IL28365A - Hydrophilic polymers,method of making same and articles obtained - Google Patents

Description

P A T E N T S & D E S I G N S O R D I N A N C E , This invention relates to novel hydrophilic polymers and processes of making same and has particular relation to such hydrophilic polymers in the form of casting syrups, friable solid foams and in powdered form, the latter form being partic-ularly adapted as a carrier for medicinally-active substances and for natural and synthetic flavors, essences, fragrances, spices, food colors, sweeteners, dyes and the like.

It is known to produce hydrophilic polymers, particularly to produce cross-linked hydrophilic polymers and, more particularly, to produce same in the form of shaped body hydro-gels in an aqueous solution by copolymerlzatlon whereby a major portion of a monoester of acrylic or methacryllc acid with a bi-functional 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 dlester of these acids and of an alcohol which has at least two esterifiable hydroxyl groups (see U.S. Patent Nos. 2, 976, 576 and 3, 220, 960) .

It is known that said prior art shaped body, hydro-phllic polymers prepared in an aqueous system are carriers for medicinally-active substances. Thus, it is known that medicinally-active substances may be dissolved in the aqueous constituent of such prior art shaped body hydrogels to provide gradual release of the medicinally-active substances; however, the resulting solutions are difficult to handle and store and the medicinal components are susceptible to air oxidation, degradation, deterioration, evaporation, etc.

Heretofore, it has been necessary to prepare a solid medicinal flavor, sweeteners, coloring agent and the like.

Additionally, in the prior art preparation, employing copolymer-lzation in an aqueous solution, it has not been possible to directly prepare a foam by the addition of the usual foaming agent B , such as sodium bicarbonate, for the reason that a soft semi-gelatinous hydrogel product resulted rather than the desired hard friable foam and it was not possible to convert such semi-gelatinous product to a friable foam or to a compact-able powder.

In addition, the said prior art process employing the conventional redox catalyst such as sodium bicarbonate and ammonium persulfate, potassium sulfate, sodium thiosulfate and ammonium persulfate or potassium sulfate, caused the polymerization reaction to go to completion at temperatures above 0°C. thereby preventing the preparation of a prepolymer preferably in the form of a liquid casting syrup which is capable of being dyed, pigmented, thickened and otherwise varied in form and thereafter cured to form solid or shaped bodies such as rods, sheets, tubes and other molded articles, or a hard, friable foam as will be hereinafter further described.

Additionally, said prior art process has resulted in an incompletely (up to about 95$) polymerized polymer and has further resulted in a polymer capable of absorbing excess amounts (more than 30# and up to 80$ by weight) when fully equilibrated in aqueous solutions.

The novel hydrophilic polymers of the present invention prepared in a water-free state, are substantially completely (about 99 ·5#) polymerized and are incapable of absorbing more than up to about 30# by weight of water when equilibrated in It now has been found that hydrophilic polymers can be prepared in a water-free system so as to permit the direct preparation of liquid casting syrups in prepolymer form which can be used for direct in situ polymerization in the form of castings of shaped bodies, films and coatings, which can be treated with conventional foaming agents such as sodium bicarbonate to result in hard, friable foams which can be directly formed into the swelled state or ground directly to powder form.

It also has been found that hydrophilic polymers can be prepared in a water-free system so as to permit ready preparation of the hydrophilic polymer products in powdered form. An object of the present invention is to prepare said hydrophilic polymers in a water-free system to permit their direct conversion to a powdered foam whereby the powdered polymers are especially adapted as carriers for medicinally-active substances, natural or synthetic flavors, essences, fragrances, spices and the like. The polymeric powders of the present invention have been found to be compact in form and have been found to provide the necessary stability and shelf life to enable their use as carriers for medicinal and flavoring substances which are susceptible to chemical reactions such as air oxidation, deterioration, evaporation and degradation.

A further advantage derived from the compactness ability of the instant powdered hydrophilic polymers is that upon encapsulation of the said powder carrying medicinally-active substances, flavors, essences and the like, greater stability and longer shelf life are provided than was heretofore possible.

Polymeric powders containing encapsulated flavors, thus providing superior flavoring solutions because encapsulation prevents air deterioration of the flavoring component and also prevents losses due to evaporation.

The liquid casting syrups of this invention are pre-pared by mixing a major amount of suitably purified commercial polytnerlzable monoester of an oleflnic acid containing at least one substituted hydrophillc functional group with a minor concentration of a free-radical catalyst and heating from ambient temperature to 80°C. until the polymerized portion of the monomer no longer shows water solubility. This product is then cooled to room temperature and addition of theoretical catalyst content carried out. The casting syrup can then be suitably dyed and pigmented and the fluid viscosity increased as desired by addition of appropriate thickening agents.

The casting syrup can then be cured to form products capable of being cast, formed or machined into rods, sheets, etc., for various uses. The product can exist in a rigid state, swelled state or as a foam. The polymer obtained from the cured casting liquids has good mechanical strength, reversible fluid absorption properties, the ability to retain its shape in a fluid media and to elastically recover it after deformation.

The casting syrup is also suitable, for example, for in situ polymerization in dental prosthesis, particularly for use in the preparation of denture liners and mouth guards. The absorbent qualities of the cured product permit advantageous use in other medical-surgical applications such as heart valves, vessel substitutes, dializer diaphragms, intrauterine devices and the like.

Prior to the addition of dyes, pigments, thickening are added to an excess quantity of water to form a precipitated polymer. The latter is soluble in highly polar organic solvents such as alcohols, glycols and glycol ethers. The precipitated polymer, when dissolved in polar solvents, is used as a polymer solution for the formation of films, coatings and the like. Alternately, the precipitated polymer is dried and used, for fabrication of shaped articles, by casting, injection molding, extrusion, calendaring and the like. further embodiment of the invention, hydrophllic soluble thermoplastic polymers are prepared by suspension poly merization of hydroxy eth^l methacrylate in a non-polar medium such as silicone oil or mineral oil. The monomer containing catalyst is dispersed in the non-feiyme medium in the form of small droplets which polymerize to form finely divided spheres or beads. Such beads may be dissolved in polar organic solvents for the preparation of films, coatings and the like.

Also, the beads may be used directly in the fabrication of thermoplastic shaped articles, as by injection molding, extrusion, calendaring and the like. Suspension polymerization, preferably, is conducted in an oil bath at temperatures ranging from 50 - 150°C. until bead formation is completed. The ratio of suspension oil to monomer preferably is from about $il to about 20: 1. The catalyst to monomer ratios preferably range from about 0.05 to 1.0 per 100 parts monomer.

The hydrophllic polymers of the present invention, polymerized in the water-free state, can be formed to adhere to metal, glass, rubber, plastics and other surfaces. Also, they can be cast into solid bodies which can be formed and ground into toric contact lens, which heretofore has not been solution .

Starting materials which may be utilized In accordance with the present Invention are hydroxy alkyl esters of an alpha-beta unsaturated carboxyllc acid such as 2-hydroxy ethyl meth-acrylate, hydroxy propyl methacrylate and the like. These are admixed In a water-free system with appropriate quantities of a free radical catalyst such as tertiary butyl peroctoate, iso-propyl percarbonate, benzoyl peroxide, and the like and a suitable cross-linking monomer such as ethylene glycol dimethacryl-ate, l,3-butylen¾?S£methacrylate, l, 4-butyfene?dimethacrylate or other polyfunctlonal monomerlc esters.

Free radical catalyst concentrations in the range of 0.05 g. to 1 g. catalyst per 100 g. of polymerizable hydroxy alkyl ester have been found to be adequate with the preferred quantity . the invention and its ability to retain water as a homogeneous constituent are strongly influenced by the proportion of poly-functional cross-linking agent present. For the polymer of this invention, concentrations of 0.05 to 15 g./ΙΟΟ g. of 2-hydroxy ethyl methacrylate have been found convenient, the preferred range being 0.1 to 0.2 g. cross-linking agent per 100 g. of polymerizable hydroxy alkyl ester.

