absorption capacity, and the ability to to maintain its shape in a liquid medium and to regain this shape after deformation through elastic recovery.

The pouring syrup is also suitable, for example, for in situ polymerization in the manufacture of dental prostheses especially in the manufacture of denture linings and mouth guards. The absorption capacity of the hardened product enables an advantageous application for other medical-surgical purposes, for example as heart valves, Vascular exchange material, dialysis gate diaphragms, intrauterine Devices and the like.

Prior to the addition of dyes, pigments _t thickeners and other additives, the liquid Gießsirupe in an excess Waseermenge be given, to form a Polymerisatfällung. The latter is soluble in strongly polar organic solvents such as alcohols, olycols and glycol ethers. The precipitated polymer, when it is dissolved in polar solvents, is used as a polymer solution for the formation of films, coatings and the like. Notwithstanding this, the precipitated polymer can be dried and used for the production of molded articles by glazing, injection molding, extrusion, calendering and the like.

According to a further embodiment of the invention hydrophilic, soluble, thermoplastic polymers by suspension polymerization of hydroxyethyl methacrylate in

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_ 7 -

a non-polar medium such as a silicone oil or mineral oil. Bas catalyst-containing monomers is in the non-polar medium dispersed in j? orm small droplet chsn, which then polymerize to form finely divided spheres or pearls. Such pearls can be found in polar organic ! Solvents for the production of films, coatings or the like can be solved. The beads can also be used directly for the manufacture of technical thermoplastic molded articles Find application, for example by injection molding, extrusion, calendering and the like. The suspension polymerization is preferably carried out in an oil bath at temperatures in the range of 50-150 ° 0 until pearl formation has ended is. The ratio of suspension oil to monomer is preferably about 5: 1 to about 20: 1. The ratios of catalyst to monomer are preferably about 0.05-1 * 0 parts per 100 parts of monomer.

The hydrophilic polymers according to the invention - in anhydrous Polymerized state - can be formed in such a way that they can be applied to metal, glass, rubber, plastics and other surfaces. They can also be cast into solid bodies by deforming and grinding can be converted into toric contact lenses, what was previously done with hydrophilic polymers that polymerized in aqueous solution was not possible.

The starting materials which can be used for the purposes of the present invention are hydroxyalkyl ethers α, β-unsaturated carboxylic acid, such as 2-hydroxyethyl methacrylate, the hydrosypropyl methacrylate, etc. These esters are used in an anhydrous system with suitable amounts of a free radical generating catalyst, such as tert-butyl peroctoate,

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Isopropyl percarbonate, benzoyl peroxide or the like, and with a suitable crosslinking monomer, such as ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1 "4-butylene" glycol dimethacrylate, or mixed with other polyfunctional monomeric beers.

As has been found, the application of the catalysts producing free radicals in such concentrations is twofold, which are in the order of 0.05 β to 1 g of catalyst per 100 g of polymerizable hydroxyalkyl esters are, the preferred quantity ranges between 0.1 and 0.2 g per 100 g Source material lies.

The mechanical properties that the invention Polymerizat, and its ability to retain water as a homogeneous component, are in strong Measured by the amount of polyfunctional crosslinking agent present. Concentrations of 0.05 ~ 15 g of crosslinking agent per 100 g of 2-hydroxyethyl methacrylate have proven to be uniform in size for the polymers according to the invention, the preferred range being between 0.1 and 0.2 grams of crosslinking agent per 100 grams of polymerizable hydroxyalkyl esters.

The polymerization of the abovementioned reaction components can be accelerated by the application of heat, or the application of heat can also be dispensed with by a specific selection of the catalyst and the amount thereof, and rapid polymerization can nevertheless be initiated even at room temperature. Xn the cases in which used to cure heat, temperatures have been found to from about 20 to about 15O ⁰ C to be suitable, the preferred range being between 40 and 70 ° C.

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A further object of the present invention is to create new properties in the hydrophilic polymisrisate-runchiiatorial, as will be explained in more detail below, and to improve and increase the already existing properties by adding to this material incorporates a small amount of one or more additives, which can consist of synthetic resins _p rosin esters, phenoxy resins, silicone resins, low molecular weight polyobutylenes, synthetic polymers and prolamines. The new compositions are particularly suitable for the formation of polymer mixtures which are endowed with new properties and which mean an improvement or reinforcement of the properties of the hydrophilic polymers which are already present «,

The mixture is heated or otherwise cured in the absence of compatible, volatile or non-volatile organic solvents to produce thermoset polymeric materials having properties superior to the properties of the major ingredients of the formulation. The improved properties of these new compositions of matter include improved hardness, improved adhesion, improved abrasion resistance, impact resilience and toughness, but of course the improvement need not be limited to these properties. The polymerized material provides products with improved machinability and polishability, and it can also find technical application as a molding powder or in admixture with other presomeoses. Improvements in properties of smaller dimensions can be achieved by using small amounts of other crosslinking glycol dimethacrylates.

The inventive method can also be used for the production of

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thermosetting surface coatings with improved adhesive strength on various substrates or for the production of thermosetting synthetic resins for the diffusion of foils and films with improved clarity and toughness applications Find.

In general, 2-hydroxyethyl methacrylate and the crosslinking monomeric ethylene glycol dimethacrylate are used in an amount of 10-50% by weight (preferred amount range 50 %) with 90-50% by weight of a technically available synthetic resin of the type of coumarone / indene resins or their phenol-modified modification products providing in the presence of a free radical catalyst such as tert-butyl peroctoate, isopropyl or the like is mixed, and about 30 minutes at temperatures of 40 - 200 ⁰ G heated. In order to increase the compatibility of the components with one another, organic or inorganic solvents are also used. Compatible polymers with improved properties in terms of tensile strength, modulus, hardness, thermal conductivity, etc. are formed in this way. The quantitative limits set out above are also observed for the additional components of the phenoxy resin and silicone resin type.

The resulting polymers can either be in the form of Films or rods suitable for grinding into fine powders. By mixing the Reaction components with foaming agents, v / ie sodium bicarbonate. before curing, the polymer can be obtained in the form of a foam, which can easily be acted upon with the aid of a group exercising devices can be crushed to a fine powder. The powdered polymers of the present Invention are preferably obtained from foams. As stated foaming agent quantities of 1 - 10 g per 100 g of the reaction components are sufficient.

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• AD OtVCUNAL

polymer powders obtained by any of the procedures described above are combined with natural Q & e / j? raynthetisohen GeochioacIauötofiCon or jQi.jßcna-an _p which are dissolved in a suitable solvent _f mixed ,, and the mixture is placed on a mechanical roller mill to achieve aο an intimate mixing of solution and powder «The solution is then filtered and evaporated dried in the air or by heating with air circulation. After evaporation of the solvent, the flavor or essence is retained by the powder. Because of the extremely high hydrophilicity of the hydrophilic polymer of the present invention and because it is excellent in eating with reversible liquid absorbency, "the powders in solution can be reformed as desired to provide solutions containing concentrated flavors or essences."

Ana existing plastics Austausehmateirialie · "for vessels dea human body are indeed known ^ as such but never axis the novel polymers hergsn romps ρ EO gets you to materials from iseuon and technically excellent useful properties. In addition to the properties required per se, such as chemical, physical, linear and thermal inertness, the rsatR vessels, which are made from the polymers according to the invention, are characterized by unusual colloidal properties due to which they are closely related to living tissue, and "ie constant contact with Körpergewebon are therefore for a long time? / predestined. Aue the inventive polymers manufactured articles can be sterilized by boiling, and they can continue by impregnation with a physiological solution prior to introducing tu β body

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tissue replacement made iootonic with the surrounding tissue will"

A completely unexpected advantage of the aue according to the invention Objects made of polymers consists in that due to hires reversible liquid absorption capacity Heparin dissolved in an isotonic saline solution or another anticoagulant agent in a suitable solvent can be added during the preparation of the polymer and the polymerization can then be carried out in situ can. The anticoagulant is then in exchange The vessel is present and will be used after the transplant gradually released again, thus preventing thrombus formation. Likewise, medically active substances such as Antibiotics and other active ingredients, e.g. bactericides, virus-destroying substances, fungicides that are water- or alcohol-soluble are to be added before the polymerization, or it can be the final polymer product in a solution of these substances are immersed and thus serve as a carrier.

The mechanical properties that the invention Polymers are conferred, and their ability to produce an isotonic correspondence with the surrounding body tissue, is strongly influenced by the proportion of the polyfunctional crosslinking agent that is present. How found , concentrations of 0.05-15 g per 100 g of 2-hydroxyethyl or Hydroxypropyl methaorylät appropriate, the preferred one (? range 0.1 - 1.0 g crosslinking agent per 100 g polymerizable liydroxyalkylester cheats.

Before the glosses, the Ausausohgefäß can by means of reinforcing Materials are improved in their strength, e.g.

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with fiberglass, Dacron or the like, in the most diverse Thousands of an inch and denier thicknesses that are present in the Rohrfona mold, so that the reinforcing Material from the casting solution is completely cured.

The polymerization of the casting solutions can be "accelerated" by the application of heat or, with an appropriate selection of the catalyst and the amount thereof, the application of heat can also be omitted and nevertheless rapid polymerization can be started at room temperature is applied, are lemperaturen of about 20 - adhered to 150 ⁰ G, wherein lemperaturen of 20 -. 100 ° 0 have proved to be particularly practical and the preferred range is between about 40 and 80 ° ö the reaction is advantageously anaerobic in an inert or It is known that the presence of oxygen inhibits the polymerization reaction and that either a longer reaction time is required or higher polymerization temperatures must be used.