Polymerization of the above reactants may be acceler-ated by the application of heat or, by selecting the catalyst and the amount thereof, the application of heat may be omitted and rapid polymerization induced at ambient temperatures. In instances where heat is applied for curing, temperatures ranging from about 20°C. to about 150°C. have been found to be Another object of the present invention is to produce new properties, as set forth above, and to improve and upgrade existing properties of the base hydrophilic polymer material by the incorporation therewith of a minor amount of one or more additive components selected from the group consisting of resins, rosin esters, phenoxy resins, silicone resins, low molecular weight polylsobutylenes, synthetic polymers and prolamines. The new compositions are especially adapted to form polyblends, which produce new properties and improve and upgrade existing properties of the base hydrophilic polymer.

The mixture is heated or otherwise cured in the absence of compatible volatile or non-volatile organic solvents to produce thermosetting polymeric materials having properties superior to those of the major constituent of the formulation. The upgraded properties of these new compositions of matter include, but are not necessarily limited to, improved hardness, adhesion, abrasion resistance, resiliency, and toughness. The polymerized material will yield products with improved machining and polishing characteristics and may also find use as a molding powder or polyblended with other molding compounds.

Other slight property improvements can be effected through use of small amounts of other cross-linking glycol dimethacrylate .

The method of this invention may be used to produce thermosetting surface coatings with improved adhesion to vari-ous substrates or to produce thermosetting resins for use as sheetings and films with improved clarity and toughness.

In general, 2-hydroxy ethyl methacrylate and the cross-linking monomer ethylene glycol dimethacrylate in quantities ranging from 10 to 50$ by weight (preferred range of 50$) resin of the coumarone indene type or their phenol modified counterparts in the presence of a free radical catalyst such as tertiary butyl peroctoate, isopropyl percarbonate, etc., and heated at temperatures ranging from 40 to 200°C. for approxi-mately 30 minutes. Organic or inorganic solvents are used as necessary to increase compatibility of the components. Compatible polymers having improved properties of tensile strength, modulus, hardness, thermal conductivity, etc., are formed.

The foregoing preferred proportional limitations also are employed with the phenoxy resin and the silicone resin additive components.

The resulting polymers can be prepared in the form of films or rods suitable for grinding into fine powders. By admixing foaming agents such as sodium bicarbonate with the re-actants prior to curing, the polymer may be obtained in the form of a foam which is easily disintegrated into a fine powder by means of a shearing action. The polymeric powders of this Invention are preferably obtained from foams. Quantities of 1 to 10 grams foaming agent per 100 grams of reactants have been found to be sufficient.

Polymeric powders prepared by any of the above means are mixed with natural or synthetic flavors or essences dissolved in an appropriate solvent and the mixture placed on a mechanical roller so that the solution becomes intimately mixed. The solution is then filtered and dried by air evaporation or forced heat. Upon evaporation of the solvent the flavoring or essence is retained by the, powder. Due to its extreme hydro-philicity and because the hydrophilic polymer of this invention has reversible fluid adsorption properties, the powders can be give concentrated flavors or essences. vessel substitutes for humans made from plastics are well known in themselves but when made from the polymers of the invention possess new and useful properties. In addition to the required properties such as chemical, physical and thermal inertness, vessel substitutes made from the polymers of the invention possess unusual colloidal properties which permit them to be very closely assimilated to those of living tissue and hence suitable for contact with body tissues for prolonged periods of time. Articles made from the polymers of the invention can be sterilized by boiling and, by steeping them in a physiological solution prior to insertion as a body tissue replacement, can be made isotonic with the surrounding tissue.

An unexpected advantage of articles made from the polymers of the Invention is that because of their reversible fluid adsorption properties, heparin, dissolved in isotonic salt solution, or other anticoagulants in a suitable solvent, can be added during manufacture and polymerization in situ can then be effected. The anticoagulant is then preeent In the vessel substitute for slow release after transplant to prevent thrombic formation. Medicinally-active substances, such as antibiotics and other active substances such as bacteriocides, antivirals, fungicides, which are water or alcohol soluble, may be added prior to polymerization or the end product polymer may be immersed in a solution of such substances to form a carrier.

The mechanical properties imparted to the polymer of the invention and its ability to achieve isotonicity with the surrounding tissue are strongly Influenced by the proportion of polyfunctlonal cross-linking agent present. For the polymers 2-hydroxy ethyl or hydroxy propyl methacrylate have been found to be convenient, the preferred range being 0.1 to 1.0 g. cross-linking agent per 100 g. of polymerizable hydroxy alkyl ester.

Prior to casting, the vessel substitutes may be reinforced with strengthening materials such as woven glass fibers, dacron and the like, in various rail and denier sizes present in tubular form in the mold so that the strengthening material is completely encased by the casting solution, Polymerization of the casting solutions may be accelerated by the application of heat or, by selecting the catalyst and the amount thereof, the application of heat may be omitted and rapid polymerization induced at ambient temperatures. In instances where heat is applied for curing temperatures broadly ranging from about 20 - 150°C. are used with ranges from about 20 - 100eC* being found convenient, the preferred range being about hO - 80°C. The reaction preferably is performed in an inert or anaerobic atmosphere employing carbon dioxide or nitrogen. It is known that the presence of oxygen inhibits the polymerization reaction thus requiring a longer reaction time or the use of increased polymerizing temperatures.

Additionally, the polymers of the present invention are particularly adapted for the manufacture of other prosthetic devices such as body Implants inasmuch as the liquid casting syrups in prepolymer form can be used for direct in situ polymerization. Contraceptive devices, such as intrauterine implants, diaphragms, and the like are well known in the art. A difficulty commonly encountered in the fabrication of such devices is that the material from which they are made is fre- -ø In addition, these devices frequently undergo deterioration on repeated sterilization, by boiling water or steam. The difficulties encountered in the prior art may be eliminated by fabrication of contraceptive devices comprised of the polymers of the present invention. In addition to the required properties such as chemical, physical and thermal inertness, the contraceptive devices made from the polymers of this invention possess unusual colloidal properties which permit them to be closely assimilated to living tissue. This permits them to be suitable for contact for prolonged periods of time. In order to obtain a device of suitable rigidity in such instances where this property is desired, it is preferable to blend in a filler material with the casting resin prior to final cure. The filler material may be an inert salt, such as barium sulfate, calcium carbonate, clay and the like. Another means of constructing a tissue compatible contraceptive device is by coating such a device made from another rigid plastic with the polymer composition of the present invention. Such a rigid device may be constructed of nylon, polyethylene, and the like. The poly-hydroxyalkyl ester functions to make the device more compatible with the tissue.

A further use of the present hydrophilic polymers in particulate form such as powders, beads, extrusions and the like, Is as a filter medium for tobacco smoke and other gaseous combustion products. The present hydrophilic polymer provides a non-migratory humectant carrier when it is presaturated in a polyhydric alcohol, e.g., glycerine propylene glycol, polypropylene glycol and ethylene glycol. Additionally, the hydrophilic polymers of the present invention provide an excellent retain and release other components, such as thiourea or dithio-aerythritol, which are stable against oxidation and are therefore available for reaction with the toxic, irritant or odorous combustion products of the exhaust smoke to eliminate or modify, same to non-objectionable form. Such components need only be soluble in the polyhydric alcohol, alcohol or water which is carried by the hydrophilic filtering medium. Thus, adsorption of and reaction with nitrous oxides, hydrocarbons and other combustion products in the gas stream can be had, The hydrophilic filtering medium additionally can be compounded with tobacco flavoring material to fortify or supplement the flavor lost in the train of exhaust tobacco smoke on inhalation through the present filter medium which is capable of removing some of the tars and nitrogenous combustion products which are understood to contribute the desired tobacco flavor. Additionally, specific flavoring materials such as menthol and the like also can be Incorporated into the filter material for release into the smoke train so as to improve the taste of the tobacco smoke upon inhalation.

The hydrophilic filter medium of the present invention can be readily employed for use as a chromatographic filter by means of its ability to absorb water soluble pigmented stain or color components.