The polymers according to the invention can also be used to produce other prosthesis-like devices such as Body implants, suitable being the liquid pouring syrups in the form of prepolymers for direct in situ polymerization can be used. Contraceptive devices such as uterine pads, diaphragms and the like, are known per se. Sine difficulty encountered in fabrication such devices commonly appear is that the material from which they are made, the body tissues, such as mucous membranes ^ often cause inflammation

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irritates. In addition, these devices suffer from repeated sterilization with boiling water or steam a decomposition. The difficulties encountered with the known devices are easily eliminated by that the contraceptive devices are produced from the polymers of the present invention.

In addition to the properties required per se, such as chemical, physical and thermal inertness, the contraceptive devices made from the polymers according to the invention have unusually colloidal properties which make them extremely similar to living body tissue. This makes them particularly suitable for purposes that require a longer contact time. In order to obtain a device of suitable rigidity in those cases in which this property is desired, it is advantageous to incorporate a creasing material into the casting resin prior to the final curing. The filler material can consist of an inert salt such as barium sulfate, potassium carbonate, clay or the like. Another possibility for fabricating a tissue-compatible contraceptive device is to coat such a device, which is made of some other rigid plastic, with the polymer composition according to the invention. Such a rigid device can be made of nylon, polyethylene, and the like. The puncture of the polyhydroxyalkyl ester then consists in making the device more compatible with the tissue.

Another possibility for the technical application of the hydrophilic polymers according to the invention in particulate matter

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like to state, for example in the form of powders, beads, pressed moldings and the like _f is to use it as a filter medium for iabskrauch and other gaseous products of combustion. The hydrophilic polymers according to the invention provide a non-bleeding, moistening carrier if they are presaturated in a polyhydric alcohol, for example glycerol, propylene glycol, polypropylene glycol and ethylene glycol.

In addition, the erfindungsgemäasen hydrophilic polymers provide an excellent filter media for technical purposes, since it will have the ability to use other components such as thiourea or dithioerythritol retain _s and again leave, the latter components against oxidation resistant and, therefore, for the reaction with the toxic, irritating or odorous combustion products of the blown smoke are available and convert them into a non-harmful form. It is sufficient if these components are only soluble in the polyhydric alcohol, alcohol or water which are absorbed by the hydrophilic filter medium serving as a carrier. In this way, adsorption and reaction with nitrogen aids, hydrocarbons and other combustion products can be achieved in the gas stream.

A tobacco aroma can also be mixed into the hydrophilic filter medium to enhance or replace the aroma, which has been lost in the course of inhaling the tobacco smoke through the filter medium according to the invention, which Medium some of the tar-like and titanium oxide-like combustion products, which presumably contribute to the formation of the desired tobacco aroma, can remove from the smoke. In the filter material can also contain specific aromas,

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such as menthol or the like, are also incorporated, which are then released from here into the tobacco smoke stream UDd so improve the aroma of the tobacco smoke when inhaled.

The inventive hydrophilic filter medium can thanks its ability to absorb water-soluble pigmented staining or coloring components can also be used well as a chromatography filter.

According to a further embodiment, the hydrophilic polymers according to the invention can also be used in powder form as thickeners for food, and mainly thanks to their ability to absorb water when they are dry. ·

According to a still further embodiment of the invention, the hydrophilic gel materials of the present invention can be used in the form of a bandage or bandage which contain medicaments which are then gradually released again from the hydrophilic gel material. The bandage will preferably formed from a plastic mesh material serving as a reinforcing element, onto which the hydrophilic Gel material is applied in the form of a strip or a layer by pouring.

According to a further embodiment of the invention, this is hydrophilic gel material also suitable for the absorption of water-soluble nutrients, which then under controlled conditions can be released again »This is how agar plates can be formed that absorb the water-soluble nutrients, then dried and the nutrient is essentially instantly available again after soaking in water place.

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The present invention is an excretion from United States patent application filed July 26, 1966 Serial ITo. 567 856.

The above-mentioned subjects and further developments of the invention are illustrated in the following examples which, however, merely illustrate the invention, it but are not intended to be limiting in any way.

example 1

Purified 2-hydroxyethyl methacrylate is mixed with a crosslinking monomer, ethylene glycol dimethacrylate, in a concentration of 0.15 g per 100 g of 2-hydroxyethyl methacrylate. The mixture is mixed with 90% by weight of a styrene copolymer resin (a synthetic resin sold under the trademark "Piecoflex" was used for this purpose) and 0.15 g of a vinyl polymerization catalyst which provides free radicals, namely isopropyl percarbonate, in an anaerobic atmosphere at room temperature. The solution is then poured into a mold in order to form a shaped diaphragm which is ^{cured for about 30 minutes at 200 °} C. and then removed from the mold. The diaphragm is machined and polished to provide the finished commodity.

Example 2

Purified 2-hydroxyethyl methacrylate is dimethacrylate with ethylene glycol stirred, in a concentration of 0.1 g per 100 g of 2-hydroxyethyl methaorylate. 50 parts by weight of an oumaron / indene earx are added to the mixture (an under commercial resin used under the trademark "Oumar") and 0.15 g of isopropyl percarbonate in an anaerobic atmosphere

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mephare given at room temperature. The solution will be on a steel plate poured into a film that lasted 30 minutes Cured 40 ° C to form a thermosetting film, which is characterized by a high gloss, high adhesive strength, abrasion resistance, hardness and impact strength.

Example 3

Purified 2-hydroxyethyl methacrylate is stirred with ethylene glycol dimethacrylate in a concentration of 0.1 g per 100 g of 2-hydroxyethyl methacrylate. To the mixture are added 75% by weight of a polyvinyl acetate resin (a resin sold under the trademark "Polyco" JLm was used) and 0.15 g of benzoyl peroxide in an anaerobic atmosphere at room temperature. The solution is cast on a steel plate to form a film which is ^{cured for 30 minutes at 100 °} C. and forms a thermosetting film which is distinguished by high gloss, high adhesive strength, abrasion resistance, hardness and impact strength.

Example 4

Purified 2-hydroxyethyl methacrylate is stirred with ethylene glycol dimethacrylate in a concentration of 0.05 g per 100 g of 2-hydroxyethyl methacrylate. 50% by weight of a lerpenic resin (a resin commercially available under the trademark "Piccolyte" was used for this purpose) and 0.05 g of isopropyl percarbonate are added to the mixture in an anaerobic atmosphere at room temperature. The solution is cast on a steel plate to form a film which cured 30 minutes at 40 ⁰ G, and forms a thermoset film which let distinguished by a high gloss, a high adhesive strength, abrasion resistance, hardness and impact resistance.

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Example 5

Purified 2 - hydroxyethyl methacrylate is stirred with ethylene glycol dimethacrylate in a concentration of 0.3 g per 100 g of 2-hydroxyethyl methacrylate. Dilute the mixture with 50 wt ^ of a phenolic resin (is this a ^f under the ^trademark! Diirez "used in the commercially available resin) and phere with 0.3 g of isopropyl percarbonate in an anaerobic Atmos" added at room temperature. The solution is applied to a steel plate cast into a Piim, 30 minutes cured at 40 ⁰ C, ilm to provide a thermosetting 3?, the ACTION for high gloss, high adhesion strength, Abriebfes, hardness and impact resistance is excellent.

Example 6

Purified 2-hydroxyethyl methacrylate is stirred with itbylene glycol dimathaorylate in a concentration of IfOg per 100 g of 2-hydroxyethyl ethacrylate. To the mixture is added 50% by weight of the pentaerythritol ester of a rosin resin (a resin sold under the trademark "Pentylin A" was used) and 0.2 g of isopropyl percarbonate in an anaerobic atmosphere at room temperature. The solution is cast on a steel plate to a thermosetting Piim, of 30 minutes, cured at 40 ⁰ C, so as to provide a Piim, which is distinguished by a high gloss, a high adhesive strength, abrasion resistance, hardness and impact resistance.

Yes

Purified 2-hydroxyethyl methacrylate is made with ethylene glycol dimethacrylate verrtthrt, in a concentration of 0.1 g per 100 g of 2- »hydroxyethyl methacrylate. The mixture will with 50% by weight of the glycol ester of a rosin (es

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was a under the trademark "Poly-pale ester used ¹¹ building under commercial resin), and treated with 0.15 g of isopropyl percarbonate in an anaerobic atmosphere at room temperature. The solution is cast on a steel plate to a film for 30 minutes at 40 ⁰ C. is cured to form a thermosetting film excellent in high gloss, adhesive strength, abrasion resistance, hardness and impact resistance.

Example 7b

The procedure described above is repeated with a methyl ester of a rosin (it was one marketed under the trademark "Abalyn" Resin used in place of the resin used in the previous example) so as to also obtain a thermosetting film c

Example 70

The procedure of Example 7a is repeated, namely with a hydroabstyl alcohol (it has been used under the trademark "Abitol" commercially available balsamic oil used in place of the hard used in Example 7a) and es A heat-curable film was also created.

Example 7ά

The procedure described above in Example 7a is repeated with polycaprolactam (the ^{resin sold under the trade mark w} Nylon-6 "was used in place of the resin used in Example 7a) and a thermosetting film was likewise obtained,

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IAO OVQINAL Example 7e

The procedure described in Example 7a is repeated, with a polysiloxane (here, under the Trademark "GE Silicone Resin 84" Product used in place of the resin used in Example 7a) and a molded body in the form of a decorative one was obtained Subject.

Example 8a

Purified 2-hydroxyethyl methacrylate is made with ethylene glycol dimethacrylate stirred, in a concentration of 0.1 g per 100 g of 2-Hydroxyäthylmethaerylat. The mixture will with 50% by weight of a phenoxy resin, which is used as a high molecular weight Polyhydroxyether resin characterized and made from bisphenol A. and an epichlorohydrin resin (a resin sold under the trademark "Phenoxy 8500" was used) is made and with 0.15 g of isopropyl percarbonate in one anaerobic atmosphere at room temperature. ! The solution is cast on a steel plate to form a film, the 30th Minutes at 40 ° 0 is cured and a thermosetting film which is characterized by high gloss, high adhesive strength, abrasion resistance, hardness and impact strength.

Example 8b

The procedure described above is repeated with a low molecular weight polyisobutylene, its molecular weight is in the order of magnitude of 8700 - 10 000 (it was sold under the trademark "Vistanex IM-MS" Resin located in place of the polyhydroxyether resin of the

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used example) and a thermosetting film was produced, which is characterized by high gloss, high adhesive strength, abrasion resistance, hardness and impact strength.

Example 8c

The procedure described in Example 8a above is repeated, with an alcohol-soluble shark protein made from Prolainixt spheres with a molecular weight ▼ on 40,000 - 50,000 existed (the resin sold under the trademark "Zein" was used instead of the im Example 8a used polyisobutylenes) and a thermosetting PiIm was obtained, which by a high Gloss, high adhesive strength, abrasion resistance, hardness and impact resistance is excellent.

Example 9a

2-Hydroxyethyl methacrylate (100 parts) is combined with tert-butyl peroctoate (0.05 parts) at 25 ° C. in an inert atmosphere. This mixture is combined with "nylon-6" (100 parts) in trifluoroethanol (85 parts) to give a clear solution. This solution is zweckt "producing a Torpolymerisates to 65 - 70 ⁰ C heated. The Vorpolymerisatlösung is cooled to 25 ⁰ C and then tert-butyl peroctoate (0.10 parts) and A'thylenglykoldimethacrylat (0.2 parts) was added. The viscous syrup is passed through an extruder with a diameter of 0.254 mm (0.01 inches) orifice. The squeezed fiber is directly ansohliessend led through a hot water bath which is maintained at the polymerization temperature of 80 ⁰ C. Bach 30 minutes, the solid fiber is taken out of the water, air-dried and with

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10O ⁰ C stretched.

Fabrics made from these fibers are extraordinary supple in their texture and they are very soft to the touch.

Example ffb

The process of Example 9a is repeated with the exception that a mixture of isomeric hydroxypropylmeth acrylates used in place of hydroxyethyl methacrylate will.

The "process of Example 9a is repeated _r", however, modified in that Oumol-a-hydroperoxide alo provide free radicals Yinylpolymerisatlonskatalysator is used.

2-Hydroxyethyl methacrylate (50 parts) and TiO ₂ (30 parts) are ground to a fine powder (Hegeman value 7-8) in a tube mill with a pebble filling. An additional amount of 2-Hydroxyätliylraethacrylat (50 parts) is then added together with ethylene glycol dimethacrylate (0.2 part), cobalt naphthenate, a known drying agent for metal paints or catalyst (0.1 part) and tert-butyl peroctoate (0.4 part) admitted. The resulting viscous syrup is spread on a wooden boat hull and hardened ^{at 20 ~ 35 0 O.} The "Seewaeser protective coating" obtained in this way is characterized by the fact that it can deter barnacles and also prevent algae growth.

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protection against corrosion. Furthermore, this coating prevents an increase in the speed of watercraft if it hits parts of the vehicle in contact with the water is applied.

Example 1OTj

The process of Example 10a is repeated, but with the modification that the casting syrup is applied to a steel hull and ^{hardened at 10O 0} O in the absence of cobalt naphthenate.

Ex i el 10c

The procedure of Example 10a is repeated with the difference, that a mixture of isomeric 2-hydroxyisopropyl methacrylates is used in place of hydroxyethyl methacrylate.

Example 11a

One made from 2-hydroxyethyl methacrylate (100 parts), ethylene glycol dimethaorylate (0.2 parts) and tert-butyl peroctoate (0.4 parts) existing solution is applied to a sheet of neoprene rubber and cured at 70 ° C for 1 hour. The coated film obtained in this way can easily be processed into a swimming cap which have the advantageous properties mentioned above having.

Example 11b

One made from 2-hydroxyethyl methacrylate (100 parts), ethylene glycol dimethacrylate (0.2 parts) and tert-butyl peroctoate (0.4 parts) is applied to a sheet of neoprene rubber.

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! 745187

worn, covered with a second rubber sheet eo ", that the air has no access and the whole is heated for 1 hour at 80 ⁰ C. After this time, both spolia are connected by the intermediate polymer layer firmly to one another,

Example 12a

2-Hydroxyethyl methaorylate (100 parts) is stirred with 0.05 parts tert-butyl peroctoate in a nitrogen atmosphere at a temperature of 40 ^° C. for 30 minutes. The resulting mixture is ^{cooled to 25 °} C. and so much tert-butyl peroctoate is added that the total amount of tert-butyl peroctoate added to the system is 0.15 part. At the same time ethylene glycol dimethaerylate (0.1 part) is added. The casting solution is poured into a mold in which an intrauterine device of the type described in U.S. Patent 3,200,815 can be molded and the molded article is then cured at 70 ° C.

Example 12b

The procedure of Example 12a is repeated, but with the modification that 0.2 parts of 1,3-butylene glycol dimethacrylate can be used as a crosslinking monomer.

Example 13a

2-Hydroxyethyl methacrylate (100 parts) is stirred with distilled water (50 parts) and tert-butyl peroctoate (0.1 part) in an anaerobic atmosphere at a temperature of 40 ^° C. for 20 minutes. The resulting mixture is ^{cooled to 25 °} C. and tert-butyl peroctoate (0.05 part) is added. A cross-linking monomer such as ethylene glycol dimethaorylate (0.2 ropes)

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is added at the same time as the catalyst. The casting solution is then applied by immersion impregnation to a polyethylene intrauterine gate of the type described in US Pat. No. 3,200,815 and the whole thing hardened at 70 ° 0 for 1 hour. Those products that have a sticky or adherent surface are dipped in water to dissolve any remaining unpolymerized monomer material, creating a smooth, non-sticky surface is achieved.

Example 15b

If the procedure of Example 13a is repeated in the absence of water, a casting solution is obtained which, after the Cure provides an essentially fully polymerized (to 99.5 #) polymerization product which is a has a smooth, non-adhesive surface.

Example 13c

The process of Example 13b is repeated with the difference that a catalyst mixture is used which consists of 0.05 part of tert-butyl peroctoate and 0.1 part of isopropyl percarbonate. The catalyst concentration is determined by Added isopropyl percarbonate to the theoretical value.

Example 13d

The procedure of Example 13b is repeated with the modification that BaSO ₄ (50 parts) is mixed into the system, to be precise before the casting and the final hardening.

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Example 14a

Distilled 2-Hydroxyäthylraethacrylat (100 g} with 0.1 g of tert-butyl peroctoate in an atmosphere auaeroben 15 - stirred 70 ⁰ C The resulting mixture is cooled to 25 ° 0, and it is so much tert - 40 minutes at 25.. -Butyl peroctoate is added so that the total concentration of tert-butyl peroctoate in the system is 0.2 g to 100 g of 2-Hydro2Q'ethyl methacrylate. At the same time, when the catalyst concentration is brought to the theoretical level, ethylene glycol dimethacrylate is converted into Add a concentration of 0.2 g to 100 g of 2-hydroxyethyl methaorylate: a. Danaoh is added to the casting mix in a microfibre of silicon dioxide with a particle size of 0.015 - 0.02 γ. (Available in stores under the name "Gab ~ 0 ~ 3il") mixed in to obtain a prepolymer syrup having such rheological properties as are desired for use as a denture lining base material, see below.

Pouring syrup can be applied to a denture base material consisting of a standard acrylic polymarisatraasse and, after the impression has been made, polymerized with this material in a single polymerisation stage in a standard form under conditions of time, temperature and pressure. In the molds, in which there is already a ready-made polymeric gobiss base material, the pouring syrup can be spread on and polymerized flat for the production of the impression under the standard conditions described in US Pat. No. 2,645,012 for the porping of dentures. Sd grazing Gießsirupe _f obtained for preparing the versehiedenntoii Pormartikel by? N s.itii polymerization are suitable, with the items the desired specific Eigensehaften such as mechanical reotigko.1t, a high reversible lüsDigkeitsabsorptionsvermögen 3?, Dimensional stability in liquid media and a have elastic resilience after deformation.

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Example 14b

The procedure of Example 14a is used with the difference that hydroxypropyl methacrylate is used instead des 2-Hydroxyäthy! methacrylate is used.

Example 14c

The method of Example 14a is repeated with the modification that isopropyl percarbonate as a catalyst and 1,3 ~ butylene glycol dimethaorylate as a crosslinking monomer be used.