In another embodiment of the invention the present hydrophilic polymers in powdered form also may be employed as a thickening agent in foods, particularly in view of their ability to take up water when in the dry state.

In still another embodiment of the invention, the hydrophilic gel materials of the present invention may be tion which can be slowly released from the hydrophilic gel material. Preferably, the bandage is formed of a plastic mesh reinforcement member carrying the hydrophilic gel material in the form of a strip or layer which has been cast thereon.

In still another form of the invention, the hydrophll- io gel material is adapted to carry water-soluble nutrients which can be released under controlled conditions. Thus, agar plates can be formed to carry the water soluble nutrient, then dried and available for substantially instant use upon soaking in water. : ΜΌ .· Β<37',03ύ,, filed Julj £θ,~Ί966, These and other objects and embodiments of the invention will be readily understood by reference to the following examples which are given by way of illustration without limitation: Example 1 Purified 2-hydroxy ethyl methacrylate Is stirred with a cross-linking monomer, ethylene glycol dimethacrylate, in the concentration of 0.15 grams per 100 grams 2-hydroxy ethyl methacrylate. To the mixture is added 90 per cent by weight of styrene copolymer resin (a commercial brand resin "Piccoflex" was employed) and 0.15 grams of a free-radical, vinyl polymerization catalyst, isopropyl percarbonate, in an anaerobic atmos- phere at ambient temperature. The solution is cast into a mold to form a shaped diaphragm which is cured for thirty minutes at 200eC. for approximately 30 minutes and removed from the mold. The diaphragm is machined and polished to form a finished Example 2 Purified 2-hydroxy ethyl methacrylate is stirred with ethylene glycol dimethacrylate, in the concentration of 0.1 grams per 100 grams 2-hydroxy ethyl methacrylate. To the mix-ture is added 50 per cent by weight of coumarone-indene resin (a commercial brand resin "Cumar" was employed) and 0.15 grams isopropyl percarbonate is added in an anaerobic atmosphere at ambient temperature. The solution is cast onto a steel panel in the form of a film which is cured for 30 minutes at 40°C. to form a thermosetting film characterized by high gloss, adhesion, abrasion resistance, hardness and high impact strength.

Example 3 Purified 2-hydroxy ethyl methacrylate is stirred with ethylene glycol dimethacrylate, in the concentration of 0.1 grams per 100 grams 2-hydroxy ethyl methacrylate. To the mixture is added 75 Pe** cent by weight of polyvinyl acetate resin (a commercial brand resin "Polyco" was employed) and 0.15 grams benzoyl peroxide is added in an anaerobic atmosphere at ambient temperature. The solution is cast onto a steel panel to form a film which is cured for 30 minutes at 100°C. to form a thermosetting film characterized by high gloss adhesion, abrasion resistance, hardness and high impact strength.

Example Purified 2-hydroxy ethyl methacrylate is stirred with ethylene glycol dimethacrylate, in the concentration of 0.05 grams per 100 grams 2-hydroxy ethyl methacrylate. To the mixture is added 50 per cent by weight of terpene resin (a commercial brand resin "Piccolyte" was employed) and 0.05 grams iso ambient temperature. The solution Is cast onto a steel panel to form a film which Is cured for 30 minutes at 0eC. to form a thermosetting film characterized by high gloss, adhesion, abrasion resistance, hardness and high impact strength.

Example 5 Purified 2-hydroxy ethyl methacrylate is stirred with ethylene glycol dimethacrylate, in the concentration of 0.3 grams per 100 grams 2-hydroxy ethyl methacrylate. To the mixture is added 50 per cent by weight of phenolic resin (a commer-clal brand resin "Durez" was employed) and 0.3 grams isopropyl percarbonate is added in an anaerobic atmosphere at ambient temperature. The solution is cast onto a steel panel to form a film which is cured for 30 minutes at 40eC. to form a thermosetting film characterized by high gloss, adhesion, abrasion resistance, hardness and high impact strength.

Example 6 Purified 2-hydroxy ethyl methacrylate is stirred with ethylene glycol dimethacrylate, in the concentration of 1.0 grams per 100 grams 2-hydroxy ethyl methacrylate. To the mix-ture is added 50 per cent by weight of pentaerythrltol ester of a rosin derived resin (a commercial brand resin "Pentylin A" was employed) and 0.2 grams Isopropyl percarbonate is added in an anaerobic atmosphere at ambient temperature. The solution is cast onto a steel panel to form a thermosetting film which is cured for 30 minutes at 0°C. to form a film characterized by high gloss, adhesion, abrasion resistance, hardness and high impact strength. ethylene glycol diraethacrylate in the concentration of 0.1 grams per 100 grams 2-hydroxy ethyl methacrylate . To the mixture is added 5P per cent by weight of glycol ester of a rosin resin (a commercial brand resin "Poly-pale Ester" was employed) and 0.15 grams isopropyl percarbonate is added in an anaerobic atmosphere at ambient temperature. The solution is cast onto a steel panel to form a film which is cured for 30 minutes at 0°C. to form a thermosetting film characterized by high gloss, adhesion, abrasion resistance, hardness and high impact strength.

Example 7b The foregoing process is repeated with a methyl ester of a rosin resin (a commercial bran4 resin "Abalyn" being employed to replace the resin of the previous example) to result in a thermosetting filmf Example 7c The foregoing process of Example a is repeated with a hydroabletyl aloohol (a commercial brand of a balsamic liquid "Abitol" being employed to replace the resin of Example 7a) to result in a thermosetting film.

Example 7d The foregoing process of Example 7a repeated with polycaprolactam (a commercial brand "Nylon-6" was employed to replace the resin of Example 7a) to result in a thermosetting film.

Example 7^ The foregoing process of Example 7a is repeated with polysiloxane (a commercial brand resin "0E silicone Resin 84" Example 8a Purified 2-hydroxy ethyl methacrylate is stirred with ethylene glycol dimethacrylate, in the concentration of 0.1 grams per 100 grams 2-hydroxy ethyl methacrylate. To the mix-ture is added 50 per cent by weight of phenoxy resin characterized as a high molecular polyhydroxy ether resin prepared from bisphenol A and epichlorohydrin resin (a commercial brand resin "Phenoxy 8500" was employed) and 0.15 grams isopropyl percarbon-ate is added in an anaerobic atmosphere at ambient temperature. The solution is cast onto a steel panel to form a film which is cured for 30 minutes at 40°C. to form a thermosetting film characterized by high gloss, adhesion, abrasion resistance, hardness and high impact strength.

Example 8b The foregoing process is repeated with low molecular weight polyisobutylene in the range of 8700 to 10, 000 m.w. (a commercial brand resin "Vistanex L -MS" being employed to replace the polyhydroxy ether resin of the foregoing example) to form a thermosetting film characterized by high gloss, adhesion, abrasion resistance, hardness and high impact strength.

Example 8c The foregoing process of Example 8a is repeated with an alcohol soluble protein of corn consisting of globular prolamine having a molecular weight range of 40, 000-50, 000 (a com-mercial brand resin "Zein" being employed to replace the polyisobutylene of the foregoing Example 8a) to form a thermosetting film characterized by high gloss, adhesion, abrasion resistance, hardness and high impact strength.

Example 9a 2-hydroxy ethyl methacrylate (100 parts) Is combined with t-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, form a clear solution. This is heated at 65° to 70°C. to form a prepolymer. The prepolymer solution is cooled to 25°C. and t-butyl peroctoate (0.10 parts) and ethylene glycol, dimethacrylate (0.2 parts) is added. The viscous syrup is passed through an extruder having an orifice of 0.01 in diameter. The extruded fiber is passed immediately into a heated water bath, maintained at a polymerizing temperature of 80°C. After 30 minutes the solid fiber is removed from the water, is air dried and oriented at 100°C.

Fabrics made from this fiber are extremely smooth in texture and have a high degree of softness to the touch.

Example 9b The procedure of Example 9a is repeated with the modification that isomeric hydroxy propyl methacrylate is employed in place of hydroxy ethyl methacrylate.

Example 9c The procedure of Example S& is repeated with the modification that a-cumene hydroxy peroxide is employed as the free-radical vinyl polymerization catalyst.

Example 10a 2-hydroxy ethyl methacrylate (50 parts) and Ti02 (30 parts) are ground in a pebble mill to a fine powder (Hegeman 7-8). Additional 2-hydroxy ethyl methacrylate (50 or catalyst (0.1 parts) and t-butyl peroctoate (0.4 parts). The resulting viscous syrup is painted onto a wooden boat hull and cured at 20 to 35°C. The resulting protective marine coating is characterized by its ability to discourage barnacle and algae growth and corrosion on prolonged underwater exposure.

Example 10b The procedure of Example 10a is repeated with the modification that the coating syrup is cast onto a steel hull and cured at 100°C. in the absence of cobalt naphthenate.

Example 10c The procedure of Example 10a is repeated employing an isomeric mixture of hydroxy isopropyl methacrylate isomers in place of the hydroxy ethyl methacrylate.

Example 11a A solution comprised of 2-hydroxy ethyl methacrylate (100 parts), ethylene glycol diraethacrylate (0.2 parts), and t-butyl peroctoate (0.4 parts) is cast onto a neoprene rubber sheet and heated at 70°C. for 1 hour. The resulting coated sheet is easily fabricated into a bathing cap form having the aforementioned properties.

Example lib A solution comprised of 2-hydroxy ethyl methacrylate (100 parts), ethylene glycol dimethacrylate (0.2 parts), and t-butyl peroctoate (0.4 parts) is cast onto a neoprene rubber sheet, covered by a second rubber sheet so as to exclude air, and heated at 80eC. for 1 hour. At the end of this time, both sheets are firmly bonded to one another by the Intermediate Example 12a 2-hydroxy ethyl methacrylate (100 parts) Is stirred with 0,05 parts t-butyl peroctoate in a nitrogen atmosphere at a temperature of 40°C. for 30 minutes. The resultant mixture is cooled to 2 °C. and t-butyl peroctoate added so as to make the total amount of t-butyl peroctoate added in the system 0,15 parts; Ethylene glycol dimethacrylate (0.1 parts) is added at the same time. The casting solution is poured into molds conforming to the desired shape of an intrauterine device of the type shown in U.S. Patent No. 3,200,815 and then cured at 70°C.

Example 12b The process of Example 12a is repeated, substituting 0.2 parts of 1,3-butylene glycol dimethacrylate as the cross-linking monomer.

Example 13a 2-hydroxy ethyl methacrylate (100 parts) is stirred with distilled water (50 parts) and tertiary butyl peroctoate (0.1 parts), in an anaerobic atmosphere at a temperature of 0°C. for 20 minutes. The resultant mixture is cooled to 25°C. and t-butyl peroctoate (0.05 parts) added. A cross-linking monomer such as ethylene glycol dimethacrylate (0.2 parts) is added at the same time as the catalyst. The casting solution is dip-coated onto polyethylene intrauterine devices of the type shown in U.S. Patent 3,200,815 and cured at 70°C. for 1 hour. Such products exhibiting a tacky or sticky surface are immersed in water to dissolve all the unpolymerized remaining monomer material, thereby effecting a smooth, non-tacky surface. of water, resulted in a casting solution which upon curing formed a substantially complete (99·5#) polymerized polymer product which exhibited a smooth non-tacky surface.

Example 13c The process of Example 13b is repeated, substituting a mixed catalyst consisting of 0.05 parts t-butyl peroctoate and 0.1 parts isopropyl percarbonate. Catalyst concentration is brought to theoretical by addition of isopropyl percarbonate.

Example 13d The procedure of Example 13b is repeated with the modification that BaSO^ (50 parts) is blended with the polymer system prior to casting and final cure.

Example 14a Distilled 2-hydroxy ethyl raethacrylate (100 g.) is stirred with 0.1 g. tertiary butyl peroctoate in an anaerobic atmosphere at 25-70°C. for 15-40 minutes. The resultant mixture is cooled to 25°C. and tertiary butyl peroctoate added so as to make the total concentration of tertiary butyl peroctoate in the system 0.2/100 grams of 2-hydroxy ethyl methacrylate. Ethylene glycol dimethacrylate, in the concentration of 0.2 g./ΙΟΟ g. of 2-hydroxy ethyl methacrylate is added at the same time as the catalyst concentration is brought up to the theoretical content. Micro silica of particle sizes 0.15 - 0.02 microns (commercial "Cab-O-Sil") is post added to the casting syrup to yield a pre-polymer syrup of desired rheological properties for use as a denture liner base material. The casting syrup may be spread on a standard polymeric acrylic denture base material and, after of time, temperature and pressure. In the case of existing polymerized denture bases, the casting syrup may be spread thereon and, after being impressed, polymerized under standard denture molding conditions, the latter being disclosed in U.S. Patent No. 2>6^ ,012. Casting syrups for in situ polymerization to form various articles having specific desired properties such as mechanical strength, high reversible fluid absorption properties, shape retention in fluid media and elasticity recovery after deformation are thereby formed* Example 14b The process of Example 14a is followed, substituting hydroxy propyl methacrylate for the 2-hydroxy ethyl methacrylate monomer· Example l c The process of Example 14a is followed using isopro-pyl percarbonate as the catalyst and substituting 1,3-butylene glycol dimethacrylate as the cross-linking monomer.

Example l d The process of Example 14a is followed with the excep-tion that an integral mouth guard impression is molded from an impression by use of the said casting syrup* If desired, a reinforcing center element of rubber may be dip-coated with the casting syrup so as to provide additional rigidity.

Example 15a 2-hydroxy ethyl methacrylate (100 g.) is mixed with tertiary butyl peroctoate in the quantity 0*15 g^/100 g* methacrylate* Ethylene glycol dimethacrylate, in the concentration with 1 gnu of a foaming agent, sodium bicarbonate. The mixture is heated to 70°C. and the resulting solid, friable polymeric foam is ground into fine powder of 80 mesh. The polymeric powder so formed is mixed with a natural anise flavor solution and the resultant mixture is placed on a mechanical roller for approximately 8 hours. The polymeric powder thus absorbs the flavor. The solution is then filtered and the residue dried at room temperatures.

Example 15b The process of the previous Example 15a is followed, substituting an oil of orchids perfume essence for the anise flavor.

Example 16 2-hydroxy ethyl methacrylate (100 g.) is mixed with tertiary butyl peroctoate (0.20 g.). Ethylene glycol dimeth-acrylate (0.20 g.) is added along with g. of a foaming agent, sodium bicarbonate. The mixture is heated to 70°C. and the resulting solid, friable polymeric foam is ground into fine powder of 80 mesh. The polymeric powder formed is mixed with a sufficient amount of phenoxymethyl penicillin antibiotic dissolved in ethyl alcohol to provide for gradual release of 1,200,000 units per gram, and the resultant mixture placed on a mechanical roller until the polymeric powder has absorbed the desired concentration of antibiotic. The solution is then filtered and the residue dried in vacuo.

Example 17 Suitably purified 2-hydroxy ethyl methacrylate is ate in the concentration of 0.1 g./ΙΟΟ g. 2-hydroxy ethyl meth-acrylate is added. Heparin, an antir-coagulant, is added before casting. The solution is cast into a tube or mold of known vessel thickness and diameter containing a dacron tubularly shaped strengthening material so that in use, stitching of the vessel substitute to the vessel being repaired is facilitated. The strengthening material is completely encased by the casting solution. Insertion of an appropriately sized mandril into the mold yields an arterial vessel of the desired wall thickness. The shaped article is then cured 30 minutes at 0eC, removed from the mold, washed with water and subsequently stored in an aqueous solution.

Example 18a 100 g. of 2-hydroxy ethyl methacrylate is mixed with 0.15 g. tertiary butyl peroctoate. 0.2 g. ethylene glycol di-methacrylate is added, along with 1 g. of sodium bicarbonate. The mixture is heated to 70°C. and the resulting polymer is disintegrated into pellet size particles by grinding and shearing. The pellets are mixed in a 50-50 mixture of glycerine and water for 8 hours to provide a non-migratory humectant action and dried. The resulting pellets are employed as a tobacco smoke filter in a cigarette.