Example 14d

Following the procedure of Example 14a, a full mouthguard impression is made after using the there called casting syrups. If required, the pouring syrup can be dipped onto a reinforcing element made of rubber in the middle applied and thus an additional stiffening can be achieved.

Example 15a

2-Bydroxyäthylmethacrylat (100 g) is mixed with tert-butyl peroctoate in a weight ratio of 0.15 g to 100 g of methacrylate. Ethylene glycol dimethacrylate is then added in a concentration of 0.20 g per 100 g of 2-hydroxyethyl methacrylate together with 1 g of the foaming agent sodium carbonate. The mixture is ^{heated to 70 °} C. and the solid, friable polymer foam formed is comminuted to a fine powder with a mesh screen fineness of 80 meshes. The polymer powder thus formed is mixed with a solution containing natural aniseed aroma and

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the resulting mixture is ground on a mechanical rolling mill for about δ hours. The polymer powder absorbs so the aroma. The solution is then filtered and the residue is dried at room temperature.

Example 15b

Following the procedure of Example 15a above, Bs worked and the aniseed aroma through an orchid perfume replaced.

Example 16

2-Hydroxyäthyliaethacrylat (100 g) is mixed with tert-butyl peroctoate (0.2 g). Ethylene glycol dimethacrylate (0.2 g) is then added together with 4 g of sodium bicarbonate as a foaming agent. The mixture is heated to 70 ⁰ G and the resulting solid, friable Polymerisatschaum is crushed to a fine powder of a Maschensiebfeinheit of 80 mesh. The polymer powder formed is mixed with such an amount of the antibiotic phenoxymethylpenicillin, which is dissolved in ethyl alcohol, that is sufficient to gradually set 1,200,000 units per gram free and the resulting mixture is placed on a mechanical roller mill until the polymer powder has a Has absorbed the amount of antibiotic in the desired concentration. The solution is then filtered and the residue is dried in vacuo.

Example 17

Suitably purified 2-hydroxyethyl methacrylate is with 0.15 g Ieopropylperoarbonat in an anaerobic atmosphere stirred at room temperature. Ethylene glycol dimethacrylate is then added at a concentration of 0.1 g per 100 g of 2-hydroxy

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ethyl methacrylate added. Before casting, the coagulation-inhibiting Medium heparin added. The solution is then placed in a tube or form of known strength and thickness -diameter, which is a tubular reinforcement material made of Dacron contains, poured, so that during use the suturing of the replacement vessel with the body vessel to be repaired is facilitated. The reinforcement material is from the Casting solution completely enveloped.

Having by inserting an a dedicated corresponding large dome in the shape is obtained an artificial artery of the desired wall thickness, the molded piece is then cured for 30 minutes at 40 ⁰ C, taken out from the mold, washed with water and then in a v / AES sr igen solution stored.

Example 18a

100 g of 2-hydroxyethyl methacrylate are mixed with 0.15 g of tert-butyl peroctoate. Then 0.2 g of ethylene glycol dimethacrylate are added together with 1 g of sodium bicarbonate. The mixture is heated to 70 ⁰ C and comminuting the polymer formed by grinding and cutting into particles of Piilengrösse. The parts are then soaked in a 50:50 glycerine / water mixture for 6 hours to give them a non-bleeding moisturizing power. Then they are dried. The thus obtained sheet-like particles are used as tobacco smoke filters in cigarettes.

Example 18b

The procedure of the previous example is repeated with the difference that the glycerine / water mixture is tobacco flavor is added to give the filtered Rauoh a tobacco flavor

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give and in this way the aroma, which by the Filtering out the tar constituents and other combustion products that normally give the impression of tobacco flavor when inhaled convey, has been lost, to replace.

According to a further embodiment, an alcoholic menthol solution was used together with the tobacco aroma as a flavoring agent. The alcoholic solutions can be used in such quantities that they make up 1-90 weight ^ of the hydrophilic polymer, although a lot of $ 10>, is preferred especially when glycerin is used as a humectant.

Example 18c

100 parts of 2-hydroxyethyl methacrylate are stirred with 0.05 parts of tert-butyl peroctoate for 30 minutes in a nitrogen atmosphere at 30 °. The resulting mixture is cooled to 25 ⁰ C. Another peroctoate is then added in such an amount that a total of 0.15 parts are mixed in, and at the same time 0.1 part of ethylene glycol dimethacrylate is added. The casting solution is then poured onto a plate in the form of a film and cured for 30 minutes at 70 ° 0 in order to obtain a filter element suitable for chromatography which is able to remove water-soluble stains and discoloration-forming components, such as water-soluble pigmented bodies of synthetic and natural dyes or the like.

Example 19

100 g of 2-hydroxyethyl methacrylate are mixed with 0.20 g of tert-butyl peroctoate mixed in an inert atmosphere and then 0.20 g of ethylene glycol dimethacrylate was added. The mixture is then

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a water-soluble catalyst is added before it is ^{hardened for 30 minutes at 40 °} C. in order to form a catalyst bed support. The dried carrier is able, when it is moistened with water, _c dispense the catalyst in an aqueous solution or in a moist gas stream, which are catalyzed again.

Example 20a

100 g of 2-hydroxyethyl methacrylate are mixed with 0.15 g of isopropyl percarbonate in an anaerobic atmosphere at room temperature. Then 0.1 g of ethylene glycol diraethaorylate is added. P Before pouring, a 2 # aqueous solution of merbromin is added as a universal antiseptic agent. The resulting solution is applied to a mesh fabric made of Dacron in the form of a film and a bandage ^{material is obtained after curing at 40 ° C. for 30 minutes.} The dried bandage gradually releases the antiseptic when it is immersed in or moistened with water, or when it comes into contact with the lymphatic exudate of an open wound or mucous membrane.

Example 20b

According to the working specification of Example 20a, a polie f or a PiIm in the form of a bandage is produced which has a thickness of about 0.127 - 1.5 mm. Instead of the universal antiseptic, the local antibiotic neomyoin sulfate is used before Poured in an amount of 5 mg (corresponding to an amount of 3.5 mg base) was added per gram of polymer carrier. The resulting film is used as a temporary covering material for burn wounds, and it has been found that the load of the polymer with the antibiotic on contact with the burn wounds in the meat the terrible complication of a pseudo

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domonas infection and blood poisoning and prevents Reduces fluid loss from the burned surface.

Example 21

100 g of 2-hydroxyethyl methacrylate are mixed with 0.1 g of tert-butyl peroctoate in an inert atmosphere. Then 0.15 g of ethylene glycol dimethacrylate are added. Before casting and 30 minutes long curing "at 40 ⁰ G a Mhrmedium is added constituting 50 wt ^ of polymerisation fclööung The dry plate can be stored and then immersed in water, so as to discharge the nutrient medium again, which then with Bacterial cultures can be spotted.

Example 2 2

The procedure of Example 12a is repeated, except that the (xiessolution is poured into molds, which contain the blanks of Allow contact lenses to be molded, which then after cooling and drying with the aid of conventional devices Contact lenses are ground. By compensating for the volume expansion of about $ 18 when wetting after the By grinding, the sole grinding operation can be carried out accurately and the desired dimensions are obtained.

Example 23

The procedure of Example 12a is repeated and the semolina solution is poured into molds that match the shapes of the desired prosthetic devices and body implants allow to map.

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Example 24

Bristles such as those for use in toothbrushes, cleaning brushes or the like can be prepared according to the procedure described in Example 9. Is it desired, that the bristles have additional strength, they can be shaped with an axial thread made of nylon or the like and like described in the previous example 14d - by immersion impregnation be coated, wherein the reinforcing central element can consist of rubber, plastic or the like.

Example 25a

The casting solution prepared according to the information in Example 12a is used as the base material for the pouring solution or syrup, those with peppermint oil, a flavoring, in an amount of 10 parts have been moved. The pouring solution flavored in this way is set aside and can be used to form cast products in the form of molded articles or in powder form can be used. According to a further embodiment the flavor can be added together with the catalyst used in the preparation of the polymer tea.

Example 25b

The casting solution of Example 13a is used as a basic or batch solution used and it is mixed with orchid perfume essence (10! Peile) offset. The resulting perfume carrier base solution is set aside provided for later use as a pouring solution or pouring syrup, in order to produce moldings in the form of artificial flower decorations by hardening, which are used as decorative Verpaokungsbeigabe are suitable for perfume bottles.

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Example 25c

The pouring syrup of the Ha example is made without using the made of microfine silicon dioxide. In place of the last mentioned substance, an alcoholic solution of menthol (10 parts) is added to the Gieoeirup to obtain an inentholhaltigen Yorpolyraerisat semolina syrup.

The cast syrups of Examples 12a, 13a and 14a are used as the base cast syrups and they are given a water-soluble stain and a water-soluble dye, a synthetic and a natural dye added to obtain stock solutions for later pouring and other uses.

Eb, the casting solution of Example 17 is first prepared and heparin is used in place of the anticoagulant that the antibiotic phenoxymethy! penicillin of Example 16, in Ethyl alcohol dissolved, added in such an amount that for gradual release 1 200 000 units per gram of Giesa syrup be available. The resulting pouring syrup is used as a stock solution for later pouring or for others Uses set aside. The pouring syrup and the pouring piece formed from it are either in a certain Used in shape or in powder form as a pharmaceutical carrier for the antibiotic. The application of the pouring syrup or the Molded or powdered preparations produced therefrom have the advantage that they prevent decomposition or the It is possible to avoid the loss of activity that the antibiotic suffers in the usual pharmaceutical carriers, whereby the shelf life or useful life of the antibiotic

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Preparations is extended. In addition, according to the present invention produced hydrophilic polymer the extremely desirable advantageous properties that it - regardless of whether it is in dry form or in the form of a product filled with a solvent - that Penetration of microbial and fungal contamination, such as gram-negative and gram-positive microorganisms, yeasts, Mold and viruses. This characteristic is of particular importance in the presence of contaminants Substances, such as the contamination of penicillin by various types of yeast.