Example 18b The process of the preceding example is repeated with the exception that tobacco flavor is added to the glycerine-water mixture to impart a tobacco flavor to the filtered smoke to replace the flavor lost by filtration of the tars and other combustion products which normally impart the tobacco flavor In a further embodiment, an alcoholic solution of menthol was employed as a flavoring agent along with the tobacco flavor. The alcoholic solutions may be employed so as to result in amounts ranging from 1 to 0 per cent by weight of the hydrophilic polymer, although 10 per cent is preferred, particularly if glycerine is employed as the humectant.

Example 18c 100 parts 2-hydroxy ethyl methacrylate is stirred with 0.05 parts tertiary butyl peroctoate in a nitrogen atmosphere at a temperature of 30°C. for 30 minutes. The resultant mixture is cooled to 25°C. and additional peroctoate is added to make up a total of 0.15 parts, 0.1 parts ethylene glycol dimethacrylate being added at the same time. The casting solution is poured onto a plate in the form of a film and cured at 70°C. for 30 minutes to result in a chromatographic filter element capable of absorbing water soluble stain and color components such as water-soluble pigmented bodies of synthetic and natural color dyes and the like.

Example Iff 100 g. 2-hydroxy ethyl methacrylate is mixed with 0.20 g. tertiary butyl peroctoate in an inert atmosphere and 0.20 g. ethylene glycol dimethacrylate is added. Water-soluble catalyst is added to the mixture before casting at 40°C. for minutes to form a catalytic bed support. The dried support, when wet with water, is adapted to release the catalyst in an aqueous solution or wet gas stream to be catalyzed.

Example 20a - ambient temperature. 0.1 g. ethylene glycol dimethacrylate is added. Before casting, a 2 aqueous solution of Merbromin is added as a general antiseptic. The resulting solution is cast onto a dacron mesh cloth in the form of a film to result in a bandage form upon curing for 30 minutes at 0°C. The dried bandage, upon being wetted by Immersion in water, or on contact with the lymphatic exudate of an open wound or with mucous membrane, gradually releases the antiseptic.

Example 20b A sheet or film in bandage form is made in accordance with Example 20a having a thickness range from about 5 mils to 1.5 mm. In place of the general antiseptic the topical antibiotic neomycin sulfate is added before casting in an amount of 5 mg. (equivalent to 3.5 mg base) per gram of polymeric carrier. The resultant film is employed as a temporary covering for burns, it being found that the antibiotic loading of the polymer in contact with flesh burns prevents the dreaded complication of pseudomonas injection and septicemia as well as limiting fluid loss from the burn surface.

Example 21 100 g. 2-hydroxy ethyl methacrylate is stirred with 0.1 g. tertiary butyl peroctoate in an inert atmosphere and 0.15 g» ethylene glycol, dimethacrylate is added. Before casting at 0°C. for 30 minutes, nutrient media is added to make up 50$ by weight of the polymer solution. The dry plate can be stored and thereafter immersed in water to release nutrient media for immediate staining for bacterial cultures. contact lens button which, after cooling and drying, can be ground by conventional means to form toric contact lenses. By compensating for the volumetric increase of about 18 per cent resulting from wetting the lens after grinding, the grinding operation can be performed accurately to give the desired dimensions.

Example 23 The process of Example 12a is repeated, the casting solution being poured into molds conforming to the shape of the desired prosthetic devices and body implants.

Example 24 Bristles adapted for use. in tooth brushes, cleansing brushes, and the like may be prepared by the process described in Example 9· If additional strength is desired for the bristles, they may be formed with an axial fiber of nylon or the like and dip-coated as described in the foregoing Example l4d, the reinforcing center element being of rubber, plastic or the like.

Example 25a The casting solution prepared in accordance with Example 12a is employed as a base stock casting solution or syrup to which oil of peppermint, a flavoring agent, is added in an amount of 10 parts. The flavored casting solution is set aside and can be employed as desired to form cast products in the form of shaped bodies or in powdered form. In a further embodiment, the flavoring agent is added along with the makeup catalyst.

Example 25b The casting solution of Example 13a is employed as a base or stock solution to which oil of orchids perfume essence (10 parts) is added. The resulting perfume carrying stock solution is. set aside for later employment as a casting solution or syrup to form upon curing a shaped body in the form of an artificial flower decoration adapted for use as a decorative package attachment for a perfume bottle.

Example 25c .

The casting syrup of Example 14a is prepared without the employment of micro silica. In place of the latter, an alcoholic solution of menthol (10 parts) is added to the casting syrup to yield a mentholated prepolytner casting syrup.

Example 25d The casting syrups of Examples 12a, 13a and 14a are employed as base casting syrups to which a water-soluble stain and color, a synthetic color dye and a natural color dye, respectively, are added to the base preparations to form a stock solution for later casting or other use.

Example 2j5e The casting solution of Example 17 is prepared and in place of the anti-coagulant heparin, the antibiotic phenoxy-methyl penicillin of Example 16, dissolved in ethyl alcohol, is added in an amount to provide for gradual release of 1,200,000 units per gram of casting syrup. The resulting casting syrup is set aside as a stock solution for later casting or other use. The casting syrup and the resulting cast product either in shaped or powdered preparation has the advantage that it prevents deterioration and loss of potency to which the antibiotic is subject in conventional pharmaceutical carriers, thereby extending the shelf life or expiration date of the antibiotic preparation. In addition, the hydrophilic polymer prepared in accordance with the present invention has the desirable characteristics, whether dry or solvent filled, of preventing the imbibition with microbial and fungal contaminants, such as gram negative and gram positive micro-organisms, yeast, molds and viruses. This characteristic is of particular importance in the presence of contaminants, such as preventing contamination of penicillin with various yeast forms.

Example 26 Distilled 2-hydroxy ethyl ethacrylate (100 g.) is stirred with 0.05gtertiary butyl peroctoate in an anaerobic atmosphere at 25-70°C. for 14-40 minutes. The resultant mixture is cooled to 25°C. and tertiary butyl peroctoate added so as to make the total concentration of tertiary butyl peroctoate in the system 0*15/100 grams of 2-hydroxy ethyl methacrylate. Ethylene glycol dimethacrylate, in the concentration of 0.15 g./ΙΟΟ g. of 2-hydroxy ethyl methacrylate is added at the same time as the catalyst concentration is brought up to the theoretical content. Oil of peppermint flavoring (11.10 parts) is also added to the casting syrup to yield a flavored prepolymer syrup which is suitable for storing. After curing and granulation, the flavor carrying granules are added as a flavoring releasing component to chewing gum, gelatin and antacid tablets.

Example 27 butyl peroctoate In an anaerobic atmosphere at 25-70dC. for 15-40 minutes, the amount of monomer employed being adjusted to result in 90 g. final casting syrup. The resultant mixture is cooled to 25°Ci and tertiary butyl peroctoate added so as to make the total concentration of tertiary butyl peroctoate in the system 0;15/100 grams of 2-hydroxy ethyl methacrylate i Ethylene glycol dimethacrylate, in the concentration of 0.15 gi/100 of 2-hydroxy ethyl methacrylate, is added at the same time as the catalyst concentration is brought up to the theo-retical content. Oil of peppermint (10 g.) is added to the casting syrup to form a flavored stock solution.

Example 28 The casting syrup of Example 14a is employed as a base solution to which is added ethynodiol diacetate as the progestagen component plus mestranol as the estrogen component in an amount sufficient to provide a timed daily release time of 10 to 1 parts by weight, respectively, when the casting syrup is prepared in the form of a shaped body or in powdered form. The resulting preparation is used as a body implant, or tablet for oral administration for contraception or in other therapy for fertility regulation or disturbance. One advantage of the use of the instant hydrophilic polymers as pharmaceutical carriers is that it permits a desired slow release or timed release of the active component. The release time is adjusted readily by the amount of cross-link agent employed, the surface to volume ration of the formed plastic, and the concentration or concentration gradient of the biologically active substance so incorporated. Release rate is increased by inclusion of solvent Example 29 Purified 2-hydroxy ethyl methacrylate (100 g.) is mixed with 0.2 g, of ethylene glycol diraethacrylate and 1 g. of benzoyl peroxide. The monomer solution is sprayed via a nozzle which forms fine droplets into a chamber containing nitrogen at a temperature of 150°C. After epraying of the monomer was concluded, 36 g. of polymer beads suitable for impregnation by flavors or scents was recovered from the floor of the chamber.

Example 30 Purified 2-hydroxy ethyl methacrylate (100 g.) is mixed with 15 g. of ethylene glycol diraethacrylate, 10 g. of orange oil and 0.3 g» of tertiary butyl peroctoate* The solution is poured into a 250 ml. polypropylene beaker which is placed in an oven under a nitrogen atmosphere at 80eC. for 3 hours to effect polymerization. The cast cylinder so obtained is friable, and can easily be comminuted to a powder which rapidly releases the orange oil in contact with hot water.

Example 31 In 3 cc. of 2-hydroxy ethyl methacrylate containing .2$ of ethylene glycol dimethacrylate and 0.15$ tertiary butyl peroctoate was dissolved 100 milligrams of norethandrolone (Nilevar). The solution was cast in the form of a cylinder 1 cm. 3 cm. and was polymerized at 80°C. for 3 hours in a nitrogen atmosphere. After removing from the mold, a cylinder suitable for in vivo implantation to provide prolonged release of the norethandrolone (Nilevar) was obtained for use in animal husbandry. syrup of Example 1 a with thickening agent omitted and is passed through a polymerization zone having a nitrogen atmosphere maintained at 100°C. Residue time in the zone is held at 1-1/2 hours. The coated, impregnated suture so obtained is soaked in an alcoholic solution of fluorothiouracil and penicillin, and is then dried. The surgical suture thus obtained is beneficial in preventing spread of infection and spurious cell migration along suture lines during post-operative healing.

Example 33a A rubber Foley catheter is immersed in the casting syrup of Example 14a with the thickening agent omitted, and then is removed and subjected to a temperature of 80°C. in an inert atmosphere to effect polymerization of the coating thus applied. The coated catheter is then immersed in an aqueous solution of neomycin sulfate and is then dried to provide a catheter effective in preventing infections when used in the urinary tract.

Example 33b A tube of Example 34 5 cm. in length with an outer diameter of 3 mm. and a wall thickness of 0.8 mm. is fitted at each end with a teflon felt collar adhered thereto by Silastic (silicone) adhesive. The device is employed to Join the severed ends of a ureter by suturing the ends thereof to the teflon collars. Segmented ureter replacements in the dog have func-tioned satisfactorily for over 6 months and upon sacrifice no encrustations were observed within the lumen of the polymer.

Example 33c common ducts, urethral replacement segments and lung tracheal segments. It has been found that venus tubes deep-coated with ethyl alcohol solutions of the polymer preparations of Example 34 can be placed in the inferior and superior of the vena cava for extended periods whereas uncoated plastic tubes ordinarily clot in the venous stream within minutes. Such dip-coating can be applied to thrombogenic plastics to body Insert materials and heart valve component fabrication. The polymer solution of Example 33a in aqueous ethyl alcohol also is adapted to be cast in situ as a film on moist internal body surfaces as by brush-coating on the abraded surfaces of bowel to deter adhesion formation.

Example 3 100 g. of casting syrup of Example 33a was added to three times its volume of water with vigorous agitation. The white precipitate so obtained was Isolated by filtration and dried to yield 9.0 g. of polymer showing an intrinsic viscosity of 1.03 when dissolved in absolute methanol. The polymer, as dissolved in methanol, is suitable for the formation of hydro-philic coatings and films by spray coating, dip coating, casting and the like. The resulting cast polymer exhibited controlled hydrophilic properties being incapable of absorbing more than 30$ water when equilibrated in aqueous medium.

Example 35 The solution of Example 17 is used to bond heparin through absorption of benzalkoniu chloride as reported in Gott's technique (J. Surg. Research - Vol. 6, p. 274, 1966) .

Shaped articles of the hydrophilic polymer solution dialysis for the incorporation of the hemostatic agent thrombin and as carriers for estrogens, nitrogen mustard, parathormone, the transport of edema fluid and for the export of oxygen saturated solutions to a blood-plastic interface in artificial lung applications. Pellets or discs of the instant polymerlo material can be soaked in oral antiseptic solutions and can be employed in the oral cavity, particularly in the buccal pouch or in the sublingual cavity for the slow release of the oral antiseptic as a breath sweetener.

Example 36a Into a flask equipped with an agitator and a heating mantle was charged 1000 grams of silicone oil; 100 grams of 2-hydroxy ethyl methacrylate and 0.33 grams of isopropyl per-carbonate. The flask was placed under a nitrogen atmosphere and the contents were rapidly agitated and heated to 100°C.

After 15 minutes at 100°C, the polymer slurry obtained was filtered hot to isolate the polymer. The polymer powder was reslurried in 300 ml. of xylene, filtered and dried. A 98$ yield of 2μ to particle si2e powder was obtained. The powder was employed in the injection molding and extrusion of shaped articles. Additionally, the powder was dissolved in ethanol to form solutions for casting hydrophilic polymer films.

Example 36b Example 36a was repeated using mineral oil in place of the silicone oil. The amount of 2-hydroxy ethyl methacrylate was increased from 100 g. to 200 g. and the quantity of isopropyl percarbonate was increased from 0.33 to 0.66 g.

A 98$ yield of polymer beads ranging in diameter from 2 to 5 Example 36c Example 36a was repeated using xylene in place of the silicone oil. The amount of 2-hydroxy ethyl methacrylate was increased from 100 g. to 300 g. and the quantity of isopropyl percarbonate was increased to 0.99 6. An 85$ yield of polymer beads was obtained.

Example 37 Poly- (2-hydroxy ethyl methacrylate) 30 g., prepared in accordance with Example 36a, was dissolved in 70 ml. of methanol. To the solution was added 4.0 g. of peppermint oil. The viscous solution was coated on an impervious plate and allowed to dry to form a film 1.0 mil thick. The dry film was stripped from the plate and was ground to form minute platelets suitable for incorporation in food products, chewing gum and toothpaste to provide prolonged release of the peppermint flavor on contact of the product with an aqueous medium. When equilibrated in aqueous medium the platelets were characterized by controlled hydrophilicity, being incapable of absorbing in excess of 30$ by weight of water.

Example 38 Example 37 was repeated with the following flavoring materials: anethole citral ethyl propionate ethyl acetate acetaldehyde biacetyl menthol spearmint expressed orange oil tobacco extract Powdere were obtained for incorporation in and on articles appropriately suited for the particular flavor incor-porated in the powder to provide for controlled release of the Example 39 Poly- (2-hydroxy ethyl methacrylate), 50 grams, prepared in accordance with Example 36a, was dissolved In 50 ml. of methanol to form a viscous dope; menthol, 12.5 g»> was dis-persed in the dope which was then forced through a spinaret to form fine filaments which were permitted to dry and thereafter were chopped to a fine powder for use in flavored products.

Example 40 To 100 ml. of the ethanolic solution of Example 36a was added 2.5 ml. of biacetyl. The solution was sprayed via a nozzle into a heated chamber having a high velocity air flow to effect spray drying of the solution. Particles ranging in size from 2 - 15 microns in diameter were recovered from the spray drying apparatus. These particles were suitable for incorpora-tion in food products to provide controlled release of the biacetyl flavor, and to prevent oxidation, deterioration or volatilization of the flavor during storage.

Example 41 3.6 grams of the powder of Example 36a is impregnated with .008 g. of Ν,Ν-dimethyl aniline by wetting the powder with an acetone solution of dimethyl aniline and allowing the mixture to dry.