Example 26

Distilled 2-0frdroxyäthylmethao: triacrylate (100 g) is mixed with 0.05 g of tert-butyl peroctoate 14-40 minutes in an anaerobic atmosphere at 25 - 70 ⁰ C stirred. The resulting mixture is cooled to 25 ⁰ C and additional tert-butyl peroctoate was added in such an amount that the Geeamtkonzentration of tert-butyl peroctoate in the system 0.15 g per 100 g of 2-hydroxyethyl methacrylate is. Ethylene glycol dimethacrylate is then added in a concentration of 0.15 g per 100 g of 2% hydroxyethyl methacrylate and at the same time the catalyst concentration is brought to the theoretical level. Peppermint oil (11.10 parts) is also added to the pourable syrup as a flavoring in order to obtain a flavored prepolymer syrup which can be stored. After hardening and granulation, the flavoring-carrying granules are added to chewing gum, gelatin and heartburn tablets as a component that gradually releases the flavor again.

Example 27 To 90 g of a basic pouring syrup, which is produced according to Example 14a

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has been assumed v / ground under stirring 0.15 g tert-butyl peroctoate within 15-40 minutes at 25 - 70 ⁰ G in an anaerobic atmosphere was added, with the amount of monomer used is set so that 90 g of a finished Gleseirups ontstehert. The mixture obtained is cooled to 25 ° 0. Sufficient tert-butyl peroctoate is added for 3 seconds that the total concentration of tert-butyl peroctoate in the system is 0.15 g per 100 g of 2-hydroxyethyl methacrylate. Ethylene glycol dimethacrylate is added in a concentration of 0.13 β per 100 g of 2-hydroxyethyl methacrylate at the same time as the catalyst concentration is brought to the theoretical level. Thereafter, peppermint oil (10 g) the casting is ^ syrup added to form the flavored stock solution "

Example 28

The pouring syrup of example Ha is used as the basic solution and ethinodiol diacetate is added to this solution as the progestogen component plus mestranol as the estrogen component, in an amount sufficient to release a timed amount of 10-1 part by weight per day, when the pouring syrup is brought into the shape of an ordinary article or in powder form. The resulting preparation is as a body implant or orally verabfolgendes preparation for the purposes of EmpfängnisveTPhütung or for other therapeutic purposes, ine etc. special for regulation of fertility or to treat fertility problems, is used. One advantage of using the present hydrophilic polymers as pharmaceutical carriers is that they allow the active substance to be released slowly or in a precisely timed manner. The time within which the active ingredient is released can easily be determined by the amount of

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th crosslinking agent, the ratio of surface area to volume in the shaped object and the concentration or the concentration gradient of the biologically active substance, which has been incorporated. The geech, indispensability The re-release of the active ingredient is increased by using solvents in the casting solution.

Example 29

Purified 2-hydroxyethyl methacrylate (100 g) is mixed with 0.2 g of ethylene glycol dimethacrylate and 1 g of benzoyl peroxide. P The monomer solution is formed by means of a nozzle which fine droplets, containing nitrogen in a chamber which is maintained at a temperature of 15O ⁰ C, is sprayed. After the spraying of the monomers had ended, 36 g of polymer beads, which are suitable for impregnation with flavorings or fragrances, could be removed from the chamber floor.

Example 30

Purified 2-hydroxyethyl methacrylate (100 g) is mixed with 15 g of ethylene glycol dimethacrylate, 10 g of orange oil and 0.3 g of tert-butyl peroctoate. The solution is poured into a 250 ml polypropylene glass beaker, which is placed in an oven for 3 hours in which a nitrogen atmosphere and a temperature of 80 ^° C. is maintained, in order to bring about the polymerization. The casting cylinder obtained in this way is friable and can easily be comminuted to a powder which quickly releases the orange oil again in contact with hot water.

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Example 21

100 g of norethandrolone (Nilevar) were dissolved in 3 ecm of 2-hydroxyethyl methacrylate containing 0.25 x ethylene glycol diraethacrylate and 0 _p 15 $> tert-butyl peroctoate. The solution was poured into the shape of a 1 cm 3 era cylinder and polymerized for 3 hours in a nitrogen atmosphere at 80 °. After removal from the mold, a cylinder is obtained which is suitable for in vivo implantation for the purpose of a long-term release of norethandrolone (Nilevar) and which is to be used in animal breeding.

A sewing thread made from raw cotton is used in the pouring syrup of the example 14a, in which, however, the thickening agent oil has been omitted istj, immersed and then passed through a polymerization zone, which is under nitrogen as a protective gas atmosphere and is kept at a temperature of 100 ° 0. The dwell time in the zone is measured at 1 1/2 hours. The coated, impregnated sewing thread obtained in this way is converted into an alcoholic solution of pluorthiouracil and penicillin dipped and then dried. The surgical suture material thus obtained has significant benefits because there is the spread of infection and unwanted cell migration along the suture prevented during postoperative healing.

Example 33a

A rubber catheter according to Foley is in the Giessirup of Example 14a, but in which the Yerdickungsmittel is omitted, dipped and then taken out and in an inert At gas atmosphere at a temperature of 8O ⁰ C exposed to cause the polymerisation of the so applied coating. Of the

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coated catheter is then dipped into an aqueous solution of neomycin sulfate and then dried, thus delivering a catheter that prevents infection when used to examine the genitourinary system.

example

A tube of Example 34 with a length of 5 inches and an outside diameter of 3 mm and a wall thickness of 0.8 ram is covered at each end with a pad made of Teflon felt, which is glued on with a Silastic ~ (silicone) adhesive, equipped. This tube equipped in this way is used to close the cut ends of a ureter connect, by sewing the end pieces of the same with the Teflon flanges. Replaced in this way in dogs Ureteral segments functioned satisfactorily for 6 months and after killing, no clouding was observed within the lumen of the polymer tube.

Example 33c

The method of Example 33a is used to coat tubes of various sizes, which are used as body vascular branches and replacement material, as ordinary cable routes, as ureteral exchange segments and as tracheal exchange segments should serve. As has been established, vein tubes containing ethyl alcoholic solutions of the polymer preparations can be used of Example 34 have been coated by dip impregnation below and above the vena cava are used for a longer period of time, whereas uncoated plastic tubes are used in the venous bloodstream usually clot within minutes. Such a coating by dipping can be done with throm-

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Curved plastics find application that attaches to the manufacture of body inlays and heart valve components. The polymer solution of Example 33a in aqueous ethyl alcohol is also well suited to be poured as a PiIm in situ onto the moist inner surfaces of the body, specifically by brushing it onto the abraded intestinal surfaces to prevent the formation of adhesions.

Example 34

100 g of the casting syrup of Example 33a were poured into three times the volume of water with vigorous stirring. The white precipitate thus obtained was dried by filtration and isolated% and yielded 9.0 g of polymer so that an intrinsic Viskosita \, b number (intrinsic viscosity) of 1.03 had when it was dissolved in absolute methanol. If the polymer is present in dissolved form in methanol, it is suitable for the production of hydrophilic coatings and films by spray coating, immersion impregnation, casting or the like. The resulting cast polymer showed a gelatinous hydrophilic behavior and was unable to absorb more than 30 fi of water when it was equilibrated in an aqueous medium,

Example 35

The solution of Example 17 is used to bind heparin by "the absorption of alkylbenzyldimethylamraonium chloride" as described as Gott's method in J. Surg. Research, Volume 6, (1966) page 274.

Shaped articles from the hydrophilic polymer solution of Example 33a can also be used for ion transfer in hemodialysis for the incorporation of the hemostatic agent thrombin

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m5187

and as a carrier for estrogen, nitrogen mustard, parathyroid hormone and the transport of edema fluid. ten and for the supply of oxygen-saturated solutions to the blood / Plastic interface can be used in artificial lungs. Pill or disk shaped bodies of the present polymeric material can be used in oral antiseptic solutions soaked and then introduced into the oral cavity, especially in the cheek pouches or in the sublingual cavity so act as a breath improver.

Example 36a

1000 g of silicone oil, 100 g of 2-hydroxyethylniethacrylate and 0.33 g of isopropyl percarbomide are placed in a flask equipped with a stirrer and a heating mantle. The flask is placed under nitrogen and stirred contents of the flask rapidly and heated to 100 ⁰ C. After 15 mlnUtiger treatment at 100 ⁰ C, the obtained polymer slurry was filtered hot to isolate the polymer. The polymer powder is again suspended in 300 ml of xylene, filtered and dried. The powder obtained with a particle size between 2 and 5 μ is obtained in a yield of 98 μa. The powder is used for the production of molded articles by injection molding and extrusion molding. In addition, the powder is dissolved in ethanol in order to obtain solutions for casting hydrophilic polymer films.