In a separate container, 9·9 g. of 2-hydroxyethyl methacrylate is mixed with 0.0214 grams of ethylene glycol di-methacrylate and O.05 grams of benzoyl peroxide. 3.6 g. of the impregnated powder, when mixed with 9.9 g. of the formulated hydroxyethyl methacrylate mixture formed a paste mixture which cured within 30 minutes with no This mixture before cure was used to line a denture without the necessity of using a molding flask and without applied heat and pressure as employed in Example 14a. The mixture before cure was applied to a. standard aorylic denture base material, and with the aid of a barrier film or bag, the denture was placed in the mouth to form the impression' of the gum and was permitted to cure in the mouth. A total curing time of 10 minutes was used, with 5 minutes curing time taking place in the mouth. The denture liner thus applied exhibited the properties of the denture liner of Example l4a.

Prepared ratios of liquid monomer to powder are from about 2 to 1 to about 4 to 1. Catalyst and activator amounts can be varied to adjust the curing time and exothermic temperatures. As will be apparent, the instant process and formulation enables chair-side preparation and cure of the denture liner directly on the gum of the patient to achieve an exact profile and fit.

Example 42 Discs of hydrophilic polymer, prepared as shaped articles from the solution of Example 34, measuring 1/4 inch in diameter and 0.5 mm. in thickness were saturated with an antibiotic solution of lincomycin hydrochloride monohydrate (Lincocin) and tested against standard staphylococcic strains' on agar plates. The zones of inhibition were compared with standardized 1 mg. discs obtained from the manufacturer. Multiple transfers of the hydrophilic polymer also were made on blood agar to determine how long the elution of the antibiotic from the gel would take place. with the same antibiotic exhibited zones of inhibition only for 48 hours. In some cases 6 transfers of the discs, each to a fresh blood agar plate, were carried out. Prom the results it was apparent that the elution of the agent from the hydrophilic polymer disc is a gradual process and extends over a significant period of time. Moreover, it appears that it is possible to heavily saturate the gel with the desired agent.

Example 43 Shaped articles made in accordance with Example 23 in the form of irregular cylinders and blocks were implanted within the right atrial chamber of the dog in order to determine the blood vascular compatibility of the hydrophilic polymer. Upon sacrifice of the dogs, after one month, it was apparent that the hydrophilic polymer did not foster thrombosis and that the only clot observed was at the point of attachment of the hydrophilic polymer article to the atrial wall.

In an in vitro study, glass test tubes coated with methyl alcohol solutions of the hydrophilic polymer made in accordance with Example 37, were filled with canine blood and clotting times were observed. It was noted that as against the controlled clotting times of 6 minutes the hydrophilic polymer coated tubes clotted at an average of 3·5 hours, thereby evidencing that the hydrophilic polymer discouraged surface thrombogenesis .

Additional desired vascular substitute properties exhibited by such implants include wettability, lubricity, conductivity, distensibility and the capability of absorbing and transporting ions of organic and inorganic compounds at Example 43a A glass plate for use as a vehicle windshield, window or mirror was coated with a methyl alcohol solution of the hydrophllic polymer made in accordance with Example 37# The resulting coating (0.005 inches thick) was light-transmitting and optically clear, adherent, and did not fog upon exposure to hot moist air. Similarly, a plastic plate of methyl raethacryl-ate for use as an aircraft windshield was so coated.

Example . 3b The procedure of Example 43a was followed to coat an optical element in the form of a camera lens having a reflection-reducing film of magnesium fluoride thereon to form a light-transmitting, optically clear, reflection-reducing, non-fogging optical element.

Example ,44 To the ethanolic solution of Example 36 was added the antibiotic chloramphenicol and the resulting solution was employed to coat a nylon suture* Example 4g To the ethanolic solution of Example 36a was added an alcoholic solution of ercurochrome . The resulting solution was applied by spraying as a wound dressing.

Example 46 3.6 grams of powder of Example 36a is impregnated with Mercurochrome from an acetone solution. The powder is then dried and dusted on a wound as a dressing to provide antiseptic action.

The foregoing examples are directed primarily to the in situ addition of dyes, pigments, thickening agents, resins, medicinally-active substances, bactericides, anti-virals, fungicides, strengthening materials, antiseptics, catalyzers, nutrient media, anti-coagulants, steroids and the like during the casting syrup preparation after the initial step in which the water-soluble uncrosslinked homopolymer of the polyhydroxy ethyl methacrylate or the like is formed and preferably at the stage of addition of the makeup catalyst. However, certain additive components, particularly pigments, thickening agents, resins and the like can be added directly to the initial monomer or during the initial polymerization.

Claims (1)

1. WHAT IS CLAIMED substantially completely phlllc polymer Incapable of absorbing more up to about thirty per cent by weight of water when equilibrated in aqueous solution comprising the polymerization product of a major amount of of an olefinio acid having at least one substituted hydrophlllc functional group with a minor amount of a dlester of one of said olefinio acids and of an alcohol having at least two esterifiable hydroxy The substantially completely polymerized hydophilie polymer in Claim 1 the form of a solid friable foam incapable of absorbing more than up to about per cent by weight of water equilibrated in aqueous The substantially completely polymerized hydrophilio polymer of Claim 1 in the form of a compatible powder of absorbing more than up to about thirty pe cent by weight of water in gel form when equilibrated in aqueous A hydrophlllc castin syrup adapted to be polymerized in to form a substantially completely polymerized hydrophilio polymer as claimed in Claim comprises a mixture of a major portion of a aonoester of an Olefinio having at least one substituted hydrophilio functional and a minor portion of a substantially completely polymerizedx polymer of said ester and a minor amount of a dlester of one of said olefinio aoids and of an alcohol having at least two esterifiable hydrophilio liquid casting syrup of Claim 4 including a additive The hydrophilio liquid casting syrup of Claim 4 wherein the additive component is soluble in a solvent of the group of water and the An alcoholic solution of the hydrophilio liquid casting syrup of Claim hydrophilio polymer of Claim 4 wherein the monoester is selected from the group consisting of hydroxy alkyl aorylates and hydrophilio of Claim 4 wherein the diester is of an acrylic or methaorylio The hydrophilio polymer of Claim 1 wherein the ester is selected from the group consisting of hydroxy alkyl aorylates and hydrophilio polymer of Claim 1 wherein the diester is of a aorylio or methaorylio A denture liner substanoe pvepared from a hydrophilio polymer claimed in Claim A hydrophilio mouth guard surface liner substance pared from a hydrophilio polymer olaimed in Claim A hydrophilio contact lens comprising a solid phllic polymeric body according to Claim A solid hydrophilio polymerlo body comprising a composition matter as olaimed in Claim together with a major amount of a natural or synthetio The body set forth in Claim 15 in the form of a 17 form of an ut 16 in the of a vessel polymeric body of Claim 15 in the form a body The in the form of a heart valve polymeric The of Claim 15 in of a diaphragm member internal A wound dressing compr sing hydrophilio polymer i mixture of major portion of a water soluble alkl aorylate or methaorylate ester and a minor portion of a substantially completely polymerized polymer of said ester and amount of a polymerizable The liquid castin of Claim 2 inoluding a additive liquid casting syrup of Claim wherein the additive component is soluble solvent of the group of water and the An alooholio solution the hydrophilic liquid casting syrup of Claim glass element having a light transmitting opticall coating thereon comprising a of a major amount a wate soluble aorylate or methaorylate as claimed in Claim 10 and a minor amount of agent The glass element of Claim 33 in the form of glass element of Claim 33 the form o vehicular A plastic element having a optioally coating thereon comprising a copolymer of a major amount of a water soluble aorylate o methaorylate as in Claim 10 and a minor amount a copolymerizable plastic element of Claim o of plastic of Claim 36 in form of vehicular A coating layer comprising a copolymer of or as claimed in Claim 10 vith am unt polyfunctional a A friable which an of of a of an iuic acid at least substituted hydrophilic functional with of said acids of alcohol having a least two groups A which of amount of of an acid having substituted functional wit a minor t of a dioe or of of of having at two groups and foaming A comprising a hydrophilic polymer o Claim body comprising a hydrophilic polymer A tobacco smoke filter element comprising a hydrophilic polymer of Claim A chromatographic filter element comprising a hydrophilic polymer of Claim An exhaust gas filter element comprising a hydrophilic polymer of Claim A catalytic bed member comprisin a hydrophilic polymer of Claim A thickening agent oomprising a hydrophilic pilymer of Claim A laminate layer comprising a hydrophilic polymer of Claim A method of coating boat hulls comprising applying to the hulls a coating composition which contains a hydrophilio aorylate or claimed in Claim A g powder comprising a 41 powder of Claim A powder comprising a compactable powde 41 of Claim A tobacco smoke filter powder element oomprising a compact able powder of Claim A chromatographio filter powder elemen comprising oompaotable powder of Claim A surgical suture coated with the polymer of Claim A denture liner composition comprising a mixture of the polymer powder of Claim 56 a liquid comprising a major portion of a polymerizable monoester of an olefinic acid having at least one substituted functional group with a minor amount of a polymerizable diester of one of said olefinic acids and of an alcohol having at least two esterifiable hydroxyl in the presence in vinyl polymerization catalyst and an amine A denture having a liner comprised of the cured denture liner composition of A denture liner component composition comprising the polymer powder o Claim having equally distributed therein an amine polymerization A denture liner component composition comprising a liquid to lf comprisin a major portion o a moneester of olefinic acid having at least one substituted functional group with a mino amount of a diester of one of olefinic acids and of an alcohol having at least two esterifiable A waund dressing comprising an alcoholic solution of the hydrohilic polymer accordance with A wound dressing comprising the hydrophl o of Claim having a solution incorporated The hydrophllio polymer powde of having porated therein a substanoe of the group consisting of flavoring and pharmaceutical A glass element having a optioally coating thereon comprisin the polymer of Claim 67 The glass element of Claim the form of an optical 67 The glass element of Claim 5 the form of a vehlcilar A plastic element having a optically coating thereon comprising the hydrophllio polyme of pastio element Claim in the form of an optical 67 plastio element of Claim n the form of a vehicular A method of preparing a hdrophllio according to Claim which comprises admixing in the free state a major amoun of a polymerizable moneester of a acid having at one substituted functional group with a minor amount of a polymerizable dlester one of olefinic and of an alcohol having at least two esteriflable groups in the presence of an amount of a vinyl polymerization catalyst sufficient to polymerize The method of Claim 75 said monoestev is hydroxy este of an unsaturated acid and said dlester is a polymerizable one of the said unsaturated carboxyllc The method of Claim 73 74 wherein said free radical catalyst selected from group consisting of isopropyl tertiary butyl hydroxy peroxide and benzoyl The method of 73 or 74 wherein said monoester is selected from the group consisting of hydrox alkyl acrylates and The method of Claim said diesters are of an aroyllo or methaorylic method of Claim 73 wherein said comprises methacrylate and said dlester comprises ethylene glycol The method of preparing a liquid casting syrup as claimed in Claim 4 whioh in the state a major amount of monoester of eleflnio aold having at least substituted hydrophilic functional group with a miner amount of a free vinyl pilmerization catalyst in an atmosphere and heating from ambient temperatures to about until the said monomer is cooling said resulting mixture to ambient temperature and adding a minor amount of a polymerlzable dlester of one of acids having at least two hydroxy groups and of an alcohol along with an additional minor amount of one of eaid catalysts sufficient to form a liquid casting syrup adapted to by polymerized The method of Claim 79 wherein said monoester ii an hydroxy ester of an unsaturated oarboxylio aold and said dlester is a polymerlzable dlester of one of the said unsaturated carboxyllc method of Claim 79 wherein said free radical catalyst is seleoted from the group consisting of isopropyl tertiary butyl perootoate and benzoyl The method of Claim 79 wherein said monoester is selected from the group consisting of hydroxy alkyl aorylates and methsd of Claim 79 said diesters are of an aorjrllc or The of preparing a polymerio polymer according to Claim in the form of a friable foam which comprises admixing the state a majo amount of a polymerizable of an finio acid having at least one substituted hydrophillo functional group with a minor amount of a polymerizable dlester of one of acids having at least two esterifliable hydroyl groups with a agent the presence of an amount of a free oatalyst polymerize same in the of a friable method of Claim 84 wherein the foaming agent comprises sodiu method of preparing a paotable powder of a polymer according to Claim which comprises admixing in the state a amount of polymerizable of olefinic acid having at least one substituted hydrophillo functional group with a minor amount of a polymerizable dlester of one of olefinic acids and having at least two hydroxyl groups with a agent in the presehoe of an amount of a free vinyl polymerization oatalyst sufficient to polymerize same in the form of a friable foam and disintegrating said to powder Δ method of preparing a synthetio fiber which admixing the state a major amount of A soluble polymerlzable monoester of an oleflnio acid having at least one substituted functional group with a major amount of A synthetio resin and said mixture to form a solution of cooling said prepolymer solution to room temperature and adding a minor amount of a polymerizable dlester in the presence of a minor amount of a vinyl polymerization catalyst suffioient to polymerize same in the form of a viscous passin syrup through an extruder into a heated fluid medium maintained to polymerize same into solid fiber removing said fiber from said liquid medium and and orienting method of Claim 87 wherein the synthetio resin prises a linear A hydrophilio foam prepared by method of Claim A hydrophilio polymeric powder prepared by the method of Claim A liquid casting syrup prepared by the method of Claim A solid hydrophilio polymerio body prepared by the method of Claim A thermosetting polymerio film prepared by the method of Claim A method of preparing a hydrophilio liquid casting syrup for preparing a polymer according to which comprises admixing in the state a merizable of an olefinio acid having least one substituted functional group minor amount of a vinyl polymerization catalyst sufficient to cause substnatlal portion of the produot to ize to the cooling said reaotio product to ambient and adding a relatively major portion of suoh catalyst to form a liquid casting syrup adapted to be polymerized in Method of wherein a additive is added after the initial polymerization Method of Claim 94 wherein a additive soluble in a solvent of the group of water and the alcohols is added after the initial polymerization Method of Claim 94 wherein the liquid casting syrup reaotion product precipitated in an exoess of water to form an solid substantially completely polymerized hydrophilic solid polymer incapable of absorbing more than about thirty per cent by weight of gel form equilibrated aqueous Method of Claim 95 wherein said precipitated solid iculate reaotion product is dissolved in an alcoholic solution to form a polymer Method of Claim 95 wherein the s additive is added to liquid casting The method of Claim 94 wherein said an hydroxy ester of an unsaturated aoid and said diester is a polymerizable diester of one of the said unsaturated carboxylio method of Claim 94 wherein said free radical catalyst is from the group consisting of tertiary butyl hydroxy oxide and benzoyl The method of Claim 94 wherein said monoester is selected from the group consisting of hydrox alkyl acrylates and method of Claim 94 wherein said diesters are of an acrylic or meihaorylio A method of Claim wherein monoester comprises methacryiate and said diester comprises ethylene glycol e method of Claim wherein said admixing is performed in an inert atmosphere at a temperature range of ambient The method of Claim wherein the said additive is member of the group consisting of flavoring fragrance agents pharmaceutical ahtiseptio agents and body The method of Claim wherein said pharmacuetioal agent comprises a method of Claim 16 wherein said pharmaceutical agent comprises method of Claim 25 wherein pharmaceutical agent comprises an A of preparing a hydrophilic polymer whioh comprise rapid agitation of a of an olefinio aoid having at one stituted monoester of an olefinio acid havin at least substituted functional group with a minor amount of a of one o said olefinio acids having at least two esterifiable hydroxyl groups in the presence of an amount of a vinyl polymerization catalyst sufficient to polymerize same in the presence of medium in polymer so formed is method of Claim wherein the suspending medium selected from the consisting o silicone finic and aromatic hydrocarbons and mixtures A polymer powder prepared in accordance with Claim A surgical suture comprising fiber coated with a polymer prepared in insufficientOCRQuality