Example 36b

Example 36a is repeated using mineral oil in place of the silicone oils. The amount of 2-hydroxyethyl methacrylate is increased from 100 g to 200 g, and the amount of isopropyl percarbonate is increased from 0.33 g to 0.66 g. It will a yield of polymer beads with a diameter of 2 - 5 u

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• AD OWGlKlAL

is j, obtained from 98 i * .

Example 36a is repeated using xylene in place dee silicone oil. The 2-Hydroxyäthylmethaerylai; iaGngö is from 100 g increased to 300 g and the amount of isopropyl percarbonate increased Of99 g increased there will be an 85 $ yield of polymer beads obtain.

Example 37

■ I ■ I ill IHI I IMl I I «. IMIIII'Nwtl

30 g poly-C2-hydroxyethyl methacrylate}, which had been prepared according to the procedure of Example 36a _t galöst in 70 ml of methanol. To the solution 4.0 g Horse ££ be given erminzöl _o YiBKose solution is added to a moisture-proof plate and allowed to dry. A 0.0254 ram (1.0 mil) thick film is obtained. The dry I? Ilm is peeled off the plate and ground to form tiny little platelets that are suitable for incorporation into food, chewing gum and toothpaste and ensure that the peppermint taste is long-lasting when the product comes into contact with an aqueous medium. When the platelets are equilibrated in an aqueous medium, they are characterized by controlled hydrophilicity and they are unable to absorb more than 30% by weight.

Example 37 is repeated using the following flavorings:

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Anethole Oitral Ethyl propionate, ethyl acetate Acetaldehyde diacetyl Menthol grtine mint (spearmint)

squeezed orange juice tobacco extract

This gives powders that can be worked into and on Articles were intended that were appropriate for the particular flavoring that had been incorporated into the powder was, suitable and so a controlled release of the flavor toffmaterials during and during the moistening of the Ensure powder.

Example 39

50 g of poly (2-hydroxyethyl methacrylate), which had been prepared according to the procedure of Example 36a, are dissolved in 50 ml of methanol to form a viscous broth. 12.5 g of menthol are dispersed in this viscous solution then pressed through a spinneret to form fine threads that are allowed to dry and nernaoh into a fine one Powder intended for use in appropriately flavored products.

Example 40

To 100 ml of the ethanolic solution of Example 36a Given 2.5 ml of diacetyl. The solution is sprayed by means of a nozzle into a heated chamber in which a stream of air flows with it moved at high speed in order to achieve spray drying of the solution. From the SprUhtrookenvorrichtung can Ropes of 2 - 15 ^ * Durohmesser can be taken. These Particles are suitable for incorporation in food

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to ensure a controlled release of the diacetyl aroma and to prevent oxidation, decomposition or volatilization of the aroma toffee during storage.

Example 41

3.6 g of the powder from Example 36a are mixed with 0.008 g of Ν, ϊϊ-dimethylaniline impregnated by wetting the powder with an acetic Dime thy laniline solution and Allow the mixture to dry.

In a separate container, 9.9 g of 2-hydroxyethyl meth ~ acrylate with 0.0214 g ethylene glycol dimethacrylate and 0.05 g ^ Mixed benzoyl peroxide,

3.6 g of the impregnated powder form after adding 9.9 g of the formulated hydroxyethyl methacrylate gemisehea a paste-like mixture, which within 30 minutes without Application of heat cures to form a hydrophilic plastic article.

This mixture is used to line a denture prior to curing without the need to use a mold and apply heat and pressure as used in Example 14a. The mixture is applied to a standard acrylic denture base material prior to curing and, with the aid of a protective film or bag, the denture is placed in the mouth to form the impression of the palate. It is then allowed to set in the mouth a Gesamthärtungsdauer is maintained for 10 minutes, of which 5 minutes cured in the mouth. the thus-coated teeth panel shows the properties of the denture lining described in example 14a.

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The liquid monomer to powder ratios used in the manufacture are between about 2: 1 to about 4: 1. The amounts of catalyst and activator can be varied including the curing time and the exothermic temperatures to adjust. As can be seen, the present method and the formulations used for this enable Seat preparation and hardening of the denture lining directly on the patient's palate and this ensures an exact et) Profile and a good fit guaranteed.

Example 42

Disks of the hydrophilic polymer, which are produced as molded articles from the solution of Example 34 and a 6.35mm (1/4 inch) in diameter and 0.5mm thick with a solution of the antibiotic lincomycin hydrochloride monohydrate (Lincocin) and tested against standard Staphylocoecen strains on agar plates. the Inhalation zones are created with standardized 1 mg discs, which were obtained from the manufacturer, compared. There are multiple transfers of the hydrophilic polymer on blood agar to determine how long the antibiotic would elute from the gel "

It is found that the inhibition of the standard bacterial strain took place up to 22 days. Comparable paper disks with the same antibiotic showed zones of inhibition only for 48 hours. In some cases there will be 6 transfers of the slices, each time on a fresh blood agar plate. The results show that that the elution of the agent from the hydrophilic Polyroerisatscheibe is a gradual process and takes place over a noticeably long period of time. In addition, there is

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the impression that it is possible " ⁵ hours" to saturate the gel extremely strongly with the desired agent.

Example A3,

Shaped objects, according to Example 23 in Porm of irregular Cylinders and blocks that have been made are implanted in the dog's right atrial chamber to order To determine the blood vessel compatibility of the hydrophilic polymer. After 1 month later, the dog's iodine was administered to see that the hydrophilic polymer did not favor a thrombosis and that the only clot that could be observed was at the point where the hydrophilic ™ polymeric object was attached to an atrium wall.

In an in vitro test, test tubes containing methyl alcoholic solutions of the prepared according to Example 37, hydrophilic polymer coated, filled with dog blood; then the coagulation times are measured. It is found that compared to clotting times of 6 Tolls in control attempts with the hydrophilic polymer coated Eeagena glasses had average clotting times of 3 »5 hours, which illustrates is that the hydrophilic polymer delays a surface thrombosis considerably. |

To the other properties of the body vascular substitutes, Which appear in such implants, include wettability, slipperiness, conductivity, extensibility and the ability to ionize organic and inorganic compounds, including chlorine, sodium, potassium and phosphate ions, at high concentrations and high transit speeds.

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17 4 518

Example 43a

One for use as a vehicle windshield, window or mirror certain glass plate comes with a methy! alcoholic Solution of the hydrophilic prepared according to Example 37 Polymer coated. The resulting upper pull (Thickness 0.127 mm, corresponding to 0.005 inches) is translucent and of optical clarity, adherent and fogged not when exposed to hot, humid air. In an analogous way, a plastic plate made of methyl methacrylate, which is intended for use as a windshield in an aircraft, coated

Example 43b

The procedure of Example 43a is used to create a optical element in the form of a camera lens, which is provided with a reflection-reducing film of magnesium fluoride, to be covered and thus a translucent, optically clear, reflection-reducing, non-fogging optical element to create.

Example 44

The anti-W antibiotic chloramphenicol is added to the ethanolic solution of Example 36 and the resulting solution is used to coat a nylon sewing thread.

Example 45

An alcoholic solution of merouroohrom is added to the ethanolic solution of Example 36a. The resulting solution is applied to a wound by spraying and serves as a wound dressing.

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Example 46

3.6 g of the powder of Example 26a are with Mercusoehrom also impregnated with an acetone solution. The powder is then dried and numbed as a wound dressing on a wound to ensure an antiseptic effect.

The preceding examples © illustrate the in sifcu-addition of dyes, pigments, pre-sealing agents, Synthetic resins, medically effective sub tanas «, virus-inhibiting substances, fungicides, front Äntlsepbika, catalysts, Mhrmedisn, Steroids, or the like, during the Gie-IIJicupharB division after the beginning step in which that wuqüku · '.' öfiliohö, nichtvernetsite Homopolymer dee Polyhydroxj'äfchylmethacr, ylal; see or the like is formed and preferably at the stage of the addition of the processing catalyst, (rswisae additional components, especially pigments, thickening fluids * synthetic resins and the like, but can also directly from the starting monomers or added during the initial polymerisation.

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Claims (1)

- 50 claims Z th polymers 1. A process for the preparation of hydrophilic _P vorneft, characterized in / that Dian in a lösungsmittelfreian state enigstens has a nubstituierte hydrophilic fractional group one vast Monge of a water-soluble polymerizable Monoesters of an olefinic acid, v /, with a smaller amount of a The polymerizable diester of one of the olefinic acids mentioned, which has at least two esterifiable hydroxyl groups, is missing in the presence of such an amount of a vinyl polymerization catalyst which provides free radicals which is sufficient to polymerize the same. 2. The method according to claim 1, characterized in that daas the monoester mentioned from 3idem HydroxyallQ / leater of an α, ί3-unsaturated Carboxylic acid and the mentioned diester from a polymerizable diester of one of the mentioned a, ß ~ unsaturated « ten carboxylic acids. 3. The method according to claim 1, characterized in that said catalyst which _{produces free radicals consists of a member of the group isopropyl percarbonate P} tert-butyl peroctoate, cumene ct-hydroperoxide and benzoyl peroxide. 4. The method according to claim 1, characterized in that the » said monoester from a member of the group of Hydroxyalkyl acrylates and methacrylates. 3. The method according to claim 1, characterized in that said diesters are esters of acrylic or methacrylic acid. N§ «§ Document ΐν ^ Γΐ ^ ,,,, ^. ^ 209813/1351 • AD OWG) NAL 6. The method according to claim 1, characterized in that said monoester of a 2-hydroxyalkyl methacrylate and said diester consists of ethylene glycol dimethacrylate. 7. A process for the preparation of a liquid casting syrup, characterized in that in the solvent-free state, a predominant amount of a water-soluble polymerizable monoester of an olefinic acid _{r has} at least one substituted hydrophilic functional group, with a lesser amount of a vinyl polymerization catalyst providing free radicals in one mixed anaerobic atmosphere and the mixture is heated to a temperature between room temperature and about 80 ° 0 until the said monomer has become water-insoluble, the resulting mixture is then cooled to room temperature and a smaller amount of a polymerizable diester of one of the olefinic acids mentioned, which has at least two esterifiable hydroxyl groups, is added together with a further small amount of one of the said catalysts which is sufficient to form a liquid pourable syrup which is suitable for in situ polymerization. 8. The method according to claim 7, characterized in that one of said α said Monoester of a hydroxyalkyl ester of an a, ßungesättigten carboxylic acid and said Biester from a ä polymerizable diester is β-unsaturated carboxylic acids. 9. The method according to claim 7, characterized in that said, free radical-generating catalyst consists of a Representatives of the group isopropyl percarbonate, tert-butyl peroctoate, and benzoyl peroxide. 209813/13 51 10. The method according to claim _$ 7 characterized in that said Monoester of one representative of the group of hydroxyalkyl acrylates and methacrylates exists. 11. The method according to claim 7 »characterized in that the diesters mentioned are esters of an acrylic or methacrylic acid are. 12. Process for the production of a crosslinked, polymeric, solid, friable foam, characterized in that in the solvent-free state, a predominant amount a water-soluble polymerizable monoester of an olefinic acid having at least one substituted hydrophilic having functional group, with a smaller amount of a polymerizable diester of one of the olefinic ones mentioned Acids containing at least two esterifiable hydroxyl groups, and with a foaming agent in the presence of such Amount of free radical generating vinyl polymerization catalyst mixed together sufficient to form a solid polymerize friable foam. 13. The method according to claim 12, characterized in that the foam concentrate consists of sodium bicarbonate. 14. A method for producing a crosslinked, polymeric, compressible powder, characterized in that in In the solvent-free state, a predominant amount of a water-soluble polymerizable monoester of an olefinic Acid containing at least one substituted hydrophilic functional group with a minor amount of a water-soluble one polymerizable diester of one of the olefinic acids mentioned, which has at least two esterifiable hydroxyl groups, and with a foaming agent in the presence of such 209813/1351 17A5187 Amount of free radical generating vinyl polymerization catalyst sufficient to polymerize the same to a hard, friable foam and the The aforementioned foam is then crushed into a compressible powder. 15. A method for producing a synthetic fiber, characterized in that one in a solvent-free state larger amount of a water-soluble polymerizable monoester an olefinic acid having at least one substituted functional group with a larger one Amount of a synthetic resin mixed and heated the mixture mentioned to form a clear prepolymer solution, which said prepolymer solution cools to room temperature and a smaller amount of a polymerizable plastic in the presence added to a smaller amount of a vinyl polymerization catalyst which provides free catalysis, the latter being sufficient, in order to polymerize the same to a viscous syrup, the said syrup is passed through an extruder into a heated one liquid medium that is kept at the polymerization temperature will, leads to polymarize him to a fixed laser, one removes the mentioned Paser from the mentioned liquid medium, it dries and stretches in the air. 16. The method according to claim 15, characterized in that the synthetic resin consists of a linear polyamide, 17. Hard, friable, hydrophilic polymer foam, thereby characterized in that it is produced according to the method of claim 12. 18. Compressible, hydrophilic polymer powder, thereby characterized in that according to the method according to spoke 14 is made. 209813/1351 19. Liquid pouring syrup, characterized in that it is produced by the method according to claim 7. 20. Pest hydrophilic polymer body, characterized in that that it is produced by the method of claim 1. 21. Solid, thermosetting polymer film, characterized in that that it is produced by the method of claim 1. 22. Synthetic fiber mass, characterized in that it consists of a larger amount of a water-soluble, polymerizable Monoester of an olefinic acid, which has at least one substituted functional group, from a larger amount of a plastic and a smaller one Amount of a polymerizable diester that is at least two has esterifiable hydroxyl groups. 23. Synthetic fiber composition according to claim 22, characterized in that said plastic is made from a linear polyamide consists. 24. Synthetic fiber according to claim 22, characterized in that that said monoester from a representative of the group the hydroxyalkyl acrylates and methacrylates and the diesters consists of an ester of acrylic or methacrylic acid. 25. Hydrophilic lining compound for dentures, characterized in that that it is produced according to the working situation of the claim. 26. Hydrophilic compound for lining mouthguard surfaces, so that 209813/1351 characterized in that it is based on the working method of the Claim 1 is made " 27 = hydrophilic contact lens, characterized in that it consists of a solid, hydrophilic polymer body which is produced according to the procedure of claim 1. 28 "The method according to claim 1, characterized in that that a greater amount of a resin that comes from a natural or synthetic resin can be mixed with said monoester. 29. Solid, hydrophilic polymer body, characterized in that that according to the working method of claim 28 30 »polymer body according to claim 20, characterized in that that it is in the form of a medical-surgical device. 31. The device according to claim 30, characterized in that it is in the form of a device intended for intrauterine use Device is present. 32. Device according to claim 30, characterized in that that it is available in the form of an exchange vessel. 33. Device according to claim 30, characterized in that it is in the form of a body implant. 34. Device according to claim 30, characterized in that that it is in the form of a heart valve element. 35. Device according to claim 30, characterized in that 209813/1351 that it is in the form of a diaphragm intended for internal use. 36. Drug-delivering body, daduroh marked that it is produced according to the method of claim 1. 37. Flavor-releasing body, characterized in that that it is produced according to the procedure of claim 1. 38. Raw tobacco pilter element, characterized in that it is produced according to the method of claim 1. 39. Filter element for chromatography, characterized in that it is produced according to the method of claim 1. 40. exhaust filter element, characterized in that it is after the method of claim 1 is produced. 4-1. Catalyst bed support element, characterized in that that it is produced by the method of claim 1. 42. Thickening agent, characterized in that it is produced according to the method of claim 1. 43. Laminate, characterized in that it is produced according to the method of claim 1. 44. coating for objects exposed to sea water, characterized in that they are produced according to the method of claim 1. 209813/1351 45. bristle, characterized in that, according to the method of claim 15 is made. 46ο drug-releasing powder, characterized in that it is produced by the method of claim 14. 47. Flavor-releasing powder, characterized in that that it is produced by the method of claim 14. 48 · faba smoke filter powder element, characterized in that that it is produced by the method of claim 14. 49 «Powder element for chromatographic filters, characterized in that it is produced by the method of claim 14. 50. powder element for exhaust filters, characterized in that that it is produced by the method of claim 14. 51. A process for producing a hydrophilic ₉ liquid this syrup, characterized in that it comprises a water-soluble polymerizable Honoester an olefinic acid, the at least one substitutability te functional group in lösungsmittelireiem state, with a smaller amount of a free radical Vinylpolymerisationskatalysators blended sufficient In order to polymerize a substantial amount of the reaction product to a water-insoluble product, the reaction product mentioned is cooled to room temperature and a relatively larger amount of a single catalyst is added to form a liquid casting syrup which is suitable for in situ polymerization. 52. The method according to claim 51, characterized in that 209813/1351 a non-reactive additive is mixed in after the initial polymerization reaction. 53. The method according to claim 51, characterized in that that after the initial polymerization reaction, a non-reactive additive that is soluble in water or an alcohol is mixed in. 54. The method according to claim 51 »characterized in that the reaction product obtained from the liquid pouring syrup is precipitated in an excess of water in order to form an alcohol-soluble, solid, particulate, essentially completely polymerized, hydrophilic polymer which is not capable of more than about 30% by weight Absorb Water When It Equilibrates In Aqueous Solution will. 55. The method according to claim 52, characterized in that that the aforementioned precipitated, solid, particulate reaction product for the purpose of forming a polymer solution in a alcoholic solution is brought. 56. The method according to claim 52, characterized in that said additive is mixed into the liquid pouring syrup. 57. The method according to claim 51 »characterized in that that the monoester mentioned from a Hydrozyalkylester one α, β-unsaturated carboxylic acid and the diester mentioned consist of a polymerizable diester of one of the said α, β-unsaturated carboxylic acids. 58. The method according to claim 51, characterized in that 20 9 813/1351 the said, free radical generating catalyst a representative of the group leopropyl percarbonate, tert-butyl peroctoate, Cumene-a-hydroperoxide and benzoyl peroxide. 59. The method according to claim 51, characterized in that that the monoester mentioned consists of a representative of the group of hydroxyalkyl acrylates and methacrylates ". 60. The method according to claim 51, characterized in that the mentioned Siester from esters of acrylic or Consist of methacrylic acid. 61. The method according to claim 51, characterized in ™ de «* λ he mentioned monoester from a 2-hydroxyalkyl methacrylate and the said diesel is made from ethylene glycol disiethaerylate "exist. o2. A process according to claim 51, characterized in that the let-mentioned mixing in an inert atmosphere and in a temperature range between room temperature lind 80 ⁰ C. 63 * A process according to claim 52, characterized in that said additive consists of Gesohmackstoffe, fragrances, pharmaceutical agents, etc. antiseptic agents and body fluids from a representative of the group. 64- »The method according to claim 63, characterized in that that the mentioned pharmaceutical agent consists of a steroid ". 65. The method according to claim 63, characterized in that that said pharmaceutical agent consists of heparin. 209813/1351 66. The method according to claim 63 »characterized in that that said pharmaceutical agent consists of an antibiotic. 67 "Hydrophilic gaseous syrup, which is suitable for in situ polymerization with the formation of a solid, essentially completely thermosetting, hydrophilic polymer, the ". is unable to absorb more than about 30% by weight of water when it is equilibrated in aqueous solution, characterized in that it consists of a mixture of a larger amount of a water-soluble, at least one substituted, hydrophilic, functional group-containing monoester of an olefinic acid and a minor amount of an essentially completely polymerized polymer of said ester and a minor amount of a polymerizable diester of one of said olefinic acids which contains at least two esterifiable hydroxyl groups. 68. Hydrophilic, liquid pouring syrup according to claim 67 » characterized in that it contains a non-reactive additive component incorporated. 69. Hydrophilic, liquid pouring syrup according to claim 68, characterized in that the non-reactive additive component in a solvent such as water or an alcohol, soluble 1st. 70. An alcoholic solution of the hydrophilic liquid casting oil according to claim 67. 71. A solid, essentially completely polymerized, hydrophilic polymer that is unable to absorb more than up to about 30% by weight of water when in aqueous 209813/1351 ι /, Ci 18 / ~ 61 -. LSsung is equilibrated, characterized in that it is off the polymerization product of a major amount of a water-soluble monoester of an olefinic acid, the at least has a substituted hydrophilic functional group, and a minor amount of a dietiter of one of the olefinic ones mentioned Acids, which has at least two esterifiable hydroxyl groups. 72. Am substantially completely polymerized hydrophilic polymer according to claim 71 »characterized in that m is present in the form of a solid, friable foam which is unable to absorb more than up to about 30% by weight of water when in an aqueous solution is equilibrated, f; “A substantially fully polymerized hydrophilic A polymer according to claim 71 »characterized in that as is in the form of a compressible powder that is incapable of is to absorb more than up to about 30 ^ water by weight when equilibrated in aqueous solution, 74. A hydrophilic polymer according to claim 67 »thereby ge-1 records that the monoester consists of a representative of the i group of Bydrox ^ alky! acrylates and methacrylates. ? 5 · Hydrophilic polymer according to claim 67 »characterized in that the dies
Methacrylic acid. draws that the diester from an ester of acrylic or 76. Hydrophilic polymer according to Anspacuoh 71 »characterized in that that the monoester consists of a member of the group of hydrocyclic acrylates and methacrylates, 77. A hydrophilic polymer according to claim 71 »characterized in that that the diester consists of an ester of acrylic or methacrylic acid. 209813/1351 78. Process for the production of a hydrophilic polymer powder, characterized in that a water-soluble, polymerizable monoester of an olefinic acid, which has at least one substituted functional group, with a smaller amount of a polymerizable diester θ one of the olefinic acids mentioned, which has at least two esterifiable hydroxyl groups, is stirred with a high-speed stirrer in the presence of such an amount of a vinyl polymerization catalyst which yields free radicals sufficient to do the same in the presence of a suspension medium, in which the polymer thus formed is insoluble, to polymerize. 79. The method according to claim 78, characterized in that the suspension medium of a silicone oil, paraffinic or aromatic hydrocarbons or mixtures thereof consists. 80. Polymer powder, characterized in that it is produced according to the method of claim 78. 81. Surgical suturing material, characterized in that it consists of a fiber that is bonded with a polymer, like it is produced according to the method of claim 78, Is covered. 82. Surgical suturing material according to claim 81, characterized in that said polymer coating material a medically active substance has been incorporated as a component thereof. 83. Surgical suturing material, characterized in that it is coated with a polymer according to claim 71. 209813/1351 17451.H - 63 - 84. A method for lining a dentition, characterized in that the polymer powder of claim 80 with a liquid consisting of a predominant amount of a polymerizable ₉ water-soluble monoester of an olefinic acid, which has at least one substituted functional group, and a smaller amount of a polymerizable Diestera of one of the above-mentioned olefinic acids, which contains at least two esterifiable hydroxyl groups, is mixed in the presence of a vinyl polymerization catalyst and an area accelerator which provides free radicals, the said mixture is applied to the surface of a dentition facing the sack and the mixture hardens and makes it stick . ^ • 6-ίϋ, ßeMeB lining compound, characterized in that it consists of a mixture of the polymer powder according to claim 80 xmü. a liquid which in turn consists of a larger amount of a polymerizable, water-soluble monoester of an olefinic acid, which has at least one substituted functional group, and a smaller amount of a polymerizable diester of one of the olefinic acids mentioned, which contains at least two esterifiable hydroxyl groups, and a free one Vinj! 86. A bit, characterized in that there is an «· has clothing that consists of the hardened denture clothing mass according to claim 85. 67. POr the bituminous lining a certain component mixture, characterized in that it ver from the Polymerisatpia according to claim 80, in which a polymerization accelerator of the amine type is uniformly distributed. 209813/1351 17A5 187 88. A mixture of components determined purely for the area lining, characterized in that it consists of a liquid which in turn consists of a larger amount of a polymerizable, water-soluble monoester of an olefinic acid, having at least one substituted functional group, and a minor amount of a polymerizable piest one of the olefinic acids mentioned, which has at least two esterifiable hydroxyl groups. 89. Wound dressing, characterized in that it consists of the hydrophilic polymer of claim 71. 90. Wound dressing according to claim 89, characterized in that a medically active substance is incorporated into it is. 91. Wound dressing according to claim 89, characterized in that it is in the form of a film. 92. Wound dressing according to claim 91 »characterized in that that an elastic, reinforcing element is embedded in the film. 93. wound dressing, characterized in that it consists of a alcoholic solution of the hydrophilic polymer produced by the process of claim 78. 94. wound dressing, characterized in that it consists of the hydrophilic polymer powder of claim 78, in which a medically effective solution is incorporated. 95. A hydrophilic polymer powder according to claim 80, characterized in that marked that him an eeschmaokstoff, a fragrance or 209813/1351 - 65 a pharmaceutical agent is incorporated. 96. (glass element, characterized in that it has a translucent, has an optically clear, non-soled coating, that of a hydrophilic polymer according to claim consists. 97. Glass element according to claim 96, characterized in that it is in the form of an optical lens. 98. Glass element according to claim 96 »characterized in that that it is in the form of a vehicle windshield. 99. Plastic element, characterized in that it has a translucent, optically clear and non-fogging Has coating made of the hydrophilic polymer des Claim 78 exists. 100- plastic element according to claim 99 »characterized in that that it is in the form of an optical lens. 101. Plastic element according to claim 99 »characterized in that that it is in the form of a vehicle windshield is present. 102. Cigarette containing tobacco and a filter therefor, thereby characterized in that the filter is made of a hydrophilic polymer of a water-soluble Hydroxyalkylaerylats or -methacrylate. Cigarette according to claim 102, characterized in that the polymer consists of a copolymer of the acrylate or Methacrylate is made with a smaller amount of a poly-functional crosslinking agent. 209813/1351 Daos <contains a minor amount of a polyfunctional crosslinking agent 104. Seev / ater-protective coating, characterized in that a hydrophilic copolymer of a water-soluble hydroxyalkyl acrylates or methacrylates. Hydrophilic pouring syrup, which is used for polymerization in situ with the formation of a solid, practically completely polymerized, hydrophilic polymer is suitable, which does not absorb more than up to 30% by weight of water when in aqueous solution is equilibrated, characterized in that it is a mixture a larger proportion of a water-soluble hydroxyalkyl acrylate or methacrylate ester and a smaller proportion of a practically completely polymerized polymer this ester and a smaller amount of a polyniorizable one contains polyfunctional crosslinking agent. 106. A hydrophilic liquid pouring syrup according to claim 105, characterized in that it contains a non-reactive additive as a constituent. 107. Hydrophilic liquid pouring syrup according to claim 106, characterized characterized in that the non-reactive additive is soluble in water or alcohols as a solvent. 108. Alcoholic solution of the hydrophilic liquid sweet syrup according to claims 105 to 107. 109. Glaeeloment with a translucent, optically clear, non-fogging cover, characterized in that the Coating of a copolymer with a larger proportion of a water-soluble hydroxyalkyl acrylate or methacrylate and there is a smaller proportion of a polymerizable crosslinking agent. 209813/1351 üO "(rlceeloiittmt goraüßs A claim 109, thereby ß nfitf clans ^ s in foieia an optical lens ViK Glaselciment gßinäBS AtiBxiruoh 109i thereby ge & emiBOichnet, da £: S asinPorm a JPal «? 5CiUg ~ V / iTidechut8fiiclioiT3ß Tor ·" lies. 112, plastic element with eiüöin liohtdurohläosigen, optieoh ItIaX ¹ On ₈ nioht-bßschlagendon Üljarzug, thereby marked ₁₉ that dor Üljerziig from oinera copolyitsren an approx. Part eixiös water soluble hydroxyall ^ ylacrylatsiii izeaiagsschlagendon Üljarzugs? "consists. 113 “Plastic element according to claim 112” is thereby canceled as it is in the form of an optical lens. 114, KunBtatoiiOXement according to Ans-caeuch 112 _t characterized by cUiss öS in the form of a P. 209813/1